ALBERT

Description: Owing to their ability to be genetically expressed in live cells, fluorescent proteins have become indispensable markers in cellular and biochemical studies. These proteins can undergo a number of covalent chemical modifications that may affect their photophysical properties. Among other mechanisms, such covalent modifications may be induced by reactive oxygen species (ROS), as generated along a variety of biological pathways or through the action of ionizing radiations. In a previous report [ 1 ], we showed that the exposure of cyan fluorescent protein (ECFP) to amounts of • OH that mimic the conditions of intracellular oxidative bursts (associated with intense ROS production) leads to observable changes in its photophysical properties in the absence of any direct oxidation of the ECFP chromophore. In the present work, we analyzed the associated structural modifications of the protein in depth. Following the quantified production of • OH, we devised a complete analytical workflow based on chromatography and mass spectrometry that allowed us to fully characterize the oxidation events. While methionine, tyrosine, and phenylalanine were the only amino acids that were found to be oxidized, semi-quantitative assessment of their oxidation levels showed that the protein is preferentially oxidized at eight residue positions. To account for the preferred oxidation of a few, poorly accessible methionine residues, we propose a multi-step reaction pathway supported by data from pulsed radiolysis experiments. The described experimental workflow is widely generalizable to other fluorescent proteins, and opens the door to the identification of crucial covalent modifications that affect their photophysics. Figure Barrel structure of ECFP: residues that were found to be oxidized by .OH radicals are highlighted

Description: A synthetic redox probe structurally related to natural pyridoacridones was designed and electrochemically characterised. These heterocycles behave as DNA intercalators due to their extended planar structure that promotes stacking in between nucleic acid base pairs. Electrochemical characterization by cyclic voltammetry revealed a quasi-reversible electrochemical behaviour occurring at a mild negative potential in aqueous solution. The study of the mechanism showed that the iminoquinone redox moiety acts similarly to quinone involving a two-electron reduction coupled with proton transfer. The easily accessible potential region with respect to aqueous electro-inactive window makes the pyridoacridone ring suitable for the indirect electrochemical detection of chemically unlabelled DNA. Its usefulness as electrochemical hybridization indicator was assessed on immobilised DNA and compared to doxorubicin. The voltamperometric response of the intercalator acts as an indicator of the presence of double-stranded DNA at the electrode surface and allows the selective transduction of immobilised oligonucleotide hybridization at both macro- and microscale electrodes.

Description: The reactions of As 2 O 3 , SbCl 3 , and (BiO) 2 CO 3 with oleum (65 % SO 3 ) yielded single crystals of As(S 2 O 7 )(HS 2 O 7 ) [monoclinic, P 2 1 / c , Z = 4, a = 16.549(1), b = 6.6743(5), c = 9.9498(6) Å, β = 102.672(8)°, V = 1072.672(8) Å 3 ], Sb 2 (SO 4 ) 2 (S 2 O 7 ) [monoclinic, P 2 1 / n , Z = 4, a = 9.1586(2), b = 6.9981(2), c = 17.7956(4) Å, β = 100.9690(8)°, V = 1119.73(5) Å 3 ], and Bi 2 (S 2 O 7 ) 3 [triclinic, P , Z = 2, a = 6.5734(1), b = 10.1954(2), c = 11.5121(2) Å, α = 90.996(1)°, β = 96.976(1)°, γ = 94.870(1)°, V = 762.75(2) Å 3 ]. As(S 2 O 7 )(HS 2 O 7 ) shows the arsenic atoms in a trigonal pyramidal coordination of the oxygen atoms of one chelating S 2 O 7 2– and one monodentate HS 2 O 7 – group. The distinct As(S 2 O 7 )(HS 2 O 7 ) molecules are connected with each other by hydrogen bonds to form layers. Sb 2 (SO 4 ) 2 (S 2 O 7 ) shows the Sb 3+ cations in a seesaw-type coordination of oxygen atoms from both anions. In Bi 2 (S 2 O 7 ) 3 the Bi 3+ cations are in a square prismatic oxygen coordination of disulfate units. The antimony and the bismuth compounds exhibit complex three-dimensionally linked structures. The syntheses and the crystal structures, as well as the thermal decomposition of Sb 2 (SO 4 ) 2 (S 2 O 7 ) are presented.

Description: Silver acetate AgOAc reacts with dry liquid ammonia under the formation of colorless needle-shaped crystals of diammine silver(I) acetate [Ag(NH 3 ) 2 ]OAc ( 1 ). The compound crystallizes in the monoclinic space group P 2 1 / c with a = 8.0205(2), b = 12.4161(3), c = 6.0938(2) Å, β = 107.741(4)°, and V = 577.98(3) Å 3 at 123 K with Z = 4. The crystal structure shows the presence of almost linear [Ag(NH 3 ) 2 ] + cations, which are arranged in a corrugated chain of equidistant silver atoms. The Ag–Ag distance is 3.1089(11) Å, which falls in the range of “argentophilic” interactions. After warming to room temperature and removal of the solvent, compound 1 was found unchanged as evidenced by powder X-ray diffraction, thermogravimetric and mass-spectrometric analysis, as well as IR and Raman spectroscopy.

Description: A series of chalcogenidoantimonates, namely [Zn(NH 3 ) 6 ](Sb III 4 S 7 ) ( 1 ), [Zn(NH 3 ) 6 ]{Zn(NH 3 ) 3 Sb V S 4 } 2 · NH 3 ( 2 ), [Mn(NH 3 ) 6 ](Sb III Se 2 ) 2 ( 3 ) and [Zn(NH 3 ) 4 ]{Zn(NH 3 )Sb III Se 3 } 2 · 3NH 3 ( 4 ) are synthesized by solvothermal technique in liquid ammonia at 50 °C from elemental zinc or manganese, antimony and sulfur or selenium. 1 (space group P ) and 2 ( P ) crystallize centrosymmetrically, whereas 3 ( Pna 2 1 ) and 4 ( P 2 1 ) represent polar structures. All compounds contain discrete cationic [Zn(NH 3 ) 4 ] 2+ , [Zn(NH 3 ) 6 ] 2+ , and [Mn(NH 3 ) 6 ] 2+ ammine complexes. In the anionic structure parts, corner-connected trigonal-pyramidal SbS 3 and SbSe 3 are the characteristic building units. 1 and 4 contain 2D polymeric anions, in the latter case with Zn 2+ cations incorporated in a selenidoantimonate(III) network. The polymeric anion in the structure of 3 is a helical chain. 2 is a molecular compound and contains dinuclear anions [S 3 Sb–S–Zn(NH 3 ) 3 ] 2– with Sb V . Raman measurements show the Sb–Ch valence vibrations in the expected region between 250–370 cm –1 for 1 and at 212 cm –1 for 4 . According to the reflectance spectrum 4 is a semiconductor with an optical band gap of 2.05(5) eV.

Description: The knowledge of RNA’s role in biological systems and the recent recognition of its potential use as a reliable biotherapeutic tool increase the demand for development and validation of analytical methods for accurate analysis of RNA. Affinity chromatography is a unique technique because of the versatility of applications reliant on the affinity ligand used. Recently, an arginine-based matrix has been effectively applied in the purification of RNA because of the specific recognition mechanism for RNA molecules. This interaction is suggested to be due to the length of arginine side chain and its ability to produce good hydrogen bonding geometries, which promote multi-contact with RNA backbone or RNA bases, based on RNA folding. Thus, this work presents the development and validation of an analytical method with ultraviolet detection for the quantification of RNA using affinity chromatography with arginine amino acid as immobilized ligand. The method was validated according to International and European legislation for bioanalytical methods. The results revealed that the proposed method is suitable for the reliable detection, separation, and quantification of RNA, showing that the method is precise and accurate for concentrations up to 200 ng/μL of RNA. Furthermore, the versatility of the methodology was demonstrated by its applicability in the quantification of RNA from different eukaryotic cells and in crude samples of chemically synthesized RNA. Therefore, the proposed method demonstrates a potential multipurpose applicability in molecular biology RNA-based analysis and RNA therapeutics. Figure Proposed interactions occurring between arginine–agarose matrix and RNA molecules. Given the multiplicity of arginine side-chain interactions and depending upon RNA folding state, arginine will preferably bind to phosphate groups of RNA backbone or RNA bases.

Description: Functionalized magnetic nanoparticles have attracted much attention in sample preparation because of their excellent performance compared with traditional sample-preparation sorbents. In this review, we describe the application of magnetic nanoparticles functionalized with silica, octadecylsilane, carbon-based material, surfactants, and polymers as adsorbents for separation and preconcentration of analytes from a variety of matrices. Magnetic solid-phase extraction (MSPE) techniques, mainly reported in the last five years, are presented and discussed.

Description: Racemic mixtures of the promising anti-malarial bisindole alkoids, flinderole A–C, desmethyl flinderole C, borreverine and isoborreverine, are baseline-separated for the first time by HPLC using vancomycin-based stationary phases and partially separated by capillary electrophoresis (CE) using cyclodextrin selectors. The HPLC results compare the performance of Chirobiotic V and V2 in the polar organic and reversed phase modes and their complementary selectivity is discussed. The performance of the cyclodextrin selectors in CE, while less effective, are discussed in terms of their selectivity in normal and reversed polarity modes.

Description: A multidimensional, on-line coupled liquid chromatographic/gas chromatographic system was developed for the quantification of polycyclic aromatic hydrocarbons (PAHs). A two-dimensional liquid chromatographic system (2D-liquid chromatography (LC)), with three columns having different selectivities, was connected on-line to a two-dimensional gas chromatographic system (2D-gas chromatography (GC)). Samples were cleaned up by combining normal elution and column back-flush of the LC columns to selectively remove matrix constituents and isolate well-defined, PAH enriched fractions. Using this system, the sequential removal of polar, mono/diaromatic, olefinic and alkane compounds from crude extracts was achieved. The LC/GC coupling was performed using a fused silica transfer line into a programmable temperature vaporizer (PTV) GC injector. Using the PTV in the solvent vent mode, excess solvent was removed and the enriched PAH sample extract was injected into the GC. The 2D-GC setup consisted of two capillary columns with different stationary phase selectivities. Heart-cutting of selected PAH compounds in the first GC column (first dimension) and transfer of these to the second GC column (second dimension) increased the baseline resolutions of closely eluting PAHs. The on-line system was validated using the standard reference materials SRM 1649a (urban dust) and SRM 1975 (diesel particulate extract). The PAH concentrations measured were comparable to the certified values and the fully automated LC/GC system performed the clean-up, separation and detection of PAHs in 16 extracts in less than 24 h. The multidimensional, on-line 2D-LC/2D-GC system eliminated manual handling of the sample extracts and minimised the risk of sample loss and contamination, while increasing accuracy and precision. Figure Scheme of the 2D-LC/2D-GC system

Description: Recently, an atomic force microscopy (AFM)-based approach for quantifying the number of biological molecules conjugated to a nanoparticle surface at low number densities was reported. The number of target molecules conjugated to the analyte nanoparticle can be determined with single nanoparticle fidelity using antibody-mediated self-assembly to decorate the analyte nanoparticles with probe nanoparticles (i.e., quantitative immunostaining). This work refines the statistical models used to quantitatively interpret the observations when AFM is used to image the resulting structures. The refinements add terms to the previous statistical models to account for the physical sizes of the analyte nanoparticles, conjugated molecules, antibodies, and probe nanoparticles. Thus, a more physically realistic statistical computation can be implemented for a given sample of known qualitative composition, using the software scripts provided. Example AFM data sets, using horseradish peroxidase conjugated to gold nanoparticles, are presented to illustrate how to implement this method successfully.

Description: . Sr 2 CoOsO 6 , a new osmium based ordered semiconductor double perovskite was prepared by solid state synthesis from the respective binary oxides. Room temperature PXRD analysis shows the compound to be tetragonal [ I 4/ m ; a = 5.5503(1) Å and c = 7.9320(1) Å], whereas low temperature synchrotron data refinement has revealed a second monoclinic polymorph [ I 2/ m ; a = 5.4969(2) Å, b = 5.4979(2) Å, c = 8.0090(1) Å and γ = 90.527(1)°] with a fully ordered rocksalt arrangement of cobalt and osmium atoms over the perovskite B -sites. Heat capacity and magnetic measurements indicate that Sr 2 CoOsO 6 shows antiferromagnetic ordering below T N = 108 K followed by a second magnetic transition at T 2 = 65 K. It was shown that the change from the tetragonal to the monoclinic phase occurs at T N .

Description: . The ternary germanides RE Rh 6 Ge 4 ( RE = Y, La, Pr, Nd, Sm–Lu) were obtained by arc-melting of the elements and subsequent annealing. Single crystals were grown from bismuth fluxes. The samples were studied by X-ray diffraction on powders. The structures of five members were refined from single crystal diffraction data: LiCo 6 P 4 type, P m 2, a = 715.8(1), c = 387.33(8) pm, wR = 0.0238, 332 F 2 values for LaRh 6 Ge 4 , a = 715.0(1), c = 384.96(7) pm, wR = 0.0211, 329 F 2 values for PrRh 6 Ge 4 , a = 714.28(9), c = 382.57(6) pm, wR = 0.0136, 327 F 2 values for SmRh 6 Ge 4 , a = 714.2(1), c = 381.6(1), wR = 0.0270, 327 F 2 values for GdRh 6 Ge 4 , and a = 714.2(2), c = 379.0(1) pm, wR = 0.0273, 324 F 2 values for HoRh 6 Ge 4 with 19 variables per refinement. The RE Rh 6 Ge 4 structures have two crystallographically independent germanium sites in trigonal prismatic coordination, manifesting the close structural relationship with metal-rich phosphides. Together, the rhodium and germanium atoms build up three-dimensional [Rh 6 Ge 4 ] networks, which leave large channels for the rare earth atoms. Each rare earth atom has coordination number 20 with 12 Rh, 6 Ge, and 2 RE neighbors. Temperature dependent magnetic susceptibility measurements indicate Pauli paramagnetic behavior for YRh 6 Ge 4 , LaRh 6 Ge 4 , and LuRh 6 Ge 4 . The compounds RE Rh 6 Ge 4 ( RE = Gd–Yb) are Curie-Weiss paramagnets. Antiferromagnetic ordering was observed at 8.4(5) K (GdRh 6 Ge 4 ), 13.6(5) K (TbRh 6 Ge 4 ), 5.1(5) K (DyRh 6 Ge 4 ), and 8.9(5) K (YbRh 6 Ge 4 ). DyRh 6 Ge 4 and YbRh 6 Ge 4 show metamagnetic transitions at 2.5(5) and 45(2) kOe, respectively.

Description: Reaction of manganese(II) thiocyanate with 2-chloropyrazine leads always to the formation of a compound of composition Mn(NCS) 2 (2-chloropyrazine) 4 ( 1 - Mn/Cl ) that consists of discrete complexes, in which the manganese cation is coordinated by two terminal thiocyanato anions and four 2-chloropyrazine ligands. In contrast, with 2-methylpyrazine only an aqua complex of composition Mn(NCS) 2 (2-methylpyrazine) 2 (H 2 O) 2 ( 1 - Mn/CH 3 ) is obtained that also consists of discrete octahedrally coordinated complexes. Moreover, a few single crystals of Mn(NCS) 2 (2-chloropyrazine) 4 · Mn(NCS) 2 (2-chloropyrazine) 2 (H 2 O) 2 · 2-chloropyrazine trisolvate ( 2 - Mn/Cl ) and Mn(NCS) 2 (2-methylpyrazine) 2 (H 2 O) 2 · Mn(NCS) 2 (H 2 O) 4 ( 2 - Mn/CH 3 ) were accidently obtained but no larger amounts are available. On heating, 1 - Mn/Cl and 1 - Mn/CH 3 transforms into new compounds of composition Mn(NCS) 2 (L) 2 (L = 2-chloropyrazine) ( 4 - Mn/Cl ) and 2-methylpyrazine ( 3 - Mn/CH 3 ). Surprisingly on further heating 1 - Mn/CH 3 looses additional 2-methylpyrazine ligands and transforms into a new compound of composition Mn(NCS) 2 (2-methylpyrazine) ( 4 - Mn/CH 3 ). Compound 4 - Mn/Cl is isotypic to its cobalt(II) analog and 4 - Mn/CH 3 is isotypic to Cd(NCS) 2 (2-methylpyrazine) reported recently and therefore, both structures were refined by the Rietveld method. The crystal structures of both compounds are strongly related. They consists of dimeric units, in which each two manganese cations are linked by pairs of μ-1,3-bridging thiocyanato anions, which are further connected into layers by single μ-1, 3-bridging anionic ligands. In contrast to 4 - Mn/Cl , in 4 - Mn/CH 3 these layers are further linked into a 3D coordination network by the 2-methylpyrazine ligands. Magnetic measurements reveal that 1 - Mn/Cl , 1 - Mn/CH 3 , and 3 - Mn/CH 3 shows only Curie- or Curie-Weiss paramagnetism, whereas 4 - Mn/Cl and 4 - Mn/CH 3 shows antiferromagnetic ordering at T N = 22.9 K and at 26.5 K. The results of these investigations are compared with those obtained for related compounds.

Description: . Black platelets of Bi 39.67(7) Ru 2 Br 35.0(2) were crystallized from a melt of Bi, BiBr 3 , and Ru. In the tetragonal crystal structure [ P 4/ mbm , a = 1311.92(6) pm, c = 3018.2(4) pm at 155(5) K], cluster cations [(Bi 8 2+ )Ru 2+ (Bi 8 2+ )] are embedded in a matrix of disordered bromido-bismuthate(III) groups. A thorough analysis of the disorder in the anionic part enabled the unambiguous assignment of the cluster charge. The η 4 -coordination of the two Bi 8 2+ square antiprisms to the Ru II atom in the sandwich complex resembles the bonding of Bi 5 + and Bi 8 2+ in the clusters [(Bi 5 + )Ru + (Bi 4 Br 4 )Ru + (Bi 5 + )] and [(Bi 8 2+ )Ru + (Bi 4 Br 4 )Ru + (Bi 5 + )] as well as of Bi 4 2– in 1 ∞ [(Bi 4 2– )Ru + (Bi 4 Br 4 )Ru + ]. By combining crystal chemical considerations for all mentioned compounds and using quantum chemical calculations, a common bonding scheme for the coordination compounds of bismuth polycations and polyanions was established. The η 4 -coordinating bismuth polycations and polyanions act as six electron donors, comparable to nido -carborane ligands, Zintl anions E 9 4– and E 5 6– ( E = Si to Pb), cyclopentadienyl ligands, or the cyclobutadiene dianion. The electron count for the transition metal is 18 in all finite clusters.

Description: . Previous attempts to synthesize and isolate (thiobisphenolate) vanadium(V) dioxido complexes had always provided their dimers containing [O=V(μ-O) 2 V=O] 2+ cores, and these also dominate the solution reactivity. Hence, the behavior of their parent monomers, which represent the major species in solution, has remained uncertain. Herein we report the development of a synthetic route that allowed for the successful isolation, spectroscopic investigation, and structural characterization of the monomer PPh 4 [ S LVO 2 ] ( 3 ) [ S L 2– = 2′2-thiobis(2, 4-di- tert -butylphenolate)]. For this purpose PPh 4 [ S LVOCl 2 ] ( 1 ) had to be accessed first in order to convert it to the ethoxido compound PPh 4 [ S LVO(OEt) 2 ] ( 2 ), which is more prone to hydrolysis. Treatment of 2 with stoichiometric amounts of water followed by immediate cooling to –30 °C led to crystals of 3 . After its dissolution NMR spectra were recorded that were identical with those obtained after dissolution of its dimer, thus confirming the monomer/dimer equilibrium postulated previously. The molecular structure of 3 revealed the absence of a V ··· S interaction, which, however, stabilizes its dimer, and thus suggested the employment of a bisphenolate ligand lacking a bridging sulfur atom to obtain an analogue, which does not undergo dimerization in solution. In Et L 2– the sulfur atom is replaced by an ethylmethine unit and indeed the corresponding complex NBu 4 [ Et LVO 2 ] ( 4 ) proved to be stable as a monomer. Investigation of its potential as a catalyst for the oxidative dehydrogenation of 9-fluorenol confirmed a much lower reactivity in comparison to dimeric complexes, which is discussed.

Description: Two complexes, cis -[MnL 2 (NCS) 2 ] ( 1 ) and cis -[ZnL 2 (NCS) 2 ] ( 2 ) with asymmetrical substituted triazole ligands [L = 3, 4-dimethyl-5-(2-pyridyl)-1, 2, 4-triazole], were synthesized and characterized by elemental analysis, UV/Vis and FT-IR spectroscopy as well as thermogravimetric analyses (TGA), powder XRD, and single-crystal X-ray diffraction. In the complexes, each L molecule adopts a chelating bidentate mode by the nitrogen atoms of pyridyl and triazole. Both complexes have a similar distorted octahedral [ M N 6 ] core ( M = Mn 2+ and Zn 2+ ) with two NCS – ions in the cis position.

Description: . The multi-shaped amorphous alloy (Ni-B) powders were prepared by complexing reduction route using sodium borohydride (NaBH 4 ) as reductant with assistance of ultrasonic wave. The selected complexants, i.e. water, ammonia, salicylic acid, and ethylene diamine tetraacetic acid (EDTA) possess sequentially escalating complexation ability. The chemical composition and shapes of the product samples obtained under different conditions were characterized by X-ray powder differaction, selected area electron diffraction, and transmission electron microscope. The influence of reaction conditions such as the types of Ni-B, temperatures, NaBH 4 concentrations, and sodium hydroxide (NaOH) content on the hydrogen generation rate of hydrolysis of NaBH 4 solution were investigated in detail. The results show that the as-prepared Ni-B powders all belong to amorphous alloy with variable element contents, and the Ni-B sample prepared from EDTA complexation, possessing the best fineness and dispersity, has the strongest catalytic activity. The mean apparent activation energy of the hydrolysis reaction is 64.90 kJ · mol –1 . The NaBH 4 concentration has little impact on hydrogen generation rate, implying that the catalytic hydrolysis of NaBH 4 solution should be the pseudo zero-order reaction. Keeping the NaOH content at below 5 % could inhibit the hydrolysis of NaBH 4 solution, but the NaOH contents from 10 % to 15 % will significantly promote the hydrolysis rate of NaBH 4 . The hydrolysis reaction mechanisms, especially the effect of NaOH content on the hydrolysis reaction were also analyzed.

Description: Stem cell therapy has opened up the possibility of treating numerous degenerating diseases. However, we are still merely at the stage of identifying appropriate sources of stem cells and exploring their full differentiation potential. Thus, tracking the stem cells upon in vivo engraftment and during in vitro co-culture is very important and is an area of research embracing many pitfalls. 5-Ethynyl-2′-deoxyuridine (EdU), a rather new thymidine analog incorporated into DNA, has recently been suggested to be a novel highly valid alternative to other dyes for labeling of stem cells and subsequent tracing of their proliferation and differentiation ability. However, our results herein do not at any stage support this recommendation, since EdU severely reduces the viability of stem cells. Accordingly, we found that transplanted EdU-labeled stem cells hardly survive upon in vivo transplantation into regenerating muscle, whereas stem cells labeled in parallel with another dye survived very well and also participated in myofiber formation. Similar data were obtained upon in vitro myogenic culture, and further analysis showed that EdU reduced cell numbers by up to 88 % and increased the cell volume of remaining cells by as much as 91 %. Even at low EdU concentrations, cell survival and phenotype were substantially compromised, and the myogenic differentiation potential was inhibited. Since we examined both primary derived cells and cell lines from several species with the same result, this appears to be a common trait of EdU. We therefore suggest that EdU labeling should be avoided (or used with precaution) for stem cell tracing purposes. Figure Myoblasts were marked with DiI ( red ) and EdU ( purple ), and injected into lesioned skeletal muscle. At day 9 following transplantation, only DiI positive cells were observed and had participated in myofibre formation as (indicated by arrowheads) visualized by red fluorescence signals inside laminin ( green ) positive multinucleated myofibres. EdU was toxic to the engrafted cells, suggesting that this reagent is non-applicaple for tracing of stem cells.

Description: Synthetic cathinones are novel stimulants derived from cathinone, with amphetamines or cocaine-like effects, often labeled “not for human consumption” and considered “legal highs”. Emergence of these new designer drugs complicate interpretation of forensic and clinical cases, with introduction of many new analogs designed to circumvent legislation and vary effects and potencies. We developed a method for the simultaneous quantification of 28 synthetic cathinones, including four metabolites, in urine by liquid chromatography coupled to high resolution mass spectrometry (LC-HRMS). These cathinones include cathinone, methcathinone, and synthetic cathinones position-3’-substituted, N-alkyl-substituted, ring-substituted, methylenedioxy-substituted, and pyrrolidinyl-substituted. One mL phosphate buffer pH 6 and 25 μL IStd solution were combined with 0.25 mL urine, and subjected to solid phase cation exchange extraction (SOLA SCX). The chromatographic reverse-phase separation was achieved with a gradient mobile phase of 0.1 % formic acid in water and in acetonitrile in 20 min. We employed a Q Exactive high resolution mass spectrometer, with compounds identified and quantified by target-MSMS experiments. The assay was linear from 0.5–1 to 100 μg/L, with limits of detection of 0.25–1 μg/L. Imprecision ( n  = 20) was 〈15.9 % and accuracy ( n  = 20) 85.2–118.1 %. Extraction efficiency was 78.9–116.7 % (CV 1.4–16.7 %, n  = 5), process efficiency 57.7–104.9 %, and matrix effects from −29.5 % to 1.5 % (CV 1.9–13.1 %, n  = 10). Most synthetic cathinones were stable at 4 °C for 72 h ( n  = 27) and after 3 freeze-thaw cycles ( n  = 26), but many ( n  = 19) were not stable at room temperature for 24 h (losses up to −67.6 %). The method was applied to authentic urine specimens from synthetic cathinone users. This method provides a comprehensive confirmation method for 28 synthetic cathinones in urine, with good selectivity and specificity.

Description: The intermetallic compounds Sr 2 Au 6.52 Zn 2.48 , Sr 2 Au 6 Zn 3 , and Sr 2 Au 6 Ga 3 were obtained by induction melting of the elements in sealed tantalum tubes. Their structures were studied by X-ray diffraction on powders and refined from single crystal diffraction data: R c , a = 844.5(2), c = 2187.7(5) pm, wR 2 = 0.0411, 936 F 2 values and 20 variables for Sr 2 Au 6.52 Zn 2.48 ; a = 841.6(2), c = 2191.5(7) pm, wR 2 = 0.0126, 587 F 2 values and 19 variables for Sr 2 Au 6 Zn 3 ; and a = 841.9(2), c = 2191.1(7) pm, wR 2 = 0.0199, 660 F 2 values and 19 variables for Sr 2 Au 6 Ga 3 . The gold substructures of Sr 2 Au 6 Zn 3 and Sr 2 Au 6 Ga 3 can be considered as diamond polytypes with 6R stacking sequences (287–304 pm Au–Au in Sr 2 Au 6 Zn 3 ). The cavities formed by this network are filled in an ordered manner by strontium atoms and Zn 3 (281 pm Zn–Zn), respectively Ga 3 (286 pm Ga–Ga) triangles in a 2:1 ratio. Consequently one can describe the Sr 2 Au 6 Zn 3 and Sr 2 Au 6 Ga 3 structures as ordered substitution variants of the Zintl phase CaIn 2 . This structural relationship is discussed on the basis of a group-subgroup Scheme. Sr 2 Au 6.52 Zn 2.48 shows Zn/Au mixing on the triangle.

Description: The templated borate, [C 9 H 14 N] · [B 5 O 6 (OH) 4 ], was synthesized under hydrothermal conditions. Single crystal X-ray diffraction techonology reveals that it crystallizes in the triclinic system, space group P (No. 2). The material was also characterized by element analysis, Fourier transform infrared spectroscopy (FTIR), powder X-ray diffraction (PXRD), thermogravimetric and differential thermal analysis (TG-DTA), and luminescence spectroscopy. The compound consisted of isolated pentaborate [B 5 O 6 (OH) 4 ] – and N -butylpyridinium cations [C 9 H 14 N] + . The [B 5 O 6 (OH) 4 ] – anions are connected together by hydrogen bonds to form a three-dimensional framework, in which [C 9 H 14 N] + cations are located in. [C 9 H 14 N] · [B 5 O 6 (OH) 4 ] exhibits tunable luminescence emission at 415–458 nm by means of heating treatment from 100 to 300 °C.

Description: Two alkylimido derivatives of hexamolybdate, (Bu 4 N) 2 [Mo 6 O 18 (≡N- o -COOCH 3 C 6 H 4 )] ( 1 ) and (Bu 4 N) 2 [Mo 6 O 18 (≡N- o -COOCH 2 CH 3 C 6 H 4 )] ( 2 ), were synthesized in high purity and good yields by the reaction of [(C 4 H 9 ) 4 N] 4 [α-Mo 8 O 26 ] and methyl anthranilate or ethyl- o -aminobenzoate hydrochloride with N , N ′-dicyclohexylcarbodiimide (DCC) as a dehydrating agent in dry acetonitrile solution, which were characterized by elemental analyses, IR, UV/Vis, and 1 H NMR spectroscopy as well as ESI-MS, and single-crystal X-ray diffraction study. Compound 1 crystallizes in the monoclinic space group P 2 1 / n with one-dimensional chain structure via intramolecular hydrogen bond. Compound 2 also crystallizes in the monoclinic space group P 2 1 / n with dimer structure by intramolecular hydrogen bonds and π–π interactions between the pairs of cluster anions.

Description: Amino acid analysis (AAA) has always presented an analytical challenge in terms of sample preparation, separation, and detection. Because of the vast number of amino acids, various separation methods have been applied taking into consideration the large differences in their chemical structures, which span from nonpolar to highly polar side chains. Numerous separation methods have been developed in the past 60 years, and impressive achievements have been made in the fields of separation, derivatization, and detection of amino acids (AAs). Among the separation methods, liquid chromatography (LC) prevailed in the AAA field using either pre-column or post-column labeling techniques in order to improve either separation of AAs or selectivity and sensitivity of AAA. Of the two approaches, the post-column technique is a more rugged and reproducible method and provides excellent AAs separation relatively free from interferences. This review considers current separations combined with post-column labeling techniques for AAA, comparison with the pre-column methods, and the strategies used to develop effective post-column methodology. The focus of the article is on LC methods coupled with post-column labeling techniques and studying the reactions to achieve optimum post-column derivatization (PCD) conditions in order to increase sensitivity and selectivity using various types of detectors (UV–Vis, fluorescence, electrochemical etc.) and illustrating the versatility of the PCD methods for practical analysis. Figure Reaction‐detection scheme for the fluorescent derivative of proline with o‐pthalaldehyde reagent

Description: The cover picture shows the frontispieces of all articles published in this Special Issue with research reports from DFG priority program 1178 “Experimental Electron Density as Key to Understanding Chemical Interactions”, highlighting the diverse range of chemistry that is covered herein. Biological processes that determine the effects of drugs consist on a certain interaction between agent and receptor. This molecular recognition is influenced by the electron density distribution. Analysis of these processes enables the rational synthesis of drugs. Electron density measurements are moreover significant for the design of advanced materials with specific features, e.g. the development of new pigments. Thus, color, stability, and durability can be tuned by modifying the electron density. Selected substance classes used in chemical synthesis, drug design and material science were analyzed and their binding and recognition processes were studied and quantified by means of electron density measurements.

Description: The analysis of the oligomeric active state of a native protein usually requires the application of at least two analytical methods such as gel filtration and analytical ultracentrifugation. Both methods require a substantial amount of protein, time and/or expensive equipment. We here describe a native electrophoretic method for the identification of the native molecular weight of the recombinant wild-type cytosolic 5′-nucleotidase (cN-II) and of its mutants in subunit interfaces Y115A, F36R, K311A and G319Q. The protein was stained both with protein dye and with an activity staining method. Our results demonstrated that purified recombinant protein preparations contained substantial amounts of nucleic acids and misfolded, inactive protein. Furthermore, cN-II mutants K311A and G319Q in subunit interface assume a quaternary dimeric active form, while the only active quaternary structure of wild-type cN-II is the tetramer.

Description: Direct analysis in real time mass spectrometry (DART-MS) has become an established technique for rapid mass spectral analysis of a large variety of samples. DART-MS is capable of analyzing the sample at atmospheric pressure, essentially in the open laboratory environment. DART-MS can be applied to compounds that have been deposited or adsorbed on to surfaces or that are being desorbed therefrom into the atmosphere. This makes DART-MS suitable and well-known for analysis of ingredients of plant materials, pesticide monitoring on vegetables, forensic and safety applications such as screening for traces of explosives, warfare agents, or illicit drugs on luggage, clothes, or bank notes, etc. DART can also be used for analysis of either solid or liquid bulk materials, as may be required in quality control, or to quickly investigate the identity of a compound from chemical synthesis. Even living organisms can be subjected to DART-MS. Driven by different needs in analytical practice, the combination of the DART ionization source and interface can be configured in multiple geometries and with various accessories to adapt the setup as required. Analysis by DART-MS relies on some sort of gas-phase ionization mechanism. In DART, initial generation of the ionizing species is by use of a corona discharge in a pure helium atmosphere which delivers excited helium atoms that, upon their release into the atmosphere, will initiate a cascade of gas-phase reactions. In the end, this results in reagent ions created from atmospheric water or (solvent) vapor in the vicinity of the surface subject to analysis where they effect a chemical ionization process. DART ionization processes may generate positive or negative ions, predominantly even-electron species, but odd-electron species do also occur. The prevailing process of analyte ion formation from a given sample is highly dependent on analyte properties.

Description: In this paper, we report a new type of chiral high-performance liquid chromatography (HPLC) column—a so-called dress-up chiral column—featuring a chiral stationary phase adsorbed reversibly in a commercial fluorous HPLC column through fluorous interactions. We synthesized perfluroalkylated proline derivatives as chiral stationary phase compounds and then adsorbed them reversibly in the fluorous HPLC column through the pumping of their solutions. By using this dress-up chiral column and fluorophobic elution of an aqueous copper(II) sulfate/MeOH mixture, we could enantioseparate seven racemic amino acids within 40 min. When we washed the dress-up chiral column with fluorophilic tetrahydrofuran or MeOH, the adsorbed chiral stationary phase compounds desorbed from the column, completely destroying its enantioseparation ability. The relative standard deviation of the retention times, the number of theoretical plates, and the resolution for each of four preparations of the dress-up columns were all less than or equal to 9.53 % in 20-times repeated analysis, and were all less than or equal to 18.7 % in four different preparations, respectively.

Description: A method for evaluating the interactions between metal ions and nonionic surfactants in aqueous solutions containing high-concentration HCl, using gas pressure-driven low-pressure high-performance liquid chromatography (LP-HPLC) as a highly acid-resistant HPLC system, was developed. To construct the LP-HPLC for this purpose, poly(styrene- co -divinylbenzene)-based low-flow-resistance monolithic columns tolerant to highly acidic conditions were prepared using low-conversion thermal polymerization. Thermal polymerization at 65 °C for 1.5 h (monomer conversions, 33 % for styrene and 59 % for divinylbenzene) allowed preparation of a column with both high separation efficiency (around 60,000 plates m −1 for alkylbenzenes) and a quite low back pressure of 0.14 MPa at a linear flow rate of 1 mm s −1 (2.8 × 10 −13  m 2 in permeability). The base column prepared under the above conditions was coated with a nonionic surfactant, polyoxyethylene nonylphenyl ether (PONPE, average oxyethylene unit numbers ( n ) = 3, 7.5, 15, and 20), and used for evaluation of the interactions between PONPEs and metal ions in 6 M HCl. The interactions between PONPEs and Au(III), Ga(III), Fe(III), Zn(II), and Cu(II) were successfully evaluated using both breakthrough and chromatographic methods. Furthermore, a study of the effect of the polyoxyethylene (POE) chain length revealed that the use of PONPE with the longer POE moiety enhanced the magnitude of the interaction together with the increase in the amount of oxyethylene (OE) units coated on the monolith. Moreover, the interactions of metal ions with a single OE unit were almost constant in the range of n  = 7.5–20, whereas the suppression of the interaction between Au(III) with the shortest PONPE chain ( n  = 3) was also observed. Figure Acid-resistive gas pressure-driven low-pressure high-performance liquid chromatography was developed and applied to the evaluation of interactions between metal ions and nonionic surfactants in high-concentration HCl, in particular for the effect of polyoxyethylene length on the interaction.

Description: In this study, a fast and quantitative determination method for branched-chain amino acids (BCAAs), namely leucine, isoleucine, and valine, was developed using a pillar array column. A pillar array column with low-dispersion turns was fabricated on a 20 × 20-mm 2 microchip using multistep ultraviolet photolithography and deep reactive ion etching. The BCAAs were fluorescently labeled with 4-fluoro-7-nitro-2,1,3-benzoxadiazole (NBD-F), followed by reversed-phase separation on the pillar array column. The NBD derivatives of the three BCAAs and an internal standard (6-aminocaproic acid) were separated in 100 s. The calibration curves for the NBD-BCAAs had good linearity in the range of 0.4–20 μM, using an internal standard. The intra- and interday precisions were found to be in the ranges of 1.42–3.80 and 2.74–6.97 %, respectively. The accuracies for the NBD-BCAA were from 90.2 to 99.1 %. The method was used for the analysis of sports drink and human plasma samples. The concentrations of BCAAs determined by the developed method showed good agreements with those determined using a conventional high-performance liquid chromatography system. As BCAAs are important biomarkers of some diseases, these results showed that the developed method could be a potential diagnostic tool in clinical research.

Description: The discovery and implementation of the long-term metabolite of metandienone, namely 17β-hydroxymethyl-17α-methyl-18-norandrost-1,4,13-trien-3-one, to doping control resulted in hundreds of positive metandienone findings worldwide and impressively demonstrated that prolonged detection periods significantly increase the effectiveness of sports drug testing. For oxandrolone and other 17-methyl steroids, analogs of this metabolite have already been described, but comprehensive characterization and pharmacokinetic data are still missing. In this report, the synthesis of the two epimeric oxandrolone metabolites—17β-hydroxymethyl-17α-methyl-18-nor-2-oxa-5α-androsta-13-en-3-one and 17α-hydroxymethyl-17β-methyl-18-nor-2-oxa-5α-androsta-13-en-3-one—using a fungus ( Cunninghamella elegans ) based protocol is presented. The reference material was fully characterized by liquid chromatography nuclear magnetic resonance spectroscopy and high resolution/high accuracy mass spectrometry. To ensure a specific and sensitive detection in athlete’s urine, different analytical approaches were followed, such as liquid chromatography–tandem mass spectrometry (QqQ and Q-Orbitrap) and gas chromatography–tandem mass spectrometry, in order to detect and identify the new target analytes. The applied methods have demonstrated good specificity and no significant matrix interferences. Linearity ( R 2  〉 0.99) was tested, and precise results were obtained for the detection of the analytes (coefficient of variation 〈20 %). Limits of detection (S/N) for confirmatory and screening analysis were estimated at 1 and 2 ng/mL of urine, respectively. The assay was applied to oxandrolone post-administration samples to obtain data on the excretion of the different oxandrolone metabolites. The studied specimens demonstrated significantly longer detection periods (up to 18 days) for the new oxandrolone metabolites compared to commonly targeted metabolites such as epioxandrolone or 18-nor-oxandrolone, presenting a promising approach to improve the fight against doping.

Description: . Reactions of the coordinatively unsaturated complexes [Fe 2 (μ-P R 2 )(μ-P R ′ 2 )(CO) 5 ] [ R = R ′ = t Bu ( 1 ); R = t Bu, R ′ = Cy ( 2 )] with nitric oxide in toluene at elevated temperatures were investigated. Thus, the new complexes [Fe 2 (μ-P t Bu 2 ) 2 (NO) 4 ] ( 3 ) and [Fe 2 (μ-P t Bu 2 )(μ-PCy 2 )(NO) 4 ] ( 4 ) were obtained in good yields. The molecular structure of 3 was confirmed by X-ray diffraction study. Compound 4 was also prepared from the coordinatively saturated species [Fe 2 (μ-P t Bu 2 )(μ-PCy 2 )(CO) 6 ] ( 2a ) with nitric oxide in refluxing toluene. Further closely related reactions at 60 °C with the complex 1 and [FeRu(μ-P t Bu 2 ) 2 (CO) 5 ] ( 5 ), respectively, were investigated using preliminary crystal structure determination results.

Description: Two new materials of the composition ({CH 3 (CH 2 ) 15 (CH 3 ) 2 S} + ) 2 [CoBr 4 ] 2– ( 1 ) and ({CH 3 (CH 2 ) 15 (CH 3 ) 2 S} + ) 2 [CuBr 4 ] 2– ( 2 and 3 ), of which the latter exists in two polymorphs, were synthesized. The materials display the synthetically targeted structures, comprising of layers of complex metal ions and layers of long-chain sulfonium cations. The crystal structures of the materials were determined. The interlayer distances are around 24 Å, with metal–metal distances about 8 Å. The magnetic properties of 1 were investigated, and the material is paramagnetic. ({CH 3 (CH 2 ) 15 (CH 3 ) 2 S} + ) 2 [CuBr 4 ] 2 is polymorphic. Both polymorphs crystallize with triclinic symmetry.

Description: Coccidiostats are authorized in the European Union (EU) to be used as poultry feed additives. Maximum (residue) levels (M(R)Ls) have been set within the EU for consumer and animal protection against unintended carry-over, and monitoring is compulsory. This paper describes the single-laboratory validation of a previously developed multiplex flow cytometric immunoassay (FCIA) as screening method for coccidiostats in eggs and feed and provides and compares different approaches for the calculation of the cut-off levels which are not described in detail within Commission Decision 2002/657/EC. Comparable results were obtained between the statistical (reference) approach and the rapid approaches. With the most rapid approach, the cut-off levels for narasin/salinomycin, lasalocid, diclazuril, nicarbazin (DNC) and monensin in egg, calculated as percentages of inhibition (%B/B0), were 60, 32, 76, 80 and 84, respectively. In feed, the cut-off levels for narasin/salinomycin, lasalocid, nicarbazin (DNC) and monensin were 70, 64, 72 and 78, respectively, and could not be determined for diclazuril. For all analytes, except for diclazuril in feed, the rate of false positives (false non-compliant) in blank samples was lower than 1 %, and the rate of false negatives (false compliant) at the M(R)Ls was below 5 %. Additionally, very good correlations ( r ranging from 0.994 to 0.9994) were observed between two different analysers, a sophisticated flow cytometer (FlexMAP 3D ® ) and a more cost-efficient and transportable planar imaging detector (MAGPIX ® ), hence demonstrating adequate transferability.

Description: Administration of hormonal compounds as growth promoters in livestock farming was banned by Council Directive 96/22/EC. However, this kind of substances is sometimes reported within the framework of European monitoring residue plans. Various analytical methods have been previously developed to screen for their misuse, and they are now especially efficient for monitoring the illegal administration of synthetic and semisynthetic hormones. Nevertheless, proving an exogenous administration of hormones from natural origin (i.e., estradiol-17β or progesterone) still remains a challenge for European authorities. These target compounds are indeed always present in the animal matrix, and the establishment of reference thresholds appears very difficult because of the extreme variability existing among animals. In 2011, a metabolomics study was performed on serum samples obtained from cows treated with estradiol-17β (or its ester estradiol benzoate) and from control animals using a high-performance liquid chromatography (HPLC)-LTQ-Orbitrap system. After appropriate data processing and multivariate statistical analysis (orthogonal partial least squares discriminant analysis), it was possible to highlight one potential biomarker candidate of estradiol treatments in bovine animals. Now, this biomarker has been structurally elucidated as a dipeptide, and its usefulness has been tested through a targeted HPLC-MS/MS method. Its presence in the previous samples has been confirmed and also in additional samples from estradiol-treated animals.

Description: A bootstrapped fuzzy rule-building expert system (FuRES) and a bootstrapped t -statistical weight feature selection method were individually used to select informative features from gas chromatography/mass spectrometry (GC/MS) chemical profiles of basil plants cultivated by organic and conventional farming practices. Feature subsets were selected from two-way GC/MS data objects, total ion chromatograms, and total mass spectra, separately. Four economic classifiers based on the bootstrapped FuRES approach, i.e., fuzzy optimal associative memory (e-FOAM), e-FuRES, partial least-squares–discriminant analysis (e-PLS-DA), and soft independent modeling by class analogy (e-SIMCA), and four economic classifiers based on the bootstrapped t-weight approach, i.e., e-PLS-DA-t, e-FOAM-t, e-FuRES-t, and e-SIMCA-t, were constructed thereafter to be compared with full-size classifiers obtained from the entire GC/MS data objects (i.e., FOAM, FuRES, PLS-DA, and SIMCA). By using three features selected from two-way data objects, the average classification rates with e-FOAM, e-FuRES, e-PLS-DA, and e-SIMCA were 95.3 ± 0.5 %, 100 %, 100 %, and 91.8 ± 0.2 %, respectively. The established economic classifiers were used to classify a new validation set collected 2.5 months later with no parametric change to experimental procedure. Classification rates with e-FOAM, e-FuRES, e-PLS-DA, and e-SIMCA were 96.7 %, 100 %, 100 %, and 96.7 %, respectively. Characteristic components in basil extracts corresponding to highest-ranked useful features were putatively identified. The feature subset may prove valuable as a rapid approach for organic basil authentication.

Description: A small and very simple electromembrane extraction probe (EME-probe) was developed and coupled directly to electrospray ionization mass spectrometry (ESI-MS), and this system was used to monitor in real time in vitro metabolism by rat liver microsomes of drug substances from a small reaction (incubation) chamber (37 °C). The drug-related substances were continuously extracted from the 1.0 mL metabolic reaction mixture and into the EME-probe by an electrical potential of 2.5 V. The extraction probe consisted of a 1-mm long and 350-μm ID thin supported liquid membrane (SLM) of 2-nitrophenyl octyl ether. The drugs and formed metabolites where extracted through the SLM and directly into a 3 μL min −1 flow of 60 mM HCOOH inside the probe serving as the acceptor solution. The acceptor solution was directed into the ESI-MS-system, and the MS continuously monitored the drug-related substances extracted by the EME-probe. The extraction efficiency of the EME-probe was dependant on the applied electrical potential and the length of the SLM, and these parameters as well as the volume of the reaction chamber were set to the values mentioned above to avoid serious depletion from the reaction chamber (soft extraction). Soft extraction was mandatory in order not to affect the reaction kinetics by sample composition changes induced by the EME-probe. The EME-probe/MS-system was used to establish kinetic profiles for the in vitro metabolism of promethazine, amitriptyline and imipramine as model substances.

Description: Single crystals of Rb 2 H 2 P 2 O 6 · 2H 2 O could be obtained from aqueous solutions of hypodiphosphoric acid and rubidium carbonate. Its crystal structure was determined by X-ray diffraction and it crystallizes in the monoclinic space group P 2 1 / c with Z = 4. The salt-like title compound consists of [H 2 P 2 O 6 ] 2– units in staggered P 2 O 6 -skeleton conformation, Rb + cations, and H 2 O molecules, held together by intermolecular hydrogen bonds of the type O ··· O. The vibrational spectra (IR/FIR and Raman) of the rubidium salt were recorded and an assignment of the vibrational modes is proposed based on the point group C 2 h for the P 2 O 6 -skeleton of the anion. The thermal behavior of Rb 2 H 2 P 2 O 6 · 2H 2 O is dominated by a complex TG decay indicating a simultaneous H 2 O delivery coupled with a disproportionation of [H 2 P 2 O 6 ] 2– , what is also supported by Raman spectra of heated samples.

Description: Three metal coordination polymers {[Co(L) 2 (H 2 O) 2 ] 2+ · 2NO 3 – } n ( 1 ), {[Mn(L) 2 (H 2 O) 2 ] 2+ · 2Cl – · 3H 2 O} n ( 2 ), and [ZnL(ba) 2 ] n ( 3 ) [L = 3, 5-bis(imidazole-1-yl)pyridine and Hba = benzoic acid] were synthesized and structurally characterized by IR spectroscopy, elemental analysis, X-ray powder diffraction, and X-ray single crystal diffraction. Complex 1 shows a one-dimensional (1D) chain structure. Adjacent chains are connected by hydrogen bonding and nitrate groups to form a 3D network. Complex 2 features a 2D layer structure. A three-dimensional network is constructed through the cluster consisting of two chloride ions and three water molecules. Complex 3 shows a 1D zigzag chain structure that further twists together to form a 3D network. The X-ray powder diffraction patterns were compared with the simulated ones. Moreover, the luminescent properties of 1 – 3 were investigated in the solid state at room temperature, and the thermogravimetric analyses were carried out to study the thermal stability of the three complexes.

Description: . The reactions of FeCl 3 · 6H 2 O and 2-(2′-hydroxyphenyl)-2-thiazoline as a bidentate O-N donor thiazoline ligand (thoz) afford a five-coordinate Fe III complex [Fe(thoz) 2 Cl] with a distorted square pyramidal configuration. Complex [Fe(thoz) 2 Cl] was isolated as air-stable crystalline solids and fully characterized, including by single-crystal X-ray structure analysis. Complex [Fe(thoz) 2 Cl] shows very efficient reactivity in the oxidation of sulfides to their corresponding sulfoxides using urea hydrogen peroxide (UHP) as the oxidant at room temperature in air.

Description: Two copper(I) complexes of compositions [Cu(HL)I] 2 · EtOH ( 1 ) and [Cu(HL) 3 ]I · MeOH ( 2 ) were synthesized via the reactions of HL [HL = 2(4, 5-diphenyl-1 H -imidazol-2-yl)pyridine] and CuI in EtOH and MeOH, respectively, under solvothermal conditions. The complexes were characterized by X-ray single crystal diffraction, IR spectroscopy, and elemental analysis. Compounds 1 and 2 are catalytically active towards ketalization reaction, giving various ketals under mild conditions.

Description: Mineral samples from the Prasolovskoe epithermal Au-Ag deposit, Russia, were investigated via transmission electron microscopy (TEM). One component was identified as the mineral kurilite Ag 8 Te 3 Se according to the data obtained from electron diffraction (ED) and Fourier transform analyses of high resolution micrographs. Micrometer-sized grains of kurilite were found next to other noble metal chalcogenide domains like the hessite-type. The EDX microprobe analyses of the kurilite domains were determined with the chemical composition Ag 7.9 Au 0.1 Te 2.9 Se 1.0 which is consistent with kurilite doped by gold. Additionally noble metal polychalcogenidehalides (NMPH) were identified via ED. Monoclinic and tetragonal polymorphs of Ag 5 Te 2 Cl were observed for the first time in a mineral sample. One additional component, whose composition equates the kurilite-type component with regard to Ag, Au, Te, and Se but with a marginal chlorine component, crystallizes in a structure type known from synthetic NMPH, namely Ag 23 Te 12 X (X = Cl, Br). This phase as well as the phases Ag 10 Te 4 Br 3 and Ag 20 Te 10 Br 2 was found next to each other in an also investigated synthetic sample.

Description: We have recently developed a novel portable NIR imaging device (D-NIRs), which has a high speed and high wavelength resolution. This NIR imaging approach has been developed by utilizing D-NIRs for studying the dissolution of a model tablet containing 20 % ascorbic acid (AsA) as an active pharmaceutical ingredient and 80 % hydroxypropyl methylcellulose, where the tablet is sealed by a special cell. Diffuse reflectance NIR spectra in the 1,000 to 1,600 nm region were measured during the dissolution of the tablet. A unique band at around 1,361 nm of AsA was identified by the second derivative spectra of tablet and used for AsA distribution NIR imaging. Two-dimensional change of AsA concentration of the tablet due to water penetration is clearly shown by using the band-based image at 1,361 nm in NIR spectra obtained with high speed. Moreover, it is significantly enhanced by using the intensity ratio of two bands at 1,361 and 1,354 nm corresponding to AsA and water absorption, respectively, showing the dissolution process. The imaging results suggest that the amount of AsA in the imaged area decreases with increasing water penetration. The proposed NIR imaging approach using the intensity of a specific band or the ratio of two bands combined with the developed portable NIR imaging instrument, is a potentially useful practical way to evaluate the tablet at every moment during dissolution and to monitor the concentration distribution of each drug component in the tablet. Figure Visible photo and NIR image for tablet dissolution obtained by using a newly developed portable NIR imaging device: D-NIRs

Description: Eight chelating resins were synthesized in high yields by supporting 2-aminomethylpyridine, 2, 2′-dipyridylamine, 1, 2-phenylenediamine and 1, 2-ethylenediamine on Merrifield and Wang resins, respectively. These resins were used both as support of reducing complexes and as alkali metal sensors. 16 stable and easy to prepare reducing complexes, derived from the chelating resins and LiBH 4 and NaBH 4 , were prepared in good yields. These complexes showed chemoselectivity to reduce aldehydes in a low molar ratio and short time reactions. The fluorescence-sensing behavior of the chelating resins for alkali metal was studied. The fluorescence response of the materials where 1, 2-phenylenediamine is supported on Merrifield and Wang resins indicate that they behave as sensors for Li + and K + , respectively.

Description: The reaction of Fe 3 (CO) 12 with (C 3 H 5 ) 2 NCS 2 K in THF at room temperature afforded a red-brown solution. Treatment of the thus-obtained solution with MeI and PhCH 2 Br afforded clusters 1 , (μ-MeS)Fe 2 (CO) 6 (μ 4 -S)Fe 2 (CO) 6 (μ-CN(C 3 H 5 ) 2 ), and 2 , (μ-PhCH 2 CO)Fe 2 (CO) 6 (μ 4 -S)Fe 2 (CO) 6 (μ-CN(C 3 H 5 ) 2 ). Their structures were unambiguously determined by X-ray crystallography. Therefore, this methodology provides a novel route for the syntheses of spiro-S Fe/S clusters with aminocarbyne ligands.

Description: This study presents the preparation of 5-azido-3-nitro-1 H -1,2,4-triazole ( 1 ) in both good yield and high purity, starting from commercially available chemicals in a three step synthesis. Furthermore, several metal and nitrogen-rich salts with sodium ( 3 ), potassium ( 4 ), cesium ( 5 ), silver ( 6 ), lead ( 7 ), ammonium ( 8 ), guanidinium ( 9 ), and aminoguanidinium ( 10 ) were prepared by simple acid-base reactions. All compounds were well characterized by various means, including vibrational (IR, Raman) and multinuclear ( 1 H, 13 C, 14 N, 15 N) NMR spectroscopy, mass spectrometry, and DSC. Additionally the structure of 7 was determined by single-crystal X-ray diffraction. The sensitivities towards various outer stimuli (impact, friction, electrostatic discharge) were determined according to BAM standards. The metal salts were tested as potential primary explosives utilizing various preliminary tests.

Description: With Sharpless' and Meldal's discovery of the immensely supportive effect that metal catalysis has on Huisgen's classical 1,3-dipolar cycloaddition, azides (RN 3 ) – long underappreciated in organic synthesis – suddenly got in the focus of attention as most crucial players in sensational ‘click chemistry'. Less noisy though with the same commitment and even a much broader scope of scientific topics and objectives, the inorganic azide chemistry has made just as great strides in the last few decades. This review (Part I) gives an introductory survey of the most important results, and informs about modern developments and general trends. Particular emphasis is placed on the recent successful approaches to highly unstable homoleptic azido metal complexes of the main group and early transition elements, as well as on the enormous structural versatility caused by the ‘flexidentate' N 3 – ligand with its unsurpassed bridging capacities. The presentation in this paper of selected compounds and reactions is meant, in a way, as a prelude to the [3+2]-cycloadditions of metal azides and related species which will be covered in-depths in Part II. A large part of the comments finally deals with applications in fields such as catalysis, high explosive performance or magnetism of metal compounds containing azide, today certainly one of the most attractive research areas world-wide.

Description: The long-chain ligand, 1-phenyl-3-methyl-4-heptanoyl-pyrazol-5-one (HL) and its zinc(II) complex ZnL 2 were synthesized. The structure and the properties of ZnL 2 were characterized by elemental analysis, IR spectroscopy, X-ray diffraction, and thermogravimetric analysis. The zinc ion is five-coordinated in a square-pyramidal environment by four oxygen atoms of the HL ligands in the equatorial plane and one water molecule in the axial position. The water molecule is directly bonded to Zn 2+ and involved in intermolecular hydrogen bonding network. The complex and its corresponding ligand were screened in vitro against some strains of the human pathogenic bacteria. The metal complex exhibits higher antibacterial activity than its corresponding ligand. The complex exhibits purple effect emission as the result of fluorescence from the intraligand emission excited state.

Description: The microporous metal-organic framework Cd 2 (ABTC)(H 2 O)(DMA) 2 · H 2 O · 3DMA ( 1 ) (H 4 ABTC = 3,3′,5,5′-azobenzenetetracarboxylic acid; DMA = N , N ′-dimethylacetamide) was prepared by solvothermal reaction and characterized. X-ray structure analysis revealed that compound 1 is a three-dimensional (3D) open framework with 2D channels. The topology is based on a PtS net, constructed of 4-connected rectangular ABTC 4– units with 4-connected tetrahedral dinuclear Cd 2 (CO 2 ) 4 (H 2 O)(DMA) 2 secondary building units (SBUs). The solid-state excitation-emission spectra showed that the strongest emission peak is at 403 nm upon excitation at λ = 287 nm.

Description: P(2-SHC 6 H 4 ) 3 ( PS 3 H 3 ) reacts with GaMe 3 (1:1) to give GaMe{P(2-SC 6 H 4 ) 2 (2-SHC 6 H 4 )-κ 3 S , S′,P } ( 1 ), which could be deprotonated with NEt 3 to give [NEt 3 H][GaMe{P(2-SC 6 H 4 ) 3 -κ 3 S , S′,P }] ( 2 ). The 1:2 reaction of E (2-SHC 6 H 4 ) 3 [ E = P ( PS 3 H 3 ), As ( AsS 3 H 3 )] with GaMe 3 gave the dinuclear complexes GaMe{ E (2-SC 6 H 4 ) 2 (2-S{GaMe 2 (THF)}C 6 H 4 )-κ 3 S , S′,E } [ E = P ( 3 ), As ( 4 )]. Serendipitous hydrolysis of 4 resulted in small amounts of the hexanuclear gallium hydroxide complex cyclo -{GaMe(μ-OH)} 6 {As(2-SC 6 H 4 ) 3 -κ S , S′,S′′ } 2 ( 5 ). Complexes 1 – 4 were fully characterized, complexes 2 – 5 also by X-ray crystallography.

Description: Many in-vitro experiments performed to study the response of thiol-containing proteins to changes in environmental redox potentials use dithiothreitol (DTT) to maintain a preset redox environment throughout the experiments. However, the gradual oxidation of DTT during the course of the experiments, and the interaction between DTT and other components in the system, can significantly alter the initial redox potential and complicate data interpretation. Having an internal reporter of the actual redox potential of the assayed sample facilitates direct correlation of biochemical findings with experimental redox status. Reversed-phase high-performance liquid chromatography (RP-HPLC) is a widely used, well-established tool for analysis and purification of biomolecules, including proteins and peptides. Here, we describe a simple, robust, and quantitative RP-HPLC method we developed and tested for determination of the experimental redox potential of an in-vitro sample at the time of the experiment. It exploits the specific UV-absorbance of the oxidized intrinsic DTT in the samples and retains the high resolving power and high sensitivity of RP-HPLC with UV detection.

Description: Topological aspects of the experimental electron density in TiB 2 reconstructed on base of the multipole model are obtained from high-resolution single-crystal X-ray diffraction data. The features of electron density are compared with quantum chemical calculations and analysed in terms of Quantum Theory of Atoms in Molecules for the interpretation of atomic interactions. In spite of some differences in the Laplacian, both experimental and calculated density confirmed two main bonding interactions. The B–B bond critical point suggests a shared-type interaction with pronounced ellipticity in the boron layer, whereas B–Ti bond critical point reveals an interaction intermediate between shared and closed-shell type. Both, theory and experiment indicate a non-structured spherical topology in the penultimate shell of Ti. Integration of the electron density over the atomic basins reveals a charge transfer of 1.1 e (experiment) and 1.4 e (theory) from titanium to boron network, respectively.

Description: The use of smart supports and bioinspired materials to confine living cells and use them for field-deployable biosensors has recently attracted much attention. In particular, bioluminescent whole-cell biosensors designed to respond to different analytes or classes of analyte have been successfully implemented in portable and cost-effective analytical devices. Significant advances in detection technology, biomaterial science, and genetic engineering of cells have recently been reported. Now the challenge is to move from benchtop traditional cell-based assays to portable biosensing devices. Improvement of the analytical performance of these biosensors depends on the availability of optimized bioluminescent reporters, and promising approaches that go beyond reporter gene technology are emerging. To enable handling of cells as ready-to-use reagents, nature-inspired strategies have been used, with the objective of keeping cells in a dormant state until use. Several issues must still be investigated, for example long-term viability of cells, the possibility of performing real-time analysis, and multiplexing capability. Figure Concept of whole-cell bioluminescent biosensor

Description: The stannides Li 2 CuSn 2 and Li 2 AgSn 2 were synthesized by induction-melting (or in a muffle furnace) of the elements in sealed niobium ampoules. The new phases were characterized by powder X-ray diffraction. The structures of both stannides were investigated by X-ray diffraction on single crystals: Li 2 AuSn 2 type, I 4 1 / amd , a = 442.6(1), c = 1940.9(8) pm, wR 2 = 0.0742, 310 F 2 values for Li 2 CuSn 2 and a = 456.33(9) c = 2018.2(6) pm, wR 2 = 0.0626, 339 F 2 values for Li 2 AgSn 2 with 10 variables for each refinement. The transition metal ( T ) atoms have tetrahedral tin coordination. The T Sn 4 tetrahedra are condensed via common corners forming layers that are further condensed by Sn–Sn bonding, leading to three-dimensional [CuSn 2 ] and [AgSn 2 ] networks which leave distorted hexagonal channels for the lithium atoms. The lithium ions show considerable mobility, with activation energies of 0.29 and 0.47 eV extracted from variable temperature 7 Li solid state NMR spectra. 119 Sn Mössbauer spectra at 78 K show signals at isomer shifts of δ = 2.13(1) mm s –1 for Li 2 CuSn 2 and δ = 2.07(1) mm s –1 for Li 2 AgSn 2 . The signals show electric quadrupolar splitting because of the non spherical environment of the tin nuclei. A minor impurity of β-Sn could be identified in both spectra.

Description: The complexes [Ni 2 (L) 2 ] 2 · H 2 O ( 1 ) and [Cu 2 (L) 2 (H 2 O)] · 2CH 3 OH ( 2 ) were prepared by reaction of the chiral Schiff base ligand N -[(1 R ,2 S )-2-hydroxy-1, 2-diphenyl]-acetylacetonimine (H 2 L) with Ni II and Cu II ions, respectively, aiming to develop economically and environmentally-friendly catalysts for the hydrogenation of ketones. They have a dinuclear skeleton with axial vacant sites. The catalytic effects of the two complexes for hydrogenation of ketones were tested using dihydrogen gas as hydrogen source. They present some catalytic effects in hydrogenation of acetophenone, which has a dependence on the temperature and base used in these reactions. However, no apparent catalytic effects were found for the two complexes in hydrogenation of 4-nitroacetophenone and 4-methylacetophenone. Although the catalytic conversion in these hydrogenation reactions is low, they do represent a kind of cheap and environmentally-friendly hydrogenation catalyst.

Description: Poised to investigate the association of vanadium with physiological substrates in materials capable of exerting anticancer biological activity, pH-specific synthetic chemical reactivity between vanadium and triethyl ammonium acetate/trigonelline in aqueous and mixed organic-aqueous media led to the isolation of three new binary composite materials, namely K 2 [(MeN(+)C 5 H 4 COOH) 2 ][V 10 O 28 H 2 ] · 2H 2 O ( 1 ), [(H 2 N(+)Me 2 ) 4 ][V 10 O 28 H 2 ][Me 3 N(+)CH 2 COO(–)] 2 ( 2 ), and [(Me 3 N(+)CH 2 COOH) 4 ][V 10 O 28 H 2 ][Me 3 N(+)CH 2 COO(–)] 2 · 2H 2 O ( 3 ). 1–3 were characterized by elemental analysis, FT-IR and UV/Vis spectroscopy, Cyclic voltammetry, TGA-DTG, and X-ray crystallography. In all three compounds, the [V 10 O 28 H 2 ] 4– core unit is a common cluster assembly, with the vanadium in the +5 oxidation state. The counteracting cationic assembly in each composite material originates in the betaine starting reagent or the solvent out of which the materials crystallized. Biological activity studies of 1 and 3 in vitro in MCF-7 breast epithelial and A549 lung adenocarcinoma cell cultures show that both materials inhibit the viability of both cell lines in a dose-dependent fashion, in juxtaposition to the behavior of the betaine components present in these materials. Collectively, the herein studies a) reveal the uniquely defined synthetic methodologies and physicochemical properties of the variably assembled [V 10 O 28 H 2 ] 4– core units crystallized into the composite binary polyoxovanadate-betaine lattice structures, b) unravel the distinct cytotoxicity profile of the composite materials toward MCF-7 and A549 cells, and c) attest to their future potential as metallodrugs of pharmacological significance in anticancer activity.

Description: A combined (triplex) immunoassay for the simultaneous detection of three mycotoxins in grains was developed with superparamagnetic colour-encoded microbeads, in combination with two bead-dedicated flow cytometers. Monoclonal antibodies were coupled to the beads, and the amounts of bound mycotoxins were inversely related to the amounts of bound fluorescent labelled mycotoxins (inhibition immunoassay format). The selected monoclonal antibodies were tested for their target mycotoxins and for cross-reactivity with relevant metabolites and masked mycotoxins. In the triplex format, low levels of cross-interactions between the assays occurred at irrelevant high levels only. All three assays were influenced by the sample matrix of cereal extracts to some extent, and matrix-matched calibrations are recommended for quantitative screening purposes. In a preliminary in-house validation, the triplex assay was found to be reproducible, sensitive and sufficiently accurate for the quantitative screening at ML level. The triplex assay was critically compared to liquid chromatography–tandem mass spectrometry using reference materials and fortified blank material. Results for the quantification of ochratoxin A and zearalenone were in good agreement. However, the fumonisin assay was, due to overestimation, only suitable for qualitative judgements. Both flow cytometer platforms (Luminex 100 and FLEXMAP 3D) performed similar with respect to sensitivity with the advantages of a higher sample throughput and response range of the FLEXMAP 3D and lower cost of the Luminex 100. The priciple of the direct inhibition microbead immunoassay using fluorescent mycotoxin-reporter conjugates

Description: Molecularly imprinted polymers (MIPs) are synthetic receptors that are able to specifically bind their target molecules in complex samples, making them a versatile tool in biosensor technology. The combination of MIPs as a recognition element with quartz crystal microbalances (QCM-D with dissipation monitoring) gives a straightforward and sensitive device, which can simultaneously measure frequency and dissipation changes. In this work, bulk-polymerized l -nicotine MIPs were used to test the feasibility of l -nicotine detection in saliva and urine samples. First, l -nicotine-spiked saliva and urine were measured after dilution in demineralized water and 0.1× phosphate-buffered saline solution for proof-of-concept purposes. l -nicotine could indeed be detected specifically in the biologically relevant micromolar concentration range. After successfully testing on spiked samples, saliva was analyzed, which was collected during chewing of either nicotine tablets with different concentrations or of smokeless tobacco. The MIPs in combination with QCM-D were able to distinguish clearly between these samples: This proves the functioning of the concept with saliva, which mediates the oral uptake of nicotine as an alternative to the consumption of cigarettes. Figure Schematics of the sample-preparation procedure for l -nicotine spiked saliva- and urine samples with various concentration levels

Description: The crystal structures of the alkali aluminium thiohypodiphosphates M I AlP 2 S 6 (M I = Li, Na) are reported. NaAlP 2 S 6 crystallizes in the orthorhombic space group Fdd 2 (no. 43) with a = 8.0400(2), b = 10.9452(2), c = 20.8801(4) Å, and V = 1837.44(7) Å 3 ( Z = 8). It is isostructural with AgAlP 2 S 6 , which is consistent with the similar ionic radii of Na and Ag. In contrast, LiAlP 2 S 6 crystallizes in a different structure type which has not been observed in the large number of thiohypodiphosphates reported so far. It crystallizes in the monoclinic space group C 2/ c (no. 15) with a = 6.783(3), b = 10.365(4), c = 11.776(4) Å, β = 94.399(5)°, and V = 825.46(5) Å 3 ( Z = 4).

Description: We present the synthesis of 7-(diphenylphosphine)-indole 1 ( HPinol ) as a novel mono- and bidentate P - and N, P -ligand and its coordination chemical behaviour towards the d 6 - and d 8 -transition metals rhodium(III), palladium(II) and rhenium(I). The reaction of 1 with [Cp*RhCl 2 ] 2 in a 1:2 molar ratio leads to the formation of the P -coordinated complex [RhCl 2 ( P –( HPinol ))] ( 2 ). In the presence of the weak base NEt 3 , HCl elimination occurs by forming the neutral amido-phosphine chelated complex [RhCl( N, P –( Pinol ))] ( 3 ). The same P - and N, P -coordination is observed for palladium(II), where two ligands 1 coordinate to the metal centre forming the neutral complexes [PdCl 2 ( P – HPinol ) 2 ] ( 4 ) and [Pd( N, P – Pinol ) 2 ] ( 5 ). The reaction of Re(CO) 5 Br in the presence of NEt 3 and PPh 3 delivers the amido-phosphine complex [Re(CO) 3 PPh 3 ( N, P – Pinol )] ( 6 ). All products were characterised by multinuclear NMR spectroscopy, MS and IR spectra as well as elemental analysis. Furthermore, crystal structures of ligand 1 and all complexes 2–6 are presented.

Description: The generation of key drug metabolites for the purpose of their complete structural characterization, toxicity testing, as well as to serve as standards for quantitative studies, is a critical step in the pharmaceutical discovery and development cycle. Here, we utilized electrochemistry/mass spectrometry for the detection and subsequent generation of six phase I metabolites of simvastatin and lovastatin. Both simvastatin and lovastatin are widely used for the treatment of hypercholesterolemia. There are known drug–drug interaction issues of statin therapy, and it has been suggested that the oxidative metabolites may contribute to the cholesterol-lowering effect of both statins. Of the known phase I metabolites of simvastatin and lovastatin, none are commercially available, and chemical means for the synthesis of a very few of them have been previously reported. Here, we report that electrochemical oxidation of less than 1 mg each of simvastatin and lovastatin led to the generation of three oxidative metabolites of each parent to allow complete nuclear magnetic resonance characterization of all six metabolites. The yields obtained by the electrochemical approach were also compared with incubation of parent drug with commercially available bacterial mutant CYP102A1 enzymes, and it was found that the electrochemical approach gave higher yields than the enzymatic oxidations for the generation of most of the observed oxidative metabolites in this study. Figure Generation of statin drug metabolites by EC/MS (representative mass voltammogram shown), and recombinant CYP enzymes

Description: The binding of a natural anthocyanin to influenza neuraminidase has been studied employing mass spectrometry and molecular docking. Derived from a black elderberry extract, cyanidin-3-sambubiocide has been found to be a potent inhibitor of sialidase activity. This study reveals the molecular basis for its activity for the first time. The anthocyanin is shown by parallel experimental and computational approaches to bind in the so-called 430-cavity in the vicinity of neuraminidase residues 356–364 and 395–432. Since this antiviral compound binds remote from Asp 151 and Glu 119, two residues known to regulate neuraminidase resistance, it provides the potential for the development of a new class of antivirals against the influenza virus without this susceptibility.

Description: A monodisperse molecularly imprinted polymer (MIP) for curcumin was first prepared by precipitation polymerization using methacrylamide (MAM) and 4-vinylpyridine as functional co-monomers, divinylbenzene as a crosslinker, and a mixture of acetonitrile and toluene as a porogen. The use of MAM as the co-monomer resulted in the formation of a monodisperse MIP and non-imprinted polymer (NIP). MIP and NIP, respectively, were monodispersed with a narrow particle size distribution (3.3 ± 0.09 and 3.5 ± 0.10 μm). In addition to shape recognition, hydrophobic and hydrogen-bonding interactions affected the retention and molecular-recognition of curcumin on the MIP. The MIP for curcumin could extract curcuminoids (curcumin, demethoxycurcumin, and bisdemethoxycurcumin) in Curcuma longa L . Figure MIPs prepared with 4-VPY ( left hand ) and 4-VPY and MAM ( right hand ) as the functional monomers were polydispersed and monodispersed, respectively

Description: In the course of investigations relating to magnesia oxysulfate cement the basic magnesium salt hydrate 3Mg(OH) 2 · MgSO 4 · 8H 2 O (3–1–8 phase) was found as a metastable phase in the system Mg(OH) 2 -MgSO 4 -H 2 O at room temperature (the 5–1–2 phase is the stable phase) and was characterized by thermal analysis, Raman spectroscopy, and X-ray powder diffraction. The complex crystal structure of the 3–1–8 phase was determined from high resolution laboratory X-ray powder diffraction data [space group C 2/ c , Z = 4, a = 7.8956(1) Å, b = 9.8302(2) Å, c = 20.1769(2) Å, β = 96.2147(16)°, and V = 1556.84(4) Å 3 ]. In the crystal structure of the 3–1–8 phase, parallel double chains of edge-linked distorted Mg(OH 2 ) 2 (OH) 4 octahedra run along [–110] and [110] direction forming a pattern of crossed rods. Isolated SO 4 tetrahedra and interstitial water molecules separate the stacks of parallel double chains.

Description: An application of plasma-induced grafting of polyethylene membranes with a thin layer of molecularly imprinted polymer (MIP) was presented. High-density polyethylene (HDPE) membranes, “Vyon,” were used as a substrate for plasma grafting modification. The herbicide atrazine, one of the most popular targets of the molecular imprinting, was chosen as a template. The parameters of the plasma treatment were optimized in order to achieve a good balance between polymerization and ablation processes. Modified HDPE membranes were characterized, and the presence of the grafted polymeric layer was confirmed based on the observed weight gain, pore size measurements, and infrared spectrometry. Since there was no significant change in the porosity of the modified membranes, it was assumed that only a thin layer of the polymer was introduced on the surface. The experiments on the re-binding of the template atrazine to the membranes modified with MIP and blank polymers were performed. HDPE membranes which were grafted with polymer using continuous plasma polymerization demonstrated the best result which was expressed in an imprinted factor equal to 3, suggesting that molecular imprinting was successfully achieved. Figure Atrazine and simazine adsorption by untreated HDPE membranes and membranes plasmagrafted with molecular imprinted polymer

Description: We report a chiral high-performance liquid chromatographic enantioseparation method for free α-aminophosphonic, β-aminophosphonic, and γ-aminophosphonic acids, aminohydroxyphosphonic acids, and aromatic aminophosphinic acids with different substitution patterns. Enantioseparation of these synthons was achieved by means of high-performance liquid chromatography on CHIRALPAK ZWIX(+) and ZWIX(-) (cinchona-based chiral zwitterionic ion exchangers) under polar organic chromatographic elution conditions. Mobile phase characteristics such as acid-to-base ratio, type of counterion, and solvent composition were systematically varied in order to investigate their effect on the separation performance and to achieve optimal separation conditions for the set of analytes. Under the optimized conditions, 32 of 37 racemic aminophosphonic acids studied reached baseline separation when we employed a single generic mass-spectrometry-compatible mobile phase, with reversal of the elution order when we used (+) and (-) versions of the chiral stationary phase. Figure New zwitterionic ion-exchangers can separate free amino phosphonic acids and a change from Chiralpak ZWIX(+) to ZWIX(-) allows reversal of enantiomer elution order

Description: Zearalenone (ZEN) is a nonsteroidal estrogenic mycotoxin produced by Fusarium graminearum on maize and barley. Because most current methods of ZEN detection rely on the use of low-stability antibodies or expensive equipment, we sought to develop a rapid, low-cost determination method using aptamers instead of antibodies as the specific recognition ligands. This work describes the isolation and identification of single-stranded DNA (ssDNA) aptamers recognizing ZEN using the modified systematic evolution of ligands by exponential enrichment methodology based on magnetic beads. After 14 rounds of repeated selection, a highly enriched ssDNA library was sequenced and 12 representative sequences were assayed for their affinity and specificity. The best aptamer, 8Z 31 , with a dissociation constant ( K d ) of 41 ± 5 nM, was successfully applied in the specific detection of ZEN in binding buffer and in real samples based on a magnetic separation/preconcentration procedure. This analytical method provided a linear range from 3.14 × 10 −9 to 3.14 × 10 −5  M for ZEN, and the detection limit was 7.85 × 10 −10  M. The selected aptamers are expected to be used in the potential development of affinity columns, biosensors, or other analytical systems for the determination of ZEN in food and agricultural products. Figure Determination of dissociation constant ( K d ) and specificity of aptamers recognizing zearalenone

Description: Countercurrent chromatography (CCC) is an attractive separation method because the analytes are partitioned between two immiscible liquid phases avoiding problems related to solid stationary phase. In recent years, this technique has made great progress in separation power and detection potential. This review describes coupling strategies involving high speed CCC (HSCCC) or centrifugal partition chromatography (CPC). It includes on-line extraction–isolation, hyphenation with mass spectrometry (MS) and nuclear magnetic resonance (NMR) detectors, multidimensional CCC (MDCCC), two-dimensional CCC (2D-CCC), on-line coupling with liquid chromatography (LC), and biological tests, and innovative off-line developments. The basic principles of each method are presented and applications are summarized.

Description: The cover picture shows the synthesis and the molecular structure of a zwitterionic [4.3.0]-bicyclic aluminum-phosphorus compound with annulated C 3 P 2 and Al 2 C 2 PH heterocycles and a 3c-2e Al–H–Al bond. Treatment of the dialkynylphosphine Mes–P(–C=C–CMe 3 ) 2 ( 1 ) with diethylaluminum hydride ( 2 ) in an equimolar ratio afforded a mixture of compounds, in which a [3.2.0]-bicyclic compound 3 with annulated fourmembered AlC 2 P and five-membered P 2 C 3 heterocycles could be identified by NMR spectroscopy. Excess of the hydride 2 yielded small quantities of the zwitterionic [4.3.0]-bicyclic compound 4 , which formally resulted from the unique insertion of a diethylaluminum hydride molecule into the Al–C(vinyl) bond of the strained fourmembered heterocycle of 3 . A six-membered ring is formed which contains an Al–H–Al 3c-2e bond. More details can be found in the Article by Werner Uhl et al. on page 1181 ff.

Description: Comprehensive two-dimensional liquid chromatography (LC × LC) has received much attention because it offers much higher peak capacities than separation in a single dimension. The advantageous peak capacity makes it attractive for the separation of complex samples. Various gradient methods have been used in LC × LC systems. The use of continuous shift gradient is advantageous because it combines the peak compression effect of full gradient mode and the tailed gradient program in parallel gradient mode. Here, a comparison of LC × LC analysis of Chinese herbal medicine with full gradient mode and shift gradient mode in the second dimension was performed. A correlation between the first and second dimensions was found in full gradient mode, and this was significantly reduced with shift gradient mode. The orthogonality increased by 43.7 %. The effective peak distribution area increased significantly, which produced better separation.

Description: Using the bis(pyrazolyl)pyridinylmethane ligand α,α,α-bis(1-pyrazolyl)(2-pyridinyl)toluene {(ph)C(pz) 2 (py)} for bioinorganic inspired coordination chemistry studies, we synthesised and structurally characterised three monofacial complexes [{(ph)C(pz) 2 (py)}CoCl 2 ] ( C1 ), [{(ph)C(pz) 2 (py)}CuCl 2 ] ( C2 ), [{(ph)C(pz) 2 (py)}ZnCl 2 ] ( C3 ) and the binuclear halogenido-bridged complexes [{(ph)C(pz) 2 (py)} 2 (μ-Cl) 2 Fe 2 Cl 2 ] ( C4 ) and [{(ph)C(pz) 2 (py)} 2 (μ-Br) 2 Cu 2 Br 2 ] ( C5 ). In four of these complexes, severe disorders between pyrazolyl and pyridinyl donor groups are observed such that bis(pyrazolyl) and (pyrazolyl)(pyridinyl) coordination modes are concomitantly found. The donor competition is dissected by DFT calculation of the energy differences between the two coordination modes and NBO analysis of the donor situation. The pyrazolyl units provide with more donor strength although pyridine is considerably more basic.

Description: Metal ions poisoning can result from environmental factors, intentional action, or disruption of homeostasis. Although the origin of toxicity may be different, the treatment is similar. Chelation therapy aims to remove the excess of metal ions from tissues to stop further damage of cells. For almost every metal ion, molecules that are able to bind it and remove from the human body are known. Over the years some new chelating agents were discovered and introduced into clinical treatment. In this paper we have focused on typical chelators for metal ions, both essential and toxic for humans. The treatment of poisoning caused by essential metal ions is hard due to the risk of removing them from the biologically relevant molecules (e.g. enzymes). Acute metal ions poisoning is rather rare, so the development of chelators for such cases are historical, but prolonged toxicity of, especially, essential metal ions is extensively studied.

Description: The reactions of [Os(NO)Cl 5 ] 2– with glycine (GlyH), picolinic acid (PicoH), L -proline ( L -ProH) and D -proline ( D -ProH) afforded four novel complexes of the general formula [Os(NO)Cl 3 (AA)] – , where AA = Gly, Pico, L -Pro and D -Pro, respectively. X-ray diffraction studies have revealed that in all cases the same isomer type from three theoretically possible, has been isolated, namely mer (Cl), trans (NO, O)-[Os(NO)Cl 3 (AA)] – . Spectroscopic and electrochemical properties, behavior in aqueous solution and antiproliferative activity in three human cancer cell lines are also reported.

Description: The electron distributions in position and in momentum space of the hcp metals magnesium and zinc are investigated experimentally and compared to results of quantum-chemical calculations. Furthermore, a survey is given on recent analyses of the bonding properties of zinc and cadmium, using the method of increments. The experimental deformation densities were obtained by refining multipole models to X-ray diffraction data sets measured at 100 K with either Mo- K α (Mg) or Ag- K α (Zn) radiation. The final R F values (Valray/Jana2006) are 0.0028/0.0034 (Mg) and 0.0068/0.0068 (Zn). The differences to deformation densities obtained from periodic density functional calculations are discussed. The effect of dynamical electron correlation on the electron density was analyzed, using cluster models. Compton profiles were measured with 88.67 keV synchrotron radiation at beamline ID15B at the ESRF in Grenoble. Varied orientations of the samples allowed for probing the projected momentum distribution along the [100], [423] and [001] directions. Fourier transforms of the computed reciprocal form factor B ( r ) resulted in the corresponding theoretical Compton profiles. It is suggested that the anomalous hcp structure of zinc is favored by a kinetic balancing of the valence electrons, i.e. correlation mediated 4 s -3 d interactions.

Description: . This Research Report provides an overview on synthesis, structure, and reactivity of the recently discovered carboranylamidinate ligands. Carboranylamidinate anions of the type [( o -C 2 B 10 H 10 C(NHR)(=N R )] – ( R = i Pr, cyclohexyl) are readily accessible via addition of o -lithiocarborane to N , N ′-carbodiimides R –N=C=N– R . They combine the highly versatile characteristics of both amidinates and carboranes in one unique ligand system. Unlike simple amidinate anions, the carboranylamidinates coordinate to metal ions not as typical N , N ′-chelating ligands but adopt an unexpected κ 2 C, N -bonding mode. The free imine functionality in carboranylamidinates can be further deprotonated. The resulting dianions were demonstrated to be excellent starting materials for novel boron-rich heterocycles incorporating e.g. Si, Sn, P, or transition metals such as Ti, Zr, Rh, and Ir. Further modification of the carboranylamidinate cage structure includes the introduction of additional functional groups like –SH or –SeH as well as the selective removal of a boron atom with formation of novel nido -type dicarbollylamidinate ligands. An initial study already showed that transition metal carboranylamidinates are potentially useful as polymerization catalysts.

Description: KSbWO 6 was prepared by sol-gel method. N-doped KSbWO 6 (KSbWO 6– x N x ) was obtained by heating KSbWO 6 and urea at 400 °C. Both the compounds are characterized by powder X-ray diffraction (XRD), TEM, SEM-EDS, X-ray photo electronic spectroscopy (XPS), and UV/Vis diffuse reflectance spectroscopy (UV-DRS). A shift in the peak positions of powder XRD and XPS spectra was observed. The band gap energy ( E g ) of KSbWO 6 and N-doped KSbWO 6 was obtained from their diffused reflectance spectra. E g was reduced from 3.17 eV to 2.56 eV upon nitrogen doping in KSbWO 6 . The reduction of the E g is attributed to the lifting of valence band of N-doped KSbWO 6 , due to the mixing of O 2p states with N 2p states. The photocatalytic activity of both the samples was studied by degradation of methylene blue (MB). The nitrogen doped KSbWO 6 shows higher photocatalytic activity compared to that of KSbWO 6 .

Description: The chemistry of cytotoxic platinum(II) complexes is more or less restricted to ligand exchange reactions, derivatization of coordinated ligands is cumbersome, and subsequent purification in many cases impossible. Consequently, kinetically more inert platinum(IV) complexes found their way into the development of novel, promising anticancer drugs. Research has focused more and more during the last years on the use of platinum(IV) complexes featuring one or two axial succinato ligands in which one carboxylic acid moiety is available for further derivatization. In order to gain a deeper insight into the mechanism of action, isotopically labeled platinum(IV) complexes with axial (1,4– 13 C 2 )succinato ligands were synthesized and fully characterized by multinuclear ( 1 H, 13 C, 15 N, and 195 Pt) 1D- and 2D-NMR spectroscopy. Especially of note in this context is a long range 1 H, 13 C shift correlation signal detected between the equatorial ammine protons and the axially coordinated carboxylato moiety. Furthermore, their behavior in extracts of SW480 cancer cells was investigated. Preliminary results demonstrate that cisplatin analogs are reduced significantly faster in comparison to carboplatin analogs.

Description: The Cu II solution chemistry of synthetic derivatives of naturally occurring pseudo-octapeptides (patellamides and ascidiacyclamide) is described. The complex stabilities [mono- and dicopper(II) complexes] of five different ligands were determined by isothermal microcalorimetry (ITC), and square wave voltammetry (SQW) was used to elucidate the electrochemical properties. In agreement with published spectroscopic data, there is cooperative binding of two Cu II ions and the overall stabilities are, in agreement with known stabilities of the natural ligands and expectations based on the donor sets (two N-based heterocycles and one amide per Cu II ), only moderate ( K ≤ 10 6 ). There is a slight dependence of the stabilities on the ligand structure (configuration of the side chains), and that derived from the natural products forms the most stable complexes. Due to the complex equilibria in solution and the instability of the reduced forms, voltammetry shows complex equilibria, which preclude the full assignment of all processes. The positive reduction potentials are in agreement with relatively low complex stabilities. These observations complete earlier studies, concentrating on spectroscopy and structural aspects, and are also discussed in relation to the possible biological function of the cyclic peptides, i.e. metal ion transport, oxygen activation, carboanhydrase, and phosphatase activities.

Description: Setting out from protected L -cysteine a 2,5-diketopiperazine V can be synthesized, the reduction of which with NaBH 4 /TiCl 4 leads to (6 R ,8 aR )-7-methyl-6-(sulfanylmethyl)-thiazolidine [3,4- a ] piperazine, L 1 H as well as N , N ′-dimethyl-(2 R ,5 R )-bis(sulfanylmethyl) piperazine, L 2 H 2 , which were separated and characterized. L 2 H 2 can be obtained selectively, if V is reduced by NaBH 4 /TiCl 4 in the presence of DIEA · HCl, and it represents a precursor for a novel, chiral ligand, as after deprotonation it provides two thiolato and two amino donor functions for the coordination of a metal atom. Deprotonation of L 1 H and L 2 H 2 with NaOMe followed by treatment with NiBr 2 (dme) led to the isolation of the dimeric complexes [L 1 NiBr] 2 ( 1 ) and [L 2 Ni] 2 ( 2 ), respectively. Both were fully characterized, and cyclic voltammetry indicated the possibility of Ni II → Ni III oxidations for complex 2 . 2 can be regarded as a structural model for the A clusters of the acetyl coenzyme A synthase.

Description: Autism spectrum disorders (ASD) are a group of neurodevelopmental disorders resulting from multiple factors. Diagnosis is based on behavioural and developmental signs detected before 3 years of age, and there is no reliable biological marker. The purpose of this study was to evaluate the value of gas chromatography combined with mass spectroscopy (GC-MS) associated with multivariate statistical modeling to capture the global biochemical signature of autistic individuals. GC-MS urinary metabolic profiles of 26 autistic and 24 healthy children were obtained by liq/liq extraction, and were or were not subjected to an oximation step, and then were subjected to a persilylation step. These metabolic profiles were then processed by multivariate analysis, in particular orthogonal partial least-squares discriminant analysis (OPLS-DA, R 2 Y(cum) = 0.97, Q 2 (cum) = 0.88). Discriminating metabolites were identified. The relative concentrations of the succinate and glycolate were higher for autistic than healthy children, whereas those of hippurate, 3-hydroxyphenylacetate, vanillylhydracrylate, 3-hydroxyhippurate, 4-hydroxyphenyl-2-hydroxyacetate, 1 H -indole-3-acetate, phosphate, palmitate, stearate, and 3-methyladipate were lower. Eight other metabolites, which were not identified but characterized by a retention time plus a quantifier and its qualifier ion masses, were found to differ between the two groups. Comparison of statistical models leads to the conclusion that the combination of data obtained from both derivatization techniques leads to the model best discriminating between autistic and healthy groups of children.

Description: Mass spectrometry based technologies are promising as generalizable high-throughput assays for enzymatic activity. In one such technology, a specialized enzyme substrate probe is presented to a biological mixture potentially exhibiting enzymatic activity, followed by an in situ enrichment step using fluorous interactions and nanostructure-initiator mass spectrometry. This technology, known as Nimzyme , shows great potential but is limited by the need to synthesize custom substrate analogs. We describe a synthetic route that simplifies the production of these probes by fashioning their perfluorinated invariant portion as an alkylating agent. This way, a wide variety of compounds can be effectively transformed into enzyme activity probes. As a proof of principle, a chloramphenicol analog synthesized according to this methodology was used to detect chloramphenicol acetyltransferase activity in cell lysate. This verifies the validity of the synthetic strategy employed and constitutes the first reported application of Nimzyme to a non-carbohydrate-active enzyme. The simplified synthetic approach presented here may help advance the application of mass spectrometry to high-throughput enzyme activity determination. Figure The Nimzyme high-throughput enzyme activity assay allows for the detection of enzyme activity in cell lysate. Fluorous interactions between a specialized substrate probe and a nanostructure-initiator mass spectrometry surface allow for in situ cleanup and the subsequent collection of unambiguous mass spectra. One of the main hurdles that prevents the widespread adoption of this technology is the need to chemically synthesize the required probes. Here, we present a simplified route to derive Nimzyme probes from a wide variety of biologically interesting substrates.

Description: Carbon isotope ratio (CIR) analysis has been routinely and successfully applied to doping control analysis for many years to uncover the misuse of endogenous steroids such as testosterone. Over the years, several challenges and limitations of this approach became apparent, e.g., the influence of inadequate chromatographic separation on CIR values or the emergence of steroid preparations comprising identical CIRs as endogenous steroids. While the latter has been addressed recently by the implementation of hydrogen isotope ratios (HIR), an improved sample preparation for CIR avoiding co-eluting compounds is presented herein together with newly established reference values of those endogenous steroids being relevant for doping controls. From the fraction of glucuronidated steroids 5β-pregnane-3α,20α-diol, 5α-androst-16-en-3α-ol, 3α-Hydroxy-5β-androstane-11,17-dione, 3α-hydroxy-5α-androstan-17-one (ANDRO), 3α-hydroxy-5β-androstan-17-one (ETIO), 3β-hydroxy-androst-5-en-17-one (DHEA), 5α- and 5β-androstane-3α,17β-diol (5aDIOL and 5bDIOL), 17β-hydroxy-androst-4-en-3-one and 17α-hydroxy-androst-4-en-3-one were included. In addition, sulfate conjugates of ANDRO, ETIO, DHEA, 3β-hydroxy-5α-androstan-17-one plus 17α- and androst-5-ene-3β,17β-diol were considered and analyzed after acidic solvolysis. The results obtained for the reference population encompassing n  = 67 males and females confirmed earlier findings regarding factors influencing endogenous CIR. Variations in sample preparation influenced CIR measurements especially for 5aDIOL and 5bDIOL, the most valuable steroidal analytes for the detection of testosterone misuse. Earlier investigations on the HIR of the same reference population enabled the evaluation of combined measurements of CIR and HIR and its usefulness regarding both steroid metabolism studies and doping control analysis. The combination of both stable isotopes would allow for lower reference limits providing the same statistical power and certainty to distinguish between the endo- or exogenous origin of a urinary steroid.

Description: A method for the simultaneous analysis of nucleosides and nucleotides in infant formula using reversed-phase liquid chromatography–tandem mass spectrometry is described. This approach is advantageous for compliance testing of infant formula over other LC-MS methods in which only nucleotides or nucleosides are measured. Following sample dissolution, protein was removed by centrifugal ultrafiltration. Chromatographic analyses were performed using a C 18 stationary phase and gradient elution of an ammonium acetate/bicarbonate buffer, mass spectrometric detection and quantitation by a stable isotope-labelled internal standard technique. A single laboratory validation was performed, with spike recoveries of 80.1–112.9 % and repeatability relative standard deviations of 1.9–7.2 %. Accuracy as bias was demonstrated against reference values for NIST1849a certified reference material. The method has been validated for the analysis of bovine milk-based, soy-based, caprine milk-based and hydrolysed milk protein-based infant formulae. Figure LC-MS/MS MRM chromatogram of mixed nucleoside and nucleotide standard

Description: Melarsoprol is the only currently available drug for treatment of the late stage of African trypanosomiasis (sleeping sickness). Unfortunately, the arsenic-containing drug causes serious side effects, for which the mechanisms have not been elucidated so far. This investigation describes the study of the melarsoprol biotransformation processes by electrochemical (EC) techniques. Based on EC, potential oxidation reactions of melarsoprol are examined. Moreover, the reactivity of melarsoprol, its metabolite melarsen oxide, and their oxidation products toward the tripeptide glutathione and the proteins hemoglobin and human serum albumin is evaluated. The combination of different analytical techniques allows the identification as well as the quantification of the biotransformation products. The hyphenation of liquid chromatography (LC) and electrospray ionization mass spectrometry (ESI–MS) is applied for identification and structure elucidation, which implies the determination of exact masses and fragmentation patterns. For the selective detection of arsenic containing metabolites, LC coupled to inductively coupled plasma mass spectrometry is utilized. Based on the obtained data, the oxidative biotransformation of melarsoprol can be predicted, revealing novel species which have been suspected, but not been identified up to now. The results of the protein studies prove that melarsen oxide, the active derivative of melarsoprol, strongly binds to human hemoglobin and forms different adducts via the free cysteinyl groups of the hemoglobin α- and β-chain.

Description: A new chiral racemic ligand ( o -carboranyl)bis(2-hydroxymethyl)pyridine oCB(hmpH) 2 , that is composed of a central o -carborane unit where two arms radiate out of the cluster carbons each one containing a 2-pyridylmethylalcohol chelating arms, provides two potentially bidentate {NO} or one tetradentate {N 2 O 2 } binding pockets. An unprecedented octahedral Co II complex [CoCl 2 ( anti - oCB (hmpH) 2 ] was obtained under aerobic conditions and characterized by X-ray crystallography as well as IR and NMR spectroscopy. anti - oCB (hmpH) 2 acts as a tetradentate N 2 O 2 -ligand affording the complex as a racemic mixture of cis- α Δ-[CoCl 2 ( RR anti - oCB (hmpH) 2 )] and Λ-[CoCl 2 ( SS anti - oCB (hmpH) 2 )]. The new ligand oCB(hmpH) 2 appears to be suitable for producing a variety of new chiral-at-metal complexes.

Description: β-Lactam antibiotics, including penicillins and cephalosporins, are commonly used in veterinary medicine. Illegal use and abuse of β-lactams could cause allergy and selected bacterial resistance. BlaR-CTD, the carboxy-terminal of penicillin-recognizing protein BlaR from Bacillus licheniformis ATCC 14580, was utilized in this study to develop a receptor-based ELISA for detection and determination of β-lactam antibiotics in milk, beef, and chicken. This assay was based on directly competitive inhibition of binding of horseradish peroxidase-labeled ampicillin to the immobilized BlaR-CTD by β-lactams. The assay was developed as screening test with the option as semiquantitative assay, when the identity of a single type of residual β-lactam was known. The IC 50 values of 15 β-lactam antibiotics, including benzylpenicillin, ampicillin, amoxicillin, dicloxacillin, oxacillin, nafcillin, cefapirin, cefoperazone, cefalotin, cefazolin, cefquinome, ceftriaxone, cefotaxime, cefalexin, ceftiofur and its metabolite desfuroylceftiofur were evaluated and ranged from 0.18 to 170.81 μg L −1 . Simple sample extraction method was carried out with only phosphate-buffered saline, and the recoveries of selected β-lactam antibiotics in milk, beef, and chicken were in the range of 53.27 to 128.29 %, most ranging from 60 to 120 %. The inter-assay variability was below 30 %. Limits of detection in milk, beef, and chicken muscles with cefquinome matrix calibration were 2.10, 30.68, and 31.13 μg kg −1 , respectively. This study firstly established a rapid, simple, and accurate method for simultaneous detection of 15 β-lactams in edible tissues, among which 11 β-lactams controlled by European Union could be detected below maximum residue limits. Figure The receptor-based ELISA for blank sample (negative samples, left ) and sample containing β-lactam antibiotics (positive samples, right )

Description: In recent years, near-infrared (NIR) hyperspectral imaging has proved its suitability for quality and safety control in the cereal sector by allowing spectroscopic images to be collected at single-kernel level, which is of great interest to cereal control laboratories. Contaminants in cereals include, inter alia , impurities such as straw, grains from other crops, and insects, as well as undesirable substances such as ergot (sclerotium of Claviceps purpurea ). For the cereal sector, the presence of ergot creates a high toxicity risk for animals and humans because of its alkaloid content. A study was undertaken, in which a complete procedure for detecting ergot bodies in cereals was developed, based on their NIR spectral characteristics. These were used to build relevant decision rules based on chemometric tools and on the morphological information obtained from the NIR images. The study sought to transfer this procedure from a pilot online NIR hyperspectral imaging system at laboratory level to a NIR hyperspectral imaging system at industrial level and to validate the latter. All the analyses performed showed that the results obtained using both NIR hyperspectral imaging cameras were quite stable and repeatable. In addition, a correlation higher than 0.94 was obtained between the predicted values obtained by NIR hyperspectral imaging and those supplied by the stereo-microscopic method which is the reference method. The validation of the transferred protocol on blind samples showed that the method could identify and quantify ergot contamination, demonstrating the transferability of the method. These results were obtained on samples with an ergot concentration of 0.02 % which is less than the EC limit for cereals (intervention grains) destined for humans fixed at 0.05 %. Online Abstract Figure Pictures showing a the manual removal of ergot bodies and b the observation by the stereo-microscopic method (official method); c the metallic holder with the reference material, and d the NIR hyperspectral SisuCHEMA instrument

Description: Abstract. The title compounds NH 4 [Cu(S 2 CNH 2 ) 2 ] · H 2 O (A) and CuS 2 CNH 2 (B) were prepared from aqueous alcoholic solutions by reaction of ammoniumdithiocarbamate with copper sulfate in presence of excess cyanide as reductive. (A) crystallizes in the orthorhombic space group C 222 1 (No. 20) with a = 8.9518(6), b = 9.6414(6) and c = 10.6176(8) Å, Z = 4. (B) crystallizes in the orthorhombic space group P 2 1 2 1 2 1 (No. 19) with a = 5.9533(4), b = 6.6276(4) and c = 9.4834(5) Å, Z = 4. In the crystal structure of (A) copper has a tetrahedral surrounding of four monodentate dithiocarbamate ligands. These structural units form 2D nets stacked along [001]. Staggered chains consisting of H 2 O and NH 4 + penetrate the crystal structure along [001] yielding additional coherence via hydrogen bonds. The crystal structure of (B) comprises a three-dimensional tetrahedral framework of CuS 4 units exclusively linked by vertices. The arrangement is reminiscent of a filled β -cristobalite structure with the dithiocarbamate ligands extending into the hollow spaces. Thermal decomposition precedes stepwise finally giving Cu 2 S in each case.

Description: A thorough study on the thermoelectric potential of the layered compound SnBi 2 Te 4 is presented. Phase range studies on SnBi 2 Te 4 , unit cell parameters by powder X-ray diffraction, and electronic structure calculations (both LDA and GGA functional) were performed. Physical property measurements regarding substitution of tin and bismuth with the triel ( Tr = Ga, In, Tl) elements are presented towards the improvement of thermoelectric properties, according to Tr x Sn 1– x Bi 2 Te 4 and Tr x SnBi 2– x Te 4 . The range of inclusion was generally over 0.01 ≤ x ≤ 0.15 to monitor compound changes as well as phase purity limits. Seebeck coefficient, S , electrical conductivity, σ , and thermal conductivity, κ , were measured, yielding the dimensionless Figure of merit, ZT , data over a temperature range between 300 K and 680 K. Results of partial replacements of tin and bismuth are compared and reported. ZT max values range from 0.10 to 0.34 depending on the dopant, achieved at temperatures from 355 K to 420 K.

Description: A new two-step procedure for the synthesis of MoS 2 nanotubes using lead as a growth promoter is reported. In the first step, molybdenum suboxide nanowhiskers containing a small amount of lead atoms were created by exposing a pressed MoS 2 +Pb mixture to highly compressed shock-heated argon gas, with estimated temperatures exceeding 9900 K. In the second step, these molybdenum suboxide nanowhiskers served as templates for the sulfidization of the oxide into MoS 2 nanotubes (by using H 2 S gas in a reducing atmosphere at 820 °C). Unlike the case of WS 2 nanotubes, the synthesis of a pure phase of MoS 2 nanotubes from molybdenum oxide has proven challenging, due mostly to the volatile nature of the latter at the high requisite reaction temperatures (〉800 °C). In contrast, the nature and apparent reaction mechanism of the method reported herein are amenable to future scale-up. The high-temperature shockwave system should also facilitate the synthesis of new nanostructures from other layered materials.

Description: The reaction of RuCl 2 (PPh 3 ) 3 with N -pyrazolylpropanamide ( N -ppa) displaces a single PPh 3 producing the six-coordinate complex RuCl 2 (PPh 3 ) 2 ( N -ppa) ( 1 ). A crystal structure determination of the dichloromethane solvate RuCl 2 (PPh 3 ) 2 ( N -ppa) · 2CH 2 Cl 2 ( 1·2CH 2 Cl 2 ) revealed that the geometry about the central Ru atom is distorted octahedral with the chloride ligands in trans -position and the N -ppa acting as N , O -chelating ligand. In the solid state, RuCl 2 (PPh 3 ) 2 ( N -ppa) molecules are dimerized via N–H ··· Cl hydrogen bonds. The dimers pack as chains in the c direction and form voids that are occupied by dichloromethane solvent molecules.

Description: Four complexes with supramolecular architectures, namely, MZCA · 3H 2 O ( 1 ), [Zn(H 2 O) 6 ] 2+ · [MZCA] 2 · [H 2 O] 6 ( 2 ), [Mn(MZCA) 2 (H 2 O) 4 ] · 2H 2 O ( 3 ), and [Ni(MZCA) 2 (H 2 O) 4 ] · 2H 2 O ( 4 ) [MZCA = 3-(carboxymethyl)-2, 7-dimethyl-3H-benzo[d]imidazole-5-carboxylic acid], were synthesized and characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction. Complexes 1 and 2 display a remarkable 3D network with 1D hydrophilic channels. Complexes 3 and 4 are isostructural and exhibit a 3D structure encapsulating 1D 24-membered ring microporous channels. The UV/Vis and fluorescent spectra were measured to characterize complexes 1 – 4 . The thermal stability of complexes 2 – 4 were also examined.