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  • Chemistry  (54)
  • Animals  (2)
  • 550 - Earth sciences
  • 2000-2004
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  • 1996  (57)
  • 1
    Publication Date: 1996-01-19
    Description: About 90 percent of human pancreatic carcinomas show allelic loss at chromosome 18q. To identify candidate tumor suppressor genes on 18q, a panel of pancreatic carcinomas were analyzed for convergent sites of homozygous deletion. Twenty-five of 84 tumors had homozygous deletions at 18q21.1, a site that excludes DCC (a candidate suppressor gene for colorectal cancer) and includes DPC4, a gene similar in sequence to a Drosophila melanogaster gene (Mad) implicated in a transforming growth factor-beta (TGF-beta)-like signaling pathway. Potentially inactivating mutations in DPC4 were identified in six of 27 pancreatic carcinomas that did not have homozygous deletions at 18q21.1. These results identify DPC4 as a candidate tumor suppressor gene whose inactivation may play a role in pancreatic and possibly other human cancers.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Hahn, S A -- Schutte, M -- Hoque, A T -- Moskaluk, C A -- da Costa, L T -- Rozenblum, E -- Weinstein, C L -- Fischer, A -- Yeo, C J -- Hruban, R H -- Kern, S E -- CA62924/CA/NCI NIH HHS/ -- New York, N.Y. -- Science. 1996 Jan 19;271(5247):350-3.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Department of Pathology, Johns Hopkins University School of Medicine, Baltimore, MD 21205, USA.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/8553070" target="_blank"〉PubMed〈/a〉
    Keywords: Alleles ; Amino Acid Sequence ; Animals ; Base Sequence ; Cell Division ; Chromosome Mapping ; *Chromosomes, Human, Pair 18 ; *DNA-Binding Proteins ; Gene Deletion ; Gene Expression ; *Genes, Tumor Suppressor ; Genetic Markers ; Humans ; Mice ; Molecular Sequence Data ; Mutation ; Neoplasm Transplantation ; Pancreatic Neoplasms/*genetics/pathology ; Proteins/chemistry/*genetics/physiology ; Signal Transduction ; Smad4 Protein ; *Trans-Activators ; Transforming Growth Factor beta/physiology ; Transplantation, Heterologous ; Tumor Cells, Cultured
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 2
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    American Association for the Advancement of Science (AAAS)
    Publication Date: 1996-01-12
    Description: Early stages of T cell development are thought to include a series of coordinated interactions between thymocytes and other cells of the thymus. A monoclonal antibody specific for mouse CD81 was identified that blocked the appearance of alpha beta but not gamma delta T cells in fetal organ cultures initiated with day 14.5 thymus lobes. In reaggregation cultures with CD81-transfected fibroblasts, CD4-CD8- thymocytes differentiated into CD4+CD8+ T cells. Thus, interactions between immature thymocytes and stromal cells expressing CD81 are required and may be sufficient to induce early events associated with T cell development.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Boismenu, R -- Rhein, M -- Fischer, W H -- Havran, W L -- AI32751/AI/NIAID NIH HHS/ -- New York, N.Y. -- Science. 1996 Jan 12;271(5246):198-200.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Department of Immunology, Scripps Research Institute, La Jolla, CA 92037, USA.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/8539618" target="_blank"〉PubMed〈/a〉
    Keywords: Amino Acid Sequence ; Animals ; Antibodies, Monoclonal/immunology ; Antigens, CD/genetics/immunology/*physiology ; Antigens, CD4/analysis ; Antigens, CD8/analysis ; Antigens, CD81 ; Base Sequence ; CHO Cells ; Cell Differentiation ; Cricetinae ; Membrane Proteins/immunology/*physiology ; Mice ; Molecular Sequence Data ; Organ Culture Techniques ; Receptors, Antigen, T-Cell, alpha-beta/*analysis ; Receptors, Antigen, T-Cell, gamma-delta/analysis ; Stromal Cells/immunology ; T-Lymphocyte Subsets/cytology/*immunology ; Thymus Gland/cytology/*immunology ; Transfection
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 79 (1996), S. 1670-1682 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Absolute rate constants and their temperature dependence are determined by time-resolved electron spin resonance for the addition of Me3Ċ to 20 and of Me3CO2CĊH2 to six mono- and disubstituted alkynes in solution. For Me3Ċ the rate constants show polar alkyne-substituent effects which are, however, weaker than for the corresponding alkenes. For Me3CO2ĊH2, the rate constants do not vary strongly with alkyne substitution and probably increase with increasing reaction exothermicity. Both radicals react generally slower with alkynes than with alkenes which is discussed in terms of the state correlations. Several vinyl-type radical adducts of Me3Ċ to alkenes are characterized by electron spin resonance, and their spectral data indicate linear or bent configurations of the radical carbon depending on the substitution.
    Additional Material: 6 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 1475-1482 
    ISSN: 0009-2940
    Keywords: Allenylidene complexes ; Alkynyl complexes ; Cyclobutenylidene complexes ; Cycloadditions ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pentacarbonyl(allenylidene)chromium and -tungsten, [(CO)5—M=C=C=CR2] (M=Cr, R=C6H4CH3-p(1a), C6H4OCH3 (1b); M=W, R=C6H4CH3-p (1c), react with the alkynyl complexes [Cp(CO)2Fe—C≡CR′] (R′ = nBu (2), Ph (4)), [Cp*(CO)2Fe—C≡CnBu] (6), [Cp(CO){P(OMe)3}-Fe—C≡CnBu] (8) and [Cp(PPh3)Ni—C≡CnBu] (10) by cycloaddition of the C≡C bond of the alkynyl complexes to the Cα=Cβ bond of the allenylidene ligand to give 3a-c), (5), (7), and respectively. The cycloaddition is highly selective. The spectroscopic data of these 1,3-heterobinuclear complexes indicate a delocalized π-system (M=Cr, W; Y=[Fe(CO)2Cp], [Fe(CO)(P{OMe}3)Cp], [Fe(CO)2Cp*], [Ni(PPh3)-Cp]). X-ray structural analyses of the compounds 3a, 9a, and 11c reveal a “butterfly” conformation of the four-membered ring. Its puckering angle is 142° (3a), 152° (9a), and 151° (11c). All Complexes exhibit a moderate to strong negative solvatochromic behavior. The extent of the solvatochromic effect depends on [(CO)5M] and Y and considerably decreases when C=CR2 is replaced by e.g. CMe2.
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  • 5
    ISSN: 0009-2940
    Keywords: Thioaldehyde complexes ; Selenoaldehyde complexes ; Thietane complexes ; Selenetane complexes ; Rearrangements ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pentacarbonyl(thiobenzaldehyde)tungsten und pentacarbonyl(selenobenzaldehyde)tungsten (1a and 1b) undergo a thermal [2 + 2] cycloaddition with several vinyl ethers to give highly substituted transition metal-coordinated thietanes and selenetanes. The addition is highly regio- and stereospecific. The products undergo acid-catalyzed rearrangements, which lead to thermodynamically more stable diastereomers of the thietanes and selenetanes. The stereochemistry of both addition and rearrangement was established by reaction of deuterium-labeled vinyl ethers and by reaction of the cis and trans isomers of ethyl propenyl ether. The crystal structure of the bicyclic addition product of 1a and 3,4-dihydro-2H-pyran is reported.
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  • 6
    ISSN: 0009-2940
    Keywords: Transition-metal indium complexes ; Nickel-indium bonds ; Intramolecular Lewis base adducts ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of InBr/InBr3 or InBr/BrIn[(CH2)3NMe2]2 with the transition metal dimers [L(CO)nM]2 {L = CO, Cp, C5H4[(CH2)2NMe2]; M = Fe, Co, Ni; n = 1-3} in THF or dioxane gives in almost quantitative yield the transition metal indium complexes L(CO)nM—InBr2(Do) (Do = THF, NC7H13) and L(CO)nM—In[(CH2)3NMe2](Br) respectively. The new compounds were characterized by elemental analysis, infrared v(CO) spectroscopy, NMR, and mass spectrometry. An X-ray single crystal structure determination of (η5-C5H5)(CO)-Ni-InBr2(NC7H13) (1a) revealed a short Ni-In bond of 246.3(1) pm.
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  • 7
    ISSN: 0009-2940
    Keywords: Phospholenes ; Phosphepines ; Ring expansion reactions ; Perfluorinated diketones ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New Phospholene and Phosphepine Derivatives from λ3-Phosphorus Compounds and Hexafluoroacetone or Perfluorinated α-DiketonesThe reaction of the bis(2-chloroethyl)amino-substituted benzoxazaphosphorinone 1 with hexafluoroacetone (HFA) proceeds with insertion of the carbonyl group of HFA into the heterocycle of 1 to form the oxazaphosphepinedione 2. Triethyl phosphite (3) and triphenyl phosphite (4) react with the perfluorinated diketones 5 and 6 with formation of the pentaoxyphosphoranes 7-10 containing a dioxaphospholene ring system. The reaction of the (2-chloroethyl)amino- and bis(2-chloroethyl)amino-substituted 1,3,5,2-triazaphosphorinanediones 11-14 with the perfluorinated diketone C2F5C(:O)C(:O)CF3 (15) furnishes spirophosphorane derivatives with the dioxaphospholene ring system, 16 and 17, in two cases only. Compound 1 and 2-[bis(2-chloroethyl)-amino]-4H-1,3,2-benzodioxaphosphorin-4-one (18) react with the perfluorinated α-diketones 5 and 6 with insertion of the diketones into the heterocycle of 1 and 18 with formation of compounds 19-22 containing dioxa- and oxazaphosphepinone ring systems. The expected oxidative addition of the diketones to λ3P with formation of spirophosphoranes was not observed. Compounds 19-22 were obtained as mixtures of isomers (19a/b-22a/b). Single crystal X-ray structure analyses were conducted on 2 and 9. The seven-membered ring of 2 displays a “tub” conformation, with the O and benzo C atoms lying out of the plane of the other four atoms. The two independent molecules of 9 are similar, but differ in the degree of distortion from trigonal-bipyramidal geometry of phosphorus.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 615-622 
    ISSN: 0009-2940
    Keywords: Vinylidene complexes ; Cyclobutenylidene complexes ; Tetrahydroindenes ; Thioether complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pentacarbonyl(pentamethylenevinylidene)chromium, [(CO)5Cr=C=C(CH2)5] (1), reacts with 1-methylthio-1-propyne (2a) and N-(1-propynyl)phenothiazine (2b) by regio-specific addition of the C=C bond of the alkyne to the C=C bond of the vinylidene ligand of 1. Initially, complexes with a spirocyclic cyclobutenylidene ligand are formed, [(CO)5Cr=(CH2)5] (3) and [(CO)5-Cr=(CH2)5] (10). Subsequent thermally initiated ring expansion affords the 2-methyl-4,5,6,7-tetrahydroindenyl(methyl)thioether complex [(CO)5-Cr-S(Me)(Me-C9H10)] (4) and the N-(2-methyl-4,5,6,7-tetrahydroindenyl)phenothiazine complex [(CO)5Cr-S(C6H4)2-N-(Me-C9H10)] (11), respectively. In both complexes, 4 and 11 the ligand is coordinated to the metal via the sulfur atom. The constitutions were established by (H,H)-, (H,C)- and NOE-correlated NMR spectroscopy. In the reaction of 1 with 2a, in addition to 3 and 4, the methyl(propynyl)thioether complex [(CO)5Cr-S(Me)C≡CMe] (5) was formed. An isolable 3-methylthio-substituted cyclobutenylidene complex, [(CO)5Cr=Ph2] (9) was obtained from [(CO)5Cr=C=CPh2] (8) and 2a. The 4,5,6,7-tetrahydroindenylthioether ligand of 11 was cleaved from the metal by exposure of 11 adsorbed on silica gel to air or by treatment of 11 with [NEt4]Br in dichloromethane.
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 1061-1071 
    ISSN: 0009-2940
    Keywords: Phosphanylnaphthol ; PO ligands ; Chelate complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: P-tertiary or amino-substituted 1-phosphanylnaphth-2-yl silyl ethers 3 are synthesized by stepwise reaction of lithium 1-lithio-2-naphtholate 1 with chlorophosphanes and ClSiMe3. The free phosphanylnaphthols 4 are prepared by alcoholysis. As established by characteristic coupling constants and X-ray structural analyses (of 3c, 4c), 3 exhibit in solution and in the solid state a cis-bisecting conformation, whereas 4 prefers the opposite trans-bisecting arrangement, allowing easy protonation and formation of chelate complexes. Substitution reactions of phosphanylnaphtholates 2 with Ph2PCl and formation of chelate complexes LNi-η5-Cp and L2Pd are described. Attempts to prepare secondary and primary phosphanylnaphthols failed because of facile cleavage of the P-C(naphthyl) bond in PH-substituted 1-phosphanylnaphth-2-ols.
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  • 10
    ISSN: 0009-2940
    Keywords: Benzamidinate ; Zirconium complexes ; Allyl ligands ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Complexes of the type (siam)2Zr(allyl)2 (1a) and (siam)Zr(allyl)nClm are described (2a: n = 1, m = 2; 2b: n = 2, m = 1; 2c: n = 3, m = 0; siam: N,N′ -bis(trimethylsilyl)benzamidinato group). The molecular structure of 1a shows that both allyl groups are differently bonded. One allyl ligand is η3-, the other η1-coordinated. The X-ray crystal structure of the tris-(allyl) complex 2c shows a chiral molecule with two η3-allyl ligands. The third allyl ligand is coordinated in a mode intermediate between η3 and η1, thus serving as a model for an intermediate in the η3-η1 intramolecular rearrangement of the allyl ligands observed in solution. Temperature-dependent 1H- and 13C-NMR spectra of 1a, 2b and 2c indicate a rapid η1-η3 rearrangement of the allyl groups at 60°C. At -50°C two different coordination modes of the allyl groups can be observed in the case of 2b and 2c.
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