Interactions of phospholipid monolayers with carbohydrates

doi:10.1016/0005-2736(84)90018-X

Biochimica et Biophysica Acta (BBA) - Biomembranes

Volume 769, Issue 1, 11 January 1984, Pages 151-159

https://doi.org/10.1016/0005-2736(84)90018-X Get rights and content

Abstract

Surface pressure studies of phospholipid monomolecular films of dimyristoylphosphatidylcholine (DMPC) and dipalmitoylphosphatidylcholine (DPPC) formed at an air/water interface have been made and the effects on the films studied when various carbohydrates are present in the subphase. The results obtained show that at a given temperature, the area per molecule in a monolayer of DPPC increases with increasing concentration of the carbohydrate in the subphase. The carbohydrate which has the greatest expanding effect on the phospholipid monolayer is glycerol, followed in turn by trehalose, sucrose, glucose, raffinose, and inositol. The mechanism of monolayer expansion by glycerol is different from that observed in other carbohydrates, as the following experiments demonstrate. Below the phase transition temperature of DPPC, the area per molecule of DPPC at a pressure of 12.5 dyn/cm is the same with and without glycerol in the subphase. However, when the monolayer is heated to a temperature above the phase transition temperature for DPPC, the area/molecule on glycerol is considerably greater than the area/molecule on water at the same surface pressure. Cooling the monolayer back to the lower temperature produces an area/molecule of DPPC which is identical on both water and glycerol subphases. Glycerol therefore has no effect on the low-temperature (condensed) monolayers but causes expansion of the high-temperature (expanded) monolayers. By contrast with glycerol, both trehalose and sucrose interact with the DPPC monolayer producing an increased area/molecule over that observed on water, both with low-temperature (condensed) monolayers and with the high-temperature (expanded) monolayers. The efficiency of these carbohydrates at expanding the monolayer films (with the exception of glycerol) shows a strong correlation with their ability to stabilize membrane structure and function at low water contents.

References (28)

M.C. Phillips et al.
Biochim. Biophys. Acta
(1970)
O. Albrecht et al.
J. Coll. Int. Sci.
(1981)
D.A. Cadenhead et al.
Biochim. Biophys. Acta
(1969)
D.A. Cadenhead et al.
Biochim. Biophys. Acta
(1972)
B. Maggio et al.
FEBS Lett.
(1978)
F. Lakhdar-Ghazal et al.
Biochim. Biophys. Acta
(1981)
P.S. Low et al.
Arch. Biochem. Biophys.
(1982)
L.M. Crowe et al.
Arch. Biochem. Biophys.
(1982)
J.H. Crowe et al.
Arch. Biochem. Biophys.
(1983)
J.H. Crowe et al.
Cryobiology
(1982)

J.H. Crowe et al.

Cryobiology

(1983)

L.M. Crowe et al.

Biochim. Biophys. Acta

(1984)

D. Chapman et al.

Chem. Phys. Lipids

(1967)

P.R. Cullis et al.

Biochim. Biophys. Acta

(1979)

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In vitro Fourier transform infrared spectroscopic study of the effect of glycerol on the uptake of beclomethasone dipropionate in living respiratory cells
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Citation Excerpt :
Interestingly, the glycerol-equilibrated Calu-3 cells showed a greater rate and extent of BDP uptake in the first few hours until the 4th h, compared to glycerol-free conditions. This result might be dictated by the possibility of a time dependent replacement of headgroup solvating water with glycerol in membranal structure; although the cell membranes are stiffened by glycerol at the end of measurements, data from model systems also show a stepwise process of glycerol-PC interaction beginning with an expansion of phospholipid monolayers induced by glycerol (Crowe et al., 1984; Terakosolphan et al., 2018). This assumption is consistent with one of the kinetic parameters obtained from the Gompertz fits in Table 1 where the midpoint of BDP uptake was more quickly reached in the glycerol-equilibrated exposures which might be caused by a shorter average lag with the glycerol (ti values occur earlier), implying that the initial uptake of BDP is faster.
The quantification of drug in living cells is of increasing interest in pharmaceutical research because of its importance in understanding drug efficacy and toxicity. Label-free in situ measurement methods are advantageous for their ability to obtain chemical and time profiles without the need of labelling or extraction steps. We have previously shown that Fourier transform infrared (FTIR) spectroscopy has the potential to quantify drug in situ within living cells at micromolar level when a simple solution of drug was added to the medium. The purpose of this study was to demonstrate that the approach can evaluate more complex systems such as the effect of membrane modification by a formulation on drug uptakes. The inhaled corticosteroid, beclomethasone dipropionate (BDP), in Calu-3 respiratory epithelial cells in the absence and presence of glycerol, an excipient in some inhaled medicines was used as the model system. The FTIR method was first validated for limit of detection (LOD) and quantification (LOQ) according to published guidelines and the LOQ was found to be ∼ 20 μM, good enough to quantify BDP in the living cell. The uptake of BDP by living Calu-3 cells was found to be reduced in the presence of glycerol as expected due to the stiffening of the cell membrane by the presence of glycerol in the formulation. This study demonstrates the valuable analytical capability of live-cell FTIR to study the effect of formulation on drug transport in lungs and to evaluate drug availability to intracellular targets. We conclude that FTIR has potential to contribute widely at the frontier of live-cell studies.
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The primary drying is the longest step of the freeze-drying process and becomes one of the focuses for lyophilization cycle development inevitably, which is often approaching through a “trial and error” course and requires a labor-intensive and time-consuming endeavor. Nevertheless, drawing support from characterization techniques to understand the physic-chemical properties changing of the sample during lyophilization and their correlation with process conditions comprehensively, the freeze-drying development and optimization will get more from less.
To get the optimal lyophilization cycle in the least time, the instrumental methods assisting primary drying design are summarized. The techniques used for estimating the collapse temperature of products are reviewed at first, aiming to provide a reference on the primary drying temperature setting to guarantee product quality. The instrumental methods for primary drying end prediction are also discussed to get optimal freeze-drying protocol with higher productivity. This review highlights the practicality of the above techniques through expounding basic principles, typical measurement conditions, merits and drawbacks, interpretation of results and practical applications, etc. At last, the techniques used for residual moisture detection of lyophilized products and size determination after liposome rehydration are briefly introduced.
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In this study, the effect of polyols, erythritol, xylitol, mannitol, on a model membrane systems composed of DMPC was investigated using differential scanning calorimetry and Fourier transform infrared spectroscopy. Generally, it is considered that polyols possess strong hydrophilic properties, and either does not interact with the hydrophobic environment at all, or these interactions are very weak. To better understand the mutual interactions between polyols and the lipid system, the Langmuir technique was used to examine the molecular organization of monolayers and to calculate their thickness in the presence of polyols at the subphase. The detailed description of the interactions between polyols and DMPC molecules was complemented by the analysis of the morphology of monolayers with the application of Brewster angle microscopy. From ATR FTIR, the significant spectral shift is observed only for the PO₂⁻ stretching band, which correlates strongly with the polyol chain-length. The longer the polyol chain, the weaker the observed interactions with lipid molecules. The most important findings, obtained from thickness measurements, reveal that short-chain polyols may prevent the formation of bilayers by the DMPC molecules under high surface pressure. The changes in the organization of DMPC monolayers on the surface, as visualized by Brewster angle microscopy, showed that the domains observed for phospholipid film spread on pure water differ substantially from those containing polyols in the subphase.
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Citation Excerpt :
Indeed, when glycerosomes were prepared with DPPC or P90H, the encapsulation of diclofenac sodium salt caused a size reduction of all vesicles (liposomes and glycerosomes) compared to the corresponding empty ones, indicating that the drug intercalated in the bilayer changing the packing of the vesicular membrane and the curvature radius of the vesicles (El Maghraby et al., 2000; Manca et al., 2016, 2013b). Using DMPC, the effect of diclofenac was evident for liposomes (Table 1) and negligible for glycerosomes, probably because when DMPC is spread on water/glycerol solution an expansion of monolayer films is detected, as previously found (Crowe et al., 1984). Diclofenac loaded glycerosomes were small in size (∼106 nm, p > 0.05) and homogeneously dispersed (PI ≤ 0.237) regardless of the amount of glycerol used, while diclofenac loaded liposomes were less homogeneously dispersed (PI ≥ 0.311) but smaller (∼72 nm).
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Water appears as a common intermediary in the mechanisms of interaction of proteins and polypeptides with membranes of different lipid composition. In this review, how water modulates the interaction of peptides and proteins with lipid membranes is discussed by correlating the thermodynamic response and the structural changes of water at the membrane interphases.
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Interactions of phospholipid monolayers with carbohydrates

Abstract

Biochim. Biophys. Acta

J. Coll. Int. Sci.

Biochim. Biophys. Acta

Biochim. Biophys. Acta

FEBS Lett.

Biochim. Biophys. Acta

Arch. Biochem. Biophys.

Arch. Biochem. Biophys.

Arch. Biochem. Biophys.

Cryobiology

Cryobiology

Biochim. Biophys. Acta

Chem. Phys. Lipids

Biochim. Biophys. Acta