Peptide transport in Bacillus subtilis - structure and specificity in the extracellular solute binding proteins OppA and DppE.

Peptide transporters play important nutritional and cell signalling roles in Bacillus subtilis, which are pronounced during stationary phase adaptations and development. Three high-affinity ATP-binding cassette (ABC) family transporters are involved in peptide uptake - the oligopeptide permease (Opp), another peptide permease (App) and a less well-characterized dipeptide permease (Dpp). Here we report crystal structures of the extracellular substrate binding proteins, OppA and DppE, which serve the Opp and Dpp systems, respectively. The structure of OppA was determined in complex with endogenous peptides, modelled as Ser-Asn-Ser-Ser, and with the sporulation-promoting peptide Ser-Arg-Asn-Val-Thr, which bind with K d values of 0.4 and 2 µM, respectively, as measured by isothermal titration calorimetry. Differential scanning fluorescence experiments with a wider panel of ligands showed that OppA has highest affinity for tetra- and penta-peptides. The structure of DppE revealed the unexpected presence of a murein tripeptide (MTP) ligand, l-Ala-d-Glu-meso-DAP, in the peptide binding groove. The mode of MTP binding in DppE is different to that observed in the murein peptide binding protein, MppA, from Escherichia coli, suggesting independent evolution of these proteins from an OppA-like precursor. The presence of MTP in DppE points to a role for Dpp in the uptake and recycling of cell wall peptides, a conclusion that is supported by analysis of the genomic context of dpp, which revealed adjacent genes encoding enzymes involved in muropeptide catabolism in a gene organization that is widely conserved in Firmicutes.

Concentration dependent debundling and single tube dispersions of pristine multiwalled carbon nanotubes functionalized with double tail phospholipids.

Multiwalled carbon nanotubes (MWNTs) exist as aggregates of highly entangled tubes due to large aspect ratios and strong Van der Waals interactions among them in their native states. In order to render them suitable for any application, MWNTs need to be separated and dispersed uniformly in a solvent preferably as individual tubes. In the present work, it is demonstrated that a double tail lipid such as 1, 2-dipalmitoyl-sn-glycero-3-phosphoethanolamine (DPPE) is capable of dispersing MWNTs in ethanol. Ultra-stable suspensions were obtained by optimizing two key parameters: DPPE to MWNT weight ratio (ε) and MWNT concentration (c). Stability of the suspensions increased with the increasingεvalue up to an optimum point (ε= 1.8) and then decreased drastically beyond that. CNT dispersions withε= 1.8 were extremely stable (with a Zeta potential of 108.26 ± 2.15 mV) and could be retained in suspended form up to 3 months. Effect of MWNT concentration on disaggregation was very significant and stable suspensions could be formed for MWNT concentrations only below 0.14 mg ml-1. Above this concentration, no stable dispersions could be obtained even withε= 1.8. Compression isotherms of Langmuir monolayers of the DPPE functionalized MWNTs spread at the air water interface were highly repeatable, suggesting that the MWNTs in dispersion were present as separate tubes coated with phospholipids. SEM micrographs of the Langmuir-Blodgett (LB) films, deposited at high surface pressures on silicon wafers, show that MWNTs remain as single nanotubes with no signs of reaggregation. TEM micrographs of MWNT suspensions indicated random adsorption of DPPE on MWNTs. Our work makes it possible to explore potential applications of LB films of MWNTs (stabilized by DPPE) in the development of conducting thin films for sensor applications or as supports to immobilize catalysts for heterogenous reactions.

Interaction of dicentrinone, an antitrypanosomal aporphine alkaloid isolated from Ocotea puberula (Lauraceae), in cell membrane models at the air-water interface.

In the present work, the oxoaporphine alkaloid dicentrinone was isolated, for the first time, from leaves of Ocotea puberula (Lauraceae). This alkaloid exhibited antiparasitic activity against trypomastigote forms of Trypanosoma cruzi (IC50 of 16.4 ± 1.7 µM), similar to the positive control benznidazole (IC50 of 18.7 ± 4.1 µM), reduced mammalian cytotoxicity (CC50 > 200 µM), and a selectivity index (SI) higher than 12. These results were correlated with the effects observed using cellular membrane models, represented by 1,2-dipalmitoyl-sn-glycero-3-phosphoethanolamine (DPPE), in Langmuir monolayers. Dicentrinone was incorporated in the films, submitted to lateral compression, and characterized by tensiometry. As observed in compression-decompression and time-stability curves, dicentrinone expanded the lipid monolayers, decreased the compressional modulus of the film, and reduced the stability of the monolayer. Brewster Angle Microscopy and interfacial Infrared Spectroscopy showed that dicentrinone causes the monolayers to be segregated in phases, and to increase the number of gauche/trans conformers ratio for the lipid acyl methylene groups, indicating configurational disorder. As a result, dicentrinone caused a disturbance in the cell membrane models, altering the physicochemical properties of the lipid surface such as thermodynamic, rheological, morphological, and structural aspects. These results can be useful to understand the interactions between dicentrinone and lipid biological surfaces at the molecular level.

Ligand- and drug-binding studies of membrane proteins revealed through circular dichroism spectroscopy.

A great number of membrane proteins have proven difficult to crystallise for use in X-ray crystallographic structural determination or too complex for NMR structural studies. Circular dichroism (CD) is a fast and relatively easy spectroscopic technique to study protein conformational behaviour. In this review examples of the applications of CD and synchrotron radiation CD (SRCD) to membrane protein ligand binding interaction studies are discussed. The availability of SRCD has been an important advancement in recent progress, most particularly because it can be used to extend the spectral region in the far-UV region (important for increasing the accuracy of secondary structure estimations) and for working with membrane proteins available in only small quantities for which SRCD has facilitated molecular recognition studies. Such studies have been accomplished by probing in the near-UV region the local tertiary structure of aromatic amino acid residues upon addition of chiral or non-chiral ligands using long pathlength cells of small volume capacity. In particular, this review describes the most recent use of the technique in the following areas: to obtain quantitative data on ligand binding (exemplified by the FsrC membrane sensor kinase receptor); to distinguish between functionally similar drugs that exhibit different mechanisms of action towards membrane proteins (exemplified by secretory phospholipase A2); and to identify suitable detergent conditions to observe membrane protein-ligand interactions using stabilised proteins (exemplified by the antiseptic transporter SugE). Finally, the importance of characterising in solution the conformational behaviour and ligand binding properties of proteins in both far- and near-UV regions is discussed. This article is part of a Special Issue entitled: Structural and biophysical characterisation of membrane protein-ligand binding.

Cytotoxic bile acids, but not cytoprotective species, inhibit the ordering effect of cholesterol in model membranes at physiologically active concentrations.

Submillimolar concentrations of cytotoxic bile acids (BAs) induce cell death via apoptosis. On the other hand, several cytoprotective BAs were shown to prevent apoptosis in the same concentration range. Still, the mechanisms by which BAs trigger these opposite signaling effects remain unclear. This study was aimed to determine if cytotoxic and cytoprotective BAs, at physiologically active concentrations, are able to modulate the biophysical properties of lipid membranes, potentially translating into changes in the apoptotic threshold of cells. Binding of BAs to membranes was assessed through the variation of fluorescence parameters of suitable derivatized BAs. These derivatives partitioned with higher affinity to liquid disordered than to the cholesterol-enriched liquid ordered domains. Unlabeled BAs were also shown to have a superficial location upon interaction with the lipid membrane. Additionally, the interaction of cytotoxic BAs with membranes resulted in membrane expansion, as concluded from FRET data. Moreover, it was shown that cytotoxic BAs were able to significantly disrupt the ordering of the membrane by cholesterol at physiologically active concentrations of the BA, an effect not associated with cholesterol removal. On the other hand, cytoprotective bile acids had no effect on membrane properties. It was concluded that, given the observed effects on membrane rigidity, the apoptotic activity of cytotoxic BAs could be potentially associated with changes in plasma membrane organization (e.g. modulation of lipid domains) or with an increase in mitochondrial membrane affinity for apoptotic proteins.

A combined fluorescence spectroscopy, confocal and 2-photon microscopy approach to re-evaluate the properties of sphingolipid domains.

The aim of this study is to provide further insight about the interplay between important signaling lipids and to characterize the properties of the lipid domains formed by those lipids in membranes containing distinct composition. To this end, we have used a combination of fluorescence spectroscopy, confocal and two-photon microscopy and a stepwise approach to re-evaluate the biophysical properties of sphingolipid domains, particularly lipid rafts and ceramide (Cer)-platforms. By using this strategy we were able to show that, in binary mixtures, sphingolipids (Cer and sphingomyelin, SM) form more tightly packed gel domains than those formed by phospholipids with similar acyl chain length. In more complex lipid mixtures, the interaction between the different lipids is intricate and is strongly dictated by the Cer-to-Chol ratio. The results show that in quaternary phospholipid/SM/Chol/Cer mixtures, Cer forms gel domains that become less packed as Chol is increased. Moreover, the extent of gel phase formation is strongly reduced in these mixtures, even though Cer molar fraction is increased. These results suggest that in biological membranes, lipid domains such as rafts and ceramide platforms, might display distinctive biophysical properties depending on the local lipid composition at the site of the membrane where they are formed, further highlighting the potential role of membrane biophysical properties as an underlying mechanism for mediating specific biological processes.

Effect of a cholesterol-rich lipid environment on the enzymatic activity of reconstituted hyaluronan synthase.

Hyaluronan synthase (HAS) is a unique membrane-associated glycosyltransferase and its activity is lipid dependent. The dependence however is not well understood, especially in vertebrate systems. Here we investigated the functional association of hyaluronan synthesis in a cholesterol-rich membrane-environment. The culture of human dermal fibroblasts in lipoprotein-depleted medium attenuated the synthesis of hyaluronan. The sequestration of cellular cholesterol by methyl-ß-cyclodextrin also decreased the hyaluronan production of fibroblasts, as well as the HAS activity. To directly evaluate the effects of cholesterol on HAS activity, a recombinant human HAS2 protein with a histidine-tag was expressed as a membrane protein by using a baculovirus system, then successfully solubilized, and isolated by affinity chromatography. When the recombinant HAS2 proteins were reconstituted into liposomes composed of both saturated phosphatidylcholine and cholesterol, this provided a higher enzyme activity as compared with the liposomes formed by phosphatidylcholine alone. Cholesterol regulates HAS2 activity in a biphasic manner, depending on the molar ratio of phosphatidylcholine to cholesterol. Furthermore, the activation profiles of different lipid compositions were determined in the presence or absence of cholesterol. Cholesterol had the opposite effect on the HAS2 activity in liposomes composed of phosphatidylethanolamine or phosphatidylserine. Taken together, the present data suggests a clear functional association between HAS activity and cholesterol-dependent alterations in the physical and chemical properties of cell membranes.

Enhanced Performance and High Resistance to Efficiency Degradation of Blue Quantum-Dot Light-Emitting Diodes Using the Lewis Base Blended Hole-Transporting Layers.

The distinctive characteristics of blue quantum dots (QDs) such as their deep valence band and large bandgap give rise to an elevated hole injection barrier between the hole transport layers (HTLs) and the QD active layer. This results in an imbalance of carrier transport and injection across the device, leading to a degrading performance in QD light-emitting diodes (QLEDs). In this paper, high-efficiency and low-efficiency degradation blue CdSe/CdS/ZnS QLEDs were fabricated by using the Lewis base, 1,2-bis(diphenylphosphino)ethane (DPPE), blended with poly(9-vinylcarbazole) (PVK) (DPPE:PVK) as HTLs. The device performance of blue QLEDs can be finely adjusted by manipulating the blending ratio between DPPE and PVK. When 4 wt % DPPE was blended with PVK (4 wt % DPPE:PVK) as the HTL, the device achieved its optimal performance. Compared to the device with neat PVK as the HTL, the turn-on voltage of blue QLEDs with the 4 wt % DPPE:PVK HTL is reduced from 3.21 to 2.9 V. The maximum current efficiency (CE) and external quantum efficiency (EQE) of blue QLEDs increase from 2.92 cd A-1 and 5.89% in neat PVK to 5.75 cd A-1 and 11.75% for the 4 wt % DPPE:PVK HTL. Furthermore, the QLEDs incorporating DPPE:PVK HTLs exhibited exceptional resistance to efficiency degradation (EQE = 8.83%@L = 12,000 cd m-2 for 4 wt % DPPE:PVK as the HTL and EQE = 2.80%@L = 12,000 cd m-2 for neat PVK as the HTL). A more in-depth analysis reveals that enhanced device performance results from the chelating and bridging effect of the bidentate ligand Lewis base DPPE. These effects strengthen the binding of free metal ions in the blue QDs, reduce the charge barriers, enhance the contact between the HTLs and the QD active layer, and ultimately improve hole injection.

Barbellatanic acid, a new antitrypanosomal pseudo-disesquiterpenoid isolated from Nectandra barbellata, displayed interaction with protozoan cell membrane.

As part of our ongoing studies involving the discovery of new natural prototypes with antiprotozoal activity against Trypanosoma cruzi from Brazilian plant species, the chromatographic fractionation of hexane extract from leaves of Nectandra barbellata afforded one new pseudo-disesquiterpenoid, barbellatanic acid. The structure of this compound was elucidated by NMR and HR-ESIMS data analysis. Barbellatanic acid displayed a trypanocidal effect with IC50 of 13.2 µM to trypomastigotes and no toxicity against NCTC cells (CC50 > 200 µM), resulting in an SI value higher than 15.1. The investigation of the lethal mechanism of barbellatanic acid in trypomastigotes, using both fluorescence microscopy and spectrofluorimetric analysis, revealed a time-dependent permeation of the plasma membrane. Based on these results, this compound was incorporated in cellular membrane models built with lipid Langmuir monolayers. The interaction of barbellatanic acid with the models was inferred by tensiometric, rheological, spectroscopical, and morphological techniques, which showed that this compound altered the thermodynamic, viscoelastic, structural, and morphological properties of the film. Taking together, these results could be employed when this prodrug interacts with lipidic interfaces, such as protozoa membranes or liposomes for drug delivery systems.

Influence of DPPE surface undulations on melting temperature determination: UV/Vis spectroscopic and MD study.

One of the most distinguished quantities that describes lipid main phase transition, i.e. the transition from the gel (Lß(')) to the fluid (Lα) phase, is its melting temperature (Tm). Because melting is accompanied by a large change in enthalpy the, Lß(') â†’ Lα transition can be monitored by various calorimetric, structural and spectroscopic techniques and Tm should be the same regardless of the metric monitored or the technique employed. However, in the case of DPPE multilamellar aggregates there is a small but systematic deviation of Tm values determined by DSC and FTIR spectroscopy. The aim of this paper is to explain this discrepancy by combined UV/Vis spectroscopic and MD computational approach. Multivariate analysis performed on temperature-dependent UV/Vis spectra of DPPE suspensions demonstrated that at 55 ± 1 °C certain phenomenon causes a small but detectable change in suspension turbidity, whereas a dominant change in the latter is registered at 63.2 ± 0.4 °C that coincides with Tm value determined from DSC curve. If this effect should be ignored, the overall data give Tm value the same as FTIR spectra data (61.0 ± 0.4 °C). As the classical MD simulations suggest that about 10° below Tm certain undulations appear at the surface of DPPE bilayers, we concluded that certain discontinuities in curvature fluctuations arise at reported temperature which are to some extent coupled with lipid melting. Ultimately, such events and the associated changes in curvature affect Tm value measured by different techniques.

Interaction of isolinderanolide E obtained from Nectandra oppositifolia with biomembrane models.

A long-tail lactone, named isolinderanolide E, was obtained from Nectandra oppositifolia and incorporated in Langmuir monolayers of dipalmitoyl-phosphoethanolamine (DPPE) as a model of microbial membranes. The compound was dissolved in chloroform and mixed with DPPE to provide mixed solutions spread on the air-water interface. After solvent evaporation, mixed monolayers were formed, and surface pressure-area isotherms, dilatational rheology, Brewster angle microscopy (BAM), and infrared spectroscopy were employed to characterize the prodrug-membrane interactions. Isolinderanolide E expanded DPPE monolayers, denoting repulsive interactions. At 30 mN/m, the monolayer presented higher viscoelastic and in-plane elasticity parameters and an increased ratio of all-trans/gauche conformers of the alkyl chains, confirming molecular order. Morphology of the monolayer was analyzed by BAM, which revealed a more homogeneous distribution of Isolinderanolide E along the DPPE monolayer than the prodrug directly spread at the interface, which tends to aggregate. A molecular model proposing the molecular orientation of the amphiphilic drug is presented and explained by the distortion of the alkyl chains as well as by viscoelastic changes. In conclusion, the prodrug changes the thermodynamic, rheological, morphological, and structural properties of the DPPE monolayer, which may be essential to understand, at the molecular level, the action of bioactives in selected membrane models.

A bactericide peptide changing the static and dilatational surface elasticity properties of zwitterionic lipids at the air-water interface: Relationship with the thermodynamic, structural and morphological properties.

In this paper, we studied how different hydrophilicity degrees of the polar groups of the lipids dipalmitoylphosphatidylcholine (DPPC) and dipalmitoyl phosphatidylethanolamine (DPPE) influence the interaction of the antibiotic peptide vancomycin (VC), affecting the physicochemical properties of the monolayers, including thermodynamic, rheological, structural and morphological ones. Lipid Langmuir monolayers were prepared at air-water interfaces with VC aqueous solution as subphase and characterized with tensiometry, Brewster angle microscopy, infrared spectroscopy, dilatational, and interfacial shear rheology. The presence of PC or PE groups as polar head groups of the phospholipid monolayers modulated the interaction of VC adsorbing from the aqueous subphase since for DPPC, vancomycin condenses the monolayer, making it less stable, fluid, and more disordered. In contrast, for DPPE, vancomycin expands the monolayer, making it more stable, keeping the compressibility, and leading to the formation of interfacial aggregates, which are not observed for DPPC. We concluded thatelectrostatic interactions induced the insertion of the peptide into the polar heads of the monolayers (DPPE), while hydrophobic interactions, in addition to ion-dipole interactions, induced the adsorption of the peptide onto the polar head of the monolayers (DPPC).

[1,2-Bis(di-phenyl-phosphan-yl)ethane-κ2 P,P]chlorido-(isonicotinamide-κN)palladium(II) nitrate aceto-nitrile monosolvate.

The PdII central atom in the title complex, [PdCl(C26H24P2)(C6H6N2O)]NO3·CH3CN or [PdCl(dppe)(INAM)]NO3·CH3CN, where dppe is 1,2-bis-(di-phenyl-phosphan-yl)ethane and INAM is isonicotinamide, exists in a slightly distorted square-planar environment defined by the two P atoms of the dppe ligand, a chloride ligand and the N atom of the isonicotinamide pyridyl ring. The crystal packing in the structure is held together by hydrogen bonds between the amide of the INAM ligand and the nitrate ions that complete the outer coordination sphere. A mol-ecule of aceto-nitrile is also found in the asymmetric unit of the title complex.

Evaluation of antioxidant, anti-inflammatory and anticancer activities of diosgenin enriched Paris polyphylla rhizome extract of Indian Himalayan landraces.

ETHNOPHARMACOLOGICAL RELEVANCE: Traditional medicinal plants have gained attention as a potential therapeutic agent to combat cancer and inflammation. Diosgenin rich fresh extracts of Paris polyphylla rhizome from Indian Himalaya is traditionally used as wound healing, anti-bleeding, anti-inflammatory and anti-cancer agent by the folk healers. AIM OF THE STUDY: Present study was aimed to prepare two types of extracts from Paris polyphylla rhizome of Indian Himalayan landraces - 1. ethanolic extract of Paris polyphylla rhizome (EEPPR) and 2. Diosgenin enriched Paris polyphylla rhizome extract (DPPE), quantification of diosgenin content, and to evaluate their in vitro anti-oxidant, in vivo anti-inflammatory and in vitro cytotoxicity and anti-cancer activities of the DPPE. MATERIALS AND METHODS: Diosgenin content of EEPPR was quantified through GC-MS while diosgenin content of DPPE was quantified through HPTLC, and the diosgenin yield from EEPPR and DPPE were compared. In vitro antioxidant activities of DPPE were performed using DPPH, NOD, RP and SOD assay while in vivo anti-inflammatory activity of DPPE were evaluated in dextran induced hind paw edema in rats. In vitro cytotoxicity and anti-cancer activities of DPPE were evaluated in human breast cancer cell lines (MCF-7, MDA-MB-231), cervical cancer cell lines (HeLa) and Hep-2 cell lines. RESULTS: EEPPR obtained through cold extraction method using 70% ethanol showed maximum diosgenin content of 17.90% quantified through GC-MS while similar compounds pennogenin (3.29%), 7ß-Dehydrodiosgenin (1.90%), 7-Ketodiosgenin acetate (1.14%), and 7 ß-hydroxydiosgenin (0.55%) were detected in low concentration, and thus confirmed diosgenin as major and lead phytochemical. However, DPPE obtained through both cold and repeated hot extraction with the same solvent (70% ethanol) showed diosgenin content of 60.29% which is significantly higher (p < 0.001) than the diosgenin content in EEPPR. DPPE demonstrated significant in vitro antioxidant activities by dose-dependently quenched (p < 0.001) SOD free radicals by 76.66%, followed by DPPH (71.43%), NOD (67.35%), and RP (63.74%) at a max concentration of 2 µg/µl of ascorbic acid and test drugs with remarkable IC50 values (p < 0.01). Further, DPPE also showed potent anti-inflammatory activities by dose-dependently suppressed dextran induced paw edema in rats (p < 0.01) from 2 h to 4 h. DPPE suppressed the proliferation of MCF-7, MDA-MB-231, Hep-2 and HeLa cell lines. Maximum activity was observed in MCF-7 cells. The DPPE also induced apoptosis in MCF-7 cell lines as measured by AO/PI and DAPI staining, as well as DNA laddering, cell cycle analysis and phosphatidylserine externalization assay. The growth-inhibitory effect of DPPE on MCF-7 breast cancer cells was further confirmed from the colony-formation assay. DPPE upregulated expression of Bax and downregulated Bcl-2 and survivin mRNA transcripts. CONCLUSION: DPPE obtained through both cold and repeated hot extraction using ethanol showed significantly higher content of diosgenin than the diosgenin content detected in EEPPR. However, diosgenin yield of both the extracts (EEPPR & DPPE) clearly confirmed diosgenin as major and lead phytochemical of Paris polyphylla rhizome of Indian Himalayan landraces. Further, DPPE also demonstrated potent in vitro anti-oxidative and in vivo anti-inflammatory activities and showed in vitro cytotoxicity and significant anti-cancer (apoptosis) effects in MCF-7 breast cancer cells.

Interactions of l-arginine with Langmuir monolayers of common phospholipids at the air-water interface.

The interactions of l-arginine (l-arg) with Langmuir monolayers of three most common phospholipids, which are sodium salt of dipalmitoylphosphatidylglycerol (DPPG), dipalmitoylphosphatidylcholine (DPPC) and dipalmitoylphosphatidylethanolamine (DPPE), have been investigated at the air-water interface. The surface pressure-area (π-A) isotherms of these monolayers have been measured with a film balance and monolayer morphology has been observed by a Brewster angle microscopy (BAM). The DPPG monolayers on pure water do not show any phase transition but show irregular shaped condensed phases formed just after evaporation of the solvent at 20 °C. However, this monolayer on l-arg solution subphase indicates a first-order phase transition from liquid expanded to liquid condensed (LE-LC) phases and forms LC domains at the same temperature. With an increase in the l-arg concentration in the subphase up to 5.0 × 10-4 M, the π-A shows an overall increasingly greater expansion in the molecular area. All of the π-A isotherms recorded on ≥5.0 × 10-4 M l-arg solution subphases almost coincide with each other. These changes in the phase behavior have been explained by the fact that l-arg having guanidinium cationic group undergoes strong hydrogen bonding interaction with the anionic phosphatidylglycerol (PG-) head group. The bonding between two molecules is further strengthened by electrostatic attraction between cationic l-arg and anionic PG- ions. The BAM observation of the monolayer morphology supports this explanation. On the other hand, a very negligible interaction has been observed between l-arg and DPPC or DPPE monolayers. The π-A isotherms in the presence of l-arg for both the amphiphiles show a very little expansion only in the LE phase region, but coincide in the so called solid phase region. The monolayer morphology of both the monolayers also supports these results. This little effect of expansion in the LE region may be explained by the ion-pair formation between cationic l-arg and anionic head groups in the monolayers at lower pressures. However, due to compression at high pressure, the l-arg molecules are squeezed out from the amphiphile head groups.

Application of MCR-ALS with EFA on FT-IR spectra of lipid bilayers in the assessment of phase transition temperatures: Potential for discernment of coupled events.

Temperature-dependent transmission FT-IR spectroscopy and DSC measurements were conducted on lipid multibilayers constituted from 1,2-dipalmitoyl-sn-glycero-3-phosphocholine. Lipid multibilayers made from 1,2-dipalmitoyl-sn-glycero-3-phosphoethanolamine, which do not form a ripple phase, were examined as a reference. Spectra were analyzed using multivariate curve resolution technique with alternating least squares and evolving factor analysis (MCR-ALS with EFA) and lipid phase transition temperatures were determined. Polar parts of lipid molecules exert greater response on a ripple phase formation than non-polar ones. However, vibrational signatures of hydrocarbon chains with intramolecular origins display certain qualitative differences that pave the way for future work oriented on uncoupling the events that drive ripple phase formation.

Interfacial vibrational spectroscopy and Brewster angle microscopy distinguishing the interaction of terpineol in cell membrane models at the air-water interface.

In this paper, γ-terpineol, a known monoterpene with biological activity, including in lipidic interfaces, was incorporated in Langmuir monolayers of selected phospholipids as a model for cellular membranes. Surface pressure-area isotherms showed that selected amounts of γ-terpineol expand DPPC and DPPE monolayers and decreased the monolayer elasticity, confirming the lipid/compound interaction. Characterization with vibrational spectroscopy and Brewster angle microscopy pointed that γ-terpineol adsorbs on the polar heads of the phospholipids, affecting the gauche conformations of the aliphatic chains, and different patterns were observed for DPPC and DPPE monolayers, indicating a characteristic molecular accommodation of γ-terpineol along the polar head of the phospholipids. Therefore, distinctive interactions with DPPC and DPPE could be observed regarding the incorporation of γ-terpineol with each lipid, leading to particular molecular arrangements at the air-water interface and pointing the modulation of the interaction according to the chemical composition of the monolayer.

Lipids mediating the interaction of metronidazole with cell membrane models at the air-water interface.

In this paper, metronidazole, a known compound with microbicide effect, was incorporated in Langmuir monolayers of selected phospholipids in order to investigate the interactions of this compound with cell membrane models by using tensiometric, spectroscopic and morphological techniques. Surface pressure-area isotherms showed that selected amounts of metronidazole condense DPPC monolayers, but expand DPPE monolayers. Vibrational spectroscopy pointed that metronidazole adsorbs on the polar heads of the phospholipids, affecting the gauche conformations of the aliphatic chains, and different patterns were observed for DPPC and DPPE monolayers containing metronidazole in terms of Brewster angle microscopy images. As a result, distinctive interactions with DPPC and DPPE could be pointed regarding the incorporation of metronidazole with each lipid, leading to particular molecular arrangements at the air-water interface.

Crystal structure at 100†K of bis-[1,2-bis-(di-phenyl-phosphan-yl)ethane]-nickel(II) bis-(tri-fluoro-methane-sulfonate): a possible negative thermal expansion mol-ecular material.

In the title salt, [Ni(C26H24P2)2](CF3SO3)2 or [Ni(dppe)2]2+·(OTf-)2 [dppe = 1,2-bis-(di-phenyl-phosphan-yl)ethane and OTf- = tri-fluoro-methane-sulfonate], the Ni atom (site symmetry ) has a square-planar geometry with the bidentate ligands chelating the metal. As a result of the steric hindrance of the phenyl rings, the counter-ions are blocked from the metal coordination sphere. The dynamic disorder of the anion existing at 296 K is reduced at 100 K and based on these two temperatures, negative thermal expansion behaviour is observed.

Crystal structure of cis-[1,2-bis-(di-phenyl-phosphan-yl)ethene-κ2P,P']di-chlorido-platinum(II) chloro-form disolvate: a new polymorph.

The title compound, [PtCl2(C26H22P2)]·2CHCl3 (I), is the third monoclinic polymorph of this platinum(II) complex involving the bidentate ligand cis-1,2-bis-(di-phenyl-phosphan-yl)ethyl-ene (cis-dppe) [for the others, see: Oberhauser et al. (1998a ▸). Inorg. Chim. Acta, 274, 143-154, and Oberhauser et al. (1995 ▸). Inorg. Chim. Acta, 238, 35-43]. The structure of compound (I) was solved in the space group P21/c, with one complex mol-ecule in the asymmetric unit along with two solvate chloro-form mol-ecules. The PtII atom is ligated by two P and two Cl atoms in the equatorial plane and has a perfect square-planar coordination sphere. In the crystal, the complex mol-ecule is linked to the chloro-form solvate mol-ecules by C-H⋯Cl hydrogen bonds and face-on C-Cl⋯π inter-actions. There are also weak offset π-π inter-actions present [inter-centroid distances are 3.770 (6) and 4.096 (6) Å], linking the mol-ecules to form supra-molecular sheets that lie in the bc plane.