Trans-gauche Conformation Research Articles

Conformational disorder in the crystal structure of methyl 2-acetamido-2-deoxy-β-D-glucopyranosyl-(1→4)-2-acetamido-2-deoxy-β-D-glucopyranoside (methyl β-chitobioside) methanol monosolvate.

Methyl 2-acetamido-2-deoxy-β-D-glucopyranosyl-(1→4)-2-acetamido-2-deoxy-β-D-glucopyranoside (methyl β-chitobioside), (IV), crystallizes from aqueous methanol at room temperature to give a structure (C17H30N2O22·CH3OH) containing conformational disorder in the exocyclic hydroxymethyl group of one of its βGlcNAc residues. As observed in other X-ray structures of disaccharides containing β-(1→4) O-glycosidic linkages, inter-residue hydrogen bonding between O3H of the βGlcNAc bearing the OCH3 aglycone and O5 of the adjacent βGlcNAc is observed based on the 2.79 Å internuclear distance between the O atoms. The structure of (IV) was compared to that determined previously for 2-acetamido-2-deoxy-β-D-glucopyranosyl-(1→4)-2-acetamido-2-deoxy-β-D-glucopyranose (β-chitobiose), (III). The O-glycosidic linkage torsion angles, phi (φ) and psi (ψ), in (III) and (IV) differ by 6-8°. The N-acetyl side chain conformation in (III) and (IV) shows some context dependence, with the C1-C2-N-Ccar torsion angle 10-15° smaller for the βGlcNAc residue involved in the internal O-glycosidic linkage. In (IV), conformational disorder is observed in the exocyclic hydroxymethyl (-CH2OH) group in the βGlcNAc residue bearing the OCH3 aglycone, and a fitting of the electron density indicates an approximate 50:50 distribution of the gauche-gauche (gg) and gauche-trans (gt) conformers in the lattice. Similar behavior is not observed in (III), presumably due to the different packing structure in the vicinity of the -CH2OH substituent that affects its ability to hydrogen bond to proximal donors/acceptors. Unlike (IV), a re-examination of the previously reported electron density of (III) revealed conformational disorder in the N-acetyl side chain attached to the reducing-end βGlcNAc residue caused by rotation about the C2-N bond.

The Far-Infrared Spectrum of Methoxymethanol (CH3-O-CH2OH): A Theoretical Study.

Methoxymethanol (CH3OCH2OH), an oxygenated volatile organic compound of low stability detected in the interstellar medium, represents an example of nonrigid organic molecules showing various interacting and inseparable large-amplitude motions. The species discloses a relevant coupling among torsional modes, strong enough to prevent complete assignments using effective Hamiltonians of reduced dimensionality. Theoretical models for rotational spectroscopy can improve if they treat three vibrational coordinates together. In this paper, the nonrigid properties and the far-infrared region are analyzed using highly correlated ab initio methods and a three-dimensional vibrational model. The molecule displays two gauche-gauche (CGcg and CGcg') and one trans-gauche (Tcg) conformers, whose relative energies are very small (CGcg/CGcg'/Tcg = 0.0:641.5:792.7 cm-1). The minima are separated by relatively low barriers (1200-1500 cm-1), and the corresponding methyl torsional barriers V 3 are estimated to be 595.7, 829.0, and 683.7 cm-1, respectively. The ground vibrational state rotational constants of the most stable geometry have been computed to be A 0 = 17233.99 MHz, B 0 = 5572.58 MHz, and C 0 = 4815.55 MHz, at ΔA 0 = -3.96 MHz, ΔB 0 = 4.76 MHz, and ΔC 0 = 2.51 MHz from previous experimental data. Low-energy levels and their tunneling splittings are determined variationally up to 700 cm-1. The A/E splitting of the ground vibrational state was computed to be 0.003 cm-1, as was expected given the methyl torsional barrier (∼600 cm-1). The fundamental levels (100), (010), and (001) are predicted at 132.133 and 132.086 cm-1 (methyl torsion), 186.507 and 186.467 cm-1 (O-CH3 torsion), and 371.925 and 371.950 cm-1 (OH torsion), respectively.

Unraveling UVB effects: Catalase activity and molecular alterations in the stratum corneum

AimUltraviolet B (UVB) radiation can compromise the functionality of the skin barrier through various mechanisms. We hypothesize that UVB induce photochemical alterations in the components of the outermost layer of the skin, known as the stratum corneum (SC), and modulate its antioxidative defense mechanisms. Catalase is a well-known antioxidative enzyme found in the SC where it acts to scavenge reactive oxygen species. However, a detailed characterization of acute UVB exposure on the activity of native catalase in the SC is lacking. Moreover, the effects of UVB irradiation on the molecular dynamics and organization of the SC keratin and lipid components remain unclear. Thus, the aim of this work is to characterize consequences of UVB exposure on the structural and antioxidative properties of catalase, as well as on the molecular and global properties of the SC matrix surrounding the enzyme. ExperimentsThe effect of UVB irradiation on the catalase function is investigated by chronoamperometry with a skin covered oxygen electrode, which probes the activity of native catalase in the SC matrix. Circular dichroism is used to explore changes of the catalase secondary structure, and gel electrophoresis is used to detect fragmentation of the enzyme following the UVB exposure. UVB induced alterations of the SC molecular dynamics and structural features of the SC barrier, as well as its water sorption behavior, are investigated by a complementary set of techniques, including natural abundance 13C polarization transfer solid-state NMR, wide-angle X-ray diffraction, Fourier transform infrared (FTIR) spectroscopy, and dynamic vapor sorption microbalance. FindingsThe findings show that UVB exposure impairs the antioxidative function of catalase by deactivating both native catalase in the SC matrix and lyophilized catalase. However, UVB radiation does not alter the secondary structure of the catalase nor induce any observable enzyme fragmentation, which otherwise could explain deactivation of its function. NMR measurements on SC samples show a subtle increase in the molecular mobility of the terminal segments of the SC lipids, accompanied by a decrease in the mobility of lipid chain trans-gauche conformers after high doses of UVB exposure. At the same time, the NMR data suggest increased rigidity of the polypeptide backbone of the keratin filaments, while the molecular mobility of amino acid residues in random coil domains of keratin remain unaffected by UVB irradiation. The FTIR data show a consistent decrease in absorbance associated with lipid bond vibrations, relative to the main protein bands. Collectively, the NMR and FTIR data suggest a small modification in the composition of fluid and solid phases of the SC lipid and protein components after UVB exposure, unrelated to the hydration capacity of the SC tissue. To conclude, UVB deactivation of catalase is anticipated to elevate oxidative stress of the SC, which, when coupled with subtle changes in the molecular characteristics of the SC, may compromise the overall skin health and elevate the likelihood of developing skin disorders.

Conformation-aggregation interplay in the simplest aliphatic ethers probed under high pressure.

The structures of the simplest symmetric primary ethers [(CnH2n+1)2O, n = 1-3] determined under high pressure revealed their conformational preferences and intermolecular interactions. In three new polymorphs of diethyl ether (C2H5)2O, high pressure promotes intermolecular CH...O contacts and enforces a conversion from the trans-trans conformer present in the α, β and γ phases to the trans-gauche conformer, which is higher in energy by 6.4 kJ mol-1, in the δ phase. Two new polymorphs of dimethyl ether (CH3)2O display analogous transformations of the CH...O bonds. The crystal structure of di-n-propyl ether (C3H7)2O, determined for the first time, is remarkably stable over the whole pressure range investigated from 1.70 up to 5.30 GPa.

Strategies for acquisition of resonance assignment spectra of highly dynamic membrane proteins: a GPCR case study.

In protein nuclear magnetic resonance (NMR), chemical shift assignment provides a wealth of information. However, acquisition of high-quality solid-state NMR spectra depends on protein-specific dynamics. For membrane proteins, bilayer heterogeneity further complicates this observation. Since the efficiency of cross-polarization transfer is strongly entwined with protein dynamics, optimal temperatures for spectral sensitivity and resolution will depend not only on inherent protein dynamics, but temperature-dependent phase properties of the bilayer environment. We acquired 1-, 2-, and 3D homo- and heteronuclear experiments of the chemokine receptor CCR3 in a 7:3 phosphatidylcholine:cholesterol lipid environment. 1D direct polarization, cross polarization (CP), and T2' experiments indicate sample temperatures below - 25°C facilitate higher CP enhancement and longer-lived transverse relaxation times. T1rho experiments indicate intermediate timescales are minimized below a sample temperature of - 20°C. 2D DCP NCA experiments indicated optimal CP efficiency and resolution at a sample temperature of - 30°C, corroborated by linewidth analysis in 3D NCACX at - 30°C compared to - 5°C. This optimal temperature is concluded to be directly related the lipid phase transition, measured to be between - 20 and 15°C based on rINEPT signal of all-trans and trans-gauche lipid acyl conformations. Our results have critical implications in acquisition of SSNMR membrane protein assignment spectra, as we hypothesize that different lipid compositions with different phase transition properties influence protein dynamics and therefore the optimal acquisition temperature.

Characterization of cellulose and TEMPO-oxidized celluloses prepared from Eucalyptus globulus

Abstract Eucalyptus (Eucalyptus globulus) cellulose was isolated from wood powder by dewaxing, delignification, and subsequent 4% NaOH extraction. 2,2,6,6-Tetramethyl-piperidine-1-oxyl (TEMPO)-oxidized eucalyptus celluloses were prepared from never-dried eucalyptus cellulose (EC) in yields of 96% and 72% (based on the dry weight of EC) when oxidized with NaOCl of 5 and 10 mmol/g-EC, respectively. Their carboxy contents were 1.4 and 1.8 mmol/g, respectively, when determined by conductivity titration. The crystallinity of cellulose I for EC decreased by TEMPO-mediated oxidation, showing that the originally crystalline region in EC was partly converted to disordered regions by TEMPO-mediated oxidation. Correspondingly, the relative signal area of C6‒OH/C1 with the trans-gauche (tg) conformation attributed to crystalline cellulose I in the solid-state 13C NMR spectrum of EC decreased from 0.42 to 0.34 by TEMPO-mediated oxidation with NaOCl of 10 mmol/g-EC. TEMPO-oxidized EC prepared with NaOCl of 10 mmol/g-EC was almost completely converted into individual TEMPO-oxidized EC nanofibrils (TEMPO-ECNFs) of homogeneous widths of ∼3 nm widths and lengths of >1 μm by mechanical disintegration in water. However, the TEMPO-ECNFs contained many kinks and had uneven surfaces, probably owing to significant damage occurring on the surface cellulose molecules of crystalline cellulose microfibrils during TEMPO-mediated oxidation.

Ion Pairing of the Neurotransmitters Acetylcholine and Glutamate in Aqueous Solutions.

Neurotransmitters (NTs) play an important role in neural communication, regulating a variety of functions such as motivation, learning, memory, and muscle contraction. Their intermolecular interactions in biological media are an important factor affecting their biological activity. However, the available information on the features of these interactions is scarce and contradictory, especially, in an estimation of possible ion binding. In this paper, we present the results of a study for two well-known NTs, acetylcholine (ACh) and glutamate (Glu), with relation to the NT-inorganic ion and the NT-NT binding in a water environment. The features of NT pairing are investigated in aqueous AChCl and NaGlu solutions over a wide concentration range using the integral equation method in 1D- and 3D- reference interaction site model (RISM) approaches. The data for ACh are given for its two bioactive TG (trans, gauche) and TT (trans, trans) conformers. As was found, for both NTs, the results indicate the NT-inorganic counterion contact pair to be the predominant associate type in the concentrated solutions. In this case, the counterions occupy the vacated "water" space in the hydration shell of the onium moiety (ACh) or carboxylate groups (Glu). For ACh, the "unfolded" TT conformer demonstrates a slightly greater possibility for counterion pairing in comparison with the "folded" TG conformer. For Glu, the probability of its binding with a counterion is slightly stronger for the "side-chain" carboxylate group than for the "backbone" group. The obtained results also revealed an insignificant probability of Glu--Glu- pairing. Namely, the RISM data indicate Glu--Glu- binding by NH3+-COO- interactions. A link between the ion binding of NTs and their biological activity is discussed. This contribution adds new knowledge to our understanding of the interactions between the NTs and their molecular environment, providing further insights into the behavior of these compounds in biological media.

Isopropyl 3-deoxy-α-D-ribo-hexopyranoside (isopropyl 3-deoxy-α-D-glucopyranoside): evaluating trends in structural parameters.

Isopropyl 3-deoxy-α-D-ribo-hexopyranoside (isopropyl 3-deoxy-α-D-glucopyranoside), C9H18O5, (I), crystallizes from a methanol-ethyl acetate solvent mixture at room temperature in a 4C1 chair conformation that is slightly distorted towards the C5SC1 twist-boat form. A comparison of the structural parameters in (I), methyl α-D-glucopyranoside, (II), α-D-glucopyranosyl-(1→4)-D-glucitol (maltitol), (III), and 3-deoxy-α-D-ribo-hexopyranose (3-deoxy-α-D-glucopyranose), (IV), shows that most endocyclic and exocyclic bond lengths, valence bond angles and torsion angles in the aldohexopyranosyl rings are more affected by anomeric configuration, aglycone structure and/or the conformation of exocyclic substituents, such as hydroxymethyl groups, than by monodeoxygenation at C3. The structural effects observed in the crystal structures of (I)-(IV) were confirmed though density functional theory (DFT) calculations in computed structures (I)c-(IV)c. Exocyclic hydroxymethyl groups adopt the gauche-gauche (gg) conformation (H5 anti to O6) in (I) and (III), and the gauche-trans (gt) conformation (C4 anti to O6) in (II) and (IV). The O-glycoside linkage conformations in (I) and (III) resemble those observed in disaccharides containing β-(1→4) linkages.

Free energy of conformational change in a single chain of polyvinylidene fluoride using molecular simulations

AbstractPolyvinylidene fluoride (PVDF) has several crystal forms of which the α‐form is nonpolar, while the β‐form is polar and has the highest piezoelectric constant. α PVDF, when stretched, transforms into the β form, which has wide applications in sensors and actuators. Steered molecular dynamics simulations are used to study the transformation of a single chain of PVDF from a trans–gauche conformation to an all trans one. The Helmholtz free energy change (∆F) is estimated using Jarzynski's equality. The transformation starts at the chain ends followed by the transformation of the remaining chain. The free energy change for the transformation is found to be always positive, indicating that the TGTG' form has higher thermodynamic stability than the all trans form throughout the studied temperature range. With increasing temperature, free energy change for the transformation increases monotonically.

Effect of tetrahydrofuran on poly(methyl methacrylate) and silica in the interfacial regions of polymer nanocomposites

The effects of tetrahydrofuran (THF) on the physical properties of poly(methyl methacrylate) at (PMMA)/silica nanoparticle interfaces in polymer nanocomposites were investigated via differential scanning calorimetry (DSC), Fourier transform infrared (FT-IR) spectroscopy, and X-ray diffraction (XRD) analysis. Amorphous structures containing PMMA chains with large numbers of trans-gauche conformers were observed in the annealed samples. The amorphous structures in the samples cast from THF suspensions contained PMMA chains rich in trans–trans conformers. These amorphous structures differed from those of neat PMMA prepared without silica. Although the polymer chain mobility was reduced due to interactions between PMMA and the silica nanoparticles, trans–trans-enriched PMMA chains within the amorphous structures were less affected by these interactions. When the amorphous structures were heated above the glass transition temperature of PMMA, the proportion of trans–gauche conformers increased. When the neat PMMA samples were dried at room temperature, the glass transition temperature (Tg) increases linearly with the decrease in the amount of residual solvent. However, even if the residual solvent is extrapolated to 0 wt%, the Tg is significantly lower than the bulk Tg despite no residual solvent. The Tg of heat-dried samples heat treated at 120 °C also increases linearly with decreasing residual solvent content. However, Tg was significantly different depending on the drying temperature even with the same residual solvent amount. These results indicated that the PMMA samples dried at room temperature have a distinctly different molecular mobility from the heated sample.

Hydration features of the neurotransmitter acetylcholine

Abstract Acetylcholine (ACh) is one of the intercellular neurotransmitters (NT) involved in the transmission of nervous excitation in the central and peripheral nervous systems. Hydration is one of the factors that can affect the structure, functions and biological activity of NTs. In order to gain more detailed insights on NT hydration, we studied the ACh cation in aqueous AChCl solutions with the integral equation method in the framework of the 1D- and 3D-RISM (Reference Interaction Site Model) approaches. The concentration range from infinite dilution to 0.53 M was covered, and data were obtained for two bioactive conformers, namely the trans, gauche (TG) and the trans, trans (TT) species, which are both stable in water. For both conformers the results indicate the onium and carbonyl groups as the most favorable hydration sites, with well-defined hydration layers and large hydration numbers over the entire concentration range. The difference in hydration of the TG and TT conformers is connected with their spatial configurations. Due to its more “folded” structure, the TG conformer exhibits steric limitations for water penetration to the cation. In comparison with the “unfolded” TT conformer, the “folded” TG conformer has the decreased amount of water in the nearest environment of the onium group and the oxygen of ester group. The obtained results are discussed from the viewpoint of biological activity of TG and TT in relation to the receptors under classical description of neurotransmission and new ideas about the membrane-dependent / membrane-independent mechanism of this process. The presented results add new knowledge to understanding of the interactions between the NTs and their molecular environment.

Confocal Raman microspectroscopy as an alternative to differential scanning calorimetry to detect the impact of emulsifiers and formulations on stratum corneum lipid conformation

The purpose of this study was to investigate the impact of emulsifiers and formulations on stratum corneum (SC) lipid conformation and evaluate confocal Raman microspectroscopy (CRM) as an alternative method to differential scanning calorimetry (DSC) in this research context. To this end, four different formulations were used: three conventional creams that contained ionic and/or non-ionic emulsifiers and one surfactants-free emulsion stabilized by a polymeric emulsifier. Additionally, all emulsifiers were tested in aqueous solutions/dispersions in the respective concentrations as present in the formulations. In this study, emulsifiers and formulations were applied onto excised porcine skin during incubation in Franz diffusion cells. Subsequently, SC was isolated, dried and subjected to CRM and DSC measurement to analyse lipid structural changes after treatment. In CRM measurement, 1080 cm−1/(1130 cm−1 + 1070 cm−1) peak ratio, which represents the C-C skeleton vibration and trans-gauche conformation order of lipids, was investigated. Various emulsifiers and formulations showed different impact on SC lipid conformation. Specifically, cetearyl alcohol and sodium cetearyl sulfate mixture dispersion showed the strongest ability among all studied emulsifiers, followed by glycerol monostearate, polyoxyethylene-20-glycerol monostearate as well as their mixture. Polysorbate 60, cetyl stearyl alcohol and their mixture did not affect SC lipid structure. The results of CRM and DSC correlated very well, indicating CRM, as an alternative to DSC, can be a reliable method to investigate SC lipid conformation.

Metastable interface formation in isotactic poly(methyl methacrylate)/alumina nanoparticle mixtures

The interface structures of isotactic poly(methyl methacrylate) (it-PMMA)/alumina nanoparticle (Al2O3; ~40 nm) mixtures from tetrahydrofuran (THF) solutions were investigated by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, and differential scanning calorimetry (DSC). The mixtures of it-PMMA can form two amorphous phases with different crystallinities depending on casting conditions from THF. These structures are metastable and have different activation energies for crystal nucleus formation. The polymer interface on Al2O3 particles changes into a crystallizable amorphous phase with a trans-gauche-rich chain conformation. The interphase structure of isotactic poly(methyl methacrylate) (it-PMMA)/aluminananoparticle mixtures obtained from tetrahydrofuran (THF) solution was discussed. The it-PMMA in the mixtures forms two amorphous phases (crystallizable and incrystallizable phases) depending on casting conditions from THF. The polymer interphase on Al2O3 particles changes into a crystallizable structure with a trans-gauche rich conformation and amorphous. The interphase shows a lower Tg than the melt-cast one and is easy to crystallize at low temperature. The novel structure was formed by the conformation freezing of the polymer at Al2O3 surface.

Structure-Based Design and Synthesis of Apramycin-Paromomycin Analogues: Importance of the Configuration at the 6'-Position and Differences between the 6'-Amino and Hydroxy Series.

The preparation of a series of four analogues of the aminoglycoside antibiotics neomycin and paromomycin is described in which ring I, involved in critical binding interactions with the ribosomal target, is replaced by an apramycin-like dioxabicyclo[4.4.0]octane system. The effect of this modification is to lock the hydroxymethyl side chain of the neomycin or paromomycin ring I, as part of the dioxabicyclooctane ring, into either the gauche-gauche or the gauche-trans conformation (respectively, axial or equatorial to the bicyclic system). The antiribosomal activity of these compounds is investigated with cell-free translation assays using both bacterial ribosomes and recombinant hybrid ribosomes carrying eukaryotic decoding A site cassettes. Compounds substituted with an equatorial hydroxyl or amino group in the newly formed ring are considerably more active than their axial diastereomers, lending strong support to crystallographically derived models of aminoglycoside-ribosome interactions. One such bicyclic compound carrying an equatorial hydroxyl group has activity equal to that of the parent yet displays better ribosomal selectivity, predictive of an enhanced therapeutic index. A paromomycin analog lacking the hydroxymethyl ring I side chain is considerably less active than the parent. Antibacterial activity against model Gram negative and Gram positive bacteria is reported for selected compounds, as is activity against ESKAPE pathogens and recombinant bacteria carrying specific resistance determinants. Analogues with a bicyclic ring I carrying equatorial amino or hydroxyl groups mimicking the bound side chains of neomycin and paromomycin, respectively, show excellent activity and, by virtue of their novel structure, retain this activity in strains that are insensitive to the parent compounds.

Different Conformations of Surface Cellulose Molecules in Native Cellulose Microfibrils Revealed by Layer-by-Layer Peeling.

Layer-by-layer peeling of surface molecules of native cellulose microfibrils was performed using a repeated sequential process of 2,2,6,6-tetramethylpiperidine-1-oxyl radical-mediated oxidation followed by hot alkali extraction. Both highly crystalline algal and tunicate celluloses and low-crystalline cotton and wood celluloses were investigated. Initially, the C6-hydroxy groups of the outermost surface molecules of each algal cellulose microfibril facing the exterior had the gauche-gauche (gg) conformation, whereas those facing the interior had the gauche-trans (gt) conformation. All the other C6-hydroxy groups of the cellulose molecules inside the microfibrils contributing to crystalline cellulose I had the trans-gauche (tg) conformation. After surface peeling, the originally second-layer molecules from the microfibril surface became the outermost surface molecules, and the original tg conformation changed to gg and gt conformations. The plant cellulose microfibrils likely had disordered structures for both the outermost surface and second-layer molecules, as demonstrated using the same layer-by-layer peeling technique.

A depth-dependent profile of the lipid conformation and lateral packing order of the stratum corneum in vivo measured using Raman microscopy.

The intercellular lipid structure of the stratum corneum (SC) plays a key role in skin barrier function. A depth profile of the intercellular lipid conformation and the lipid lateral packing order were measured in vivo in the human SC using confocal Raman microscopy. The depth profiles of the 2880 cm(-1)/2850 cm(-1) peak ratio intensity, which represent the C-H stretching and lateral packing order of lipids, and the 1080 cm(-1)/(1130 cm(-1) + 1060 cm(-1)) peak ratio, which represents the C-C skeleton vibration and trans-gauche conformation order of lipids, were investigated. The influence of keratin on the lipid peaks at 2850 cm(-1) and 2880 cm(-1) was excluded by the developed mathematical algorithm. The results show that the trans-conformation and lateral packing order of the intercellular lipids reach their maximum value in the SC at 20-40% of its depth and then decrease towards the stratum granulosum. These results show that at a depth of 20-40% (normally corresponding to a depth of 4-8 μm) the SC exhibits the most ordered lipids and therefore the highest skin barrier function. The lateral packing of lipids is more disordered on the surface and in the deeper parts of the SC, which may be associated with a reduced skin barrier function.

Photochemistry of glycolaldehyde in cryogenic matrices.

The photochemistry of glycolaldehyde (GA) upon irradiation at 266 nm is investigated in argon, nitrogen, neon, and para-hydrogen matrices by IR spectroscopy. Isomerization and fragmentation processes are found to compete. The hydrogen-bonded Cis-Cis form of GA is transformed mainly to the open Trans-Trans conformer and to CO and CH3OH fragments and their mixed complexes. Different photo-induced behaviours appear depending on the matrix. In nitrogen, small amounts of Trans-Gauche and Trans-Trans conformers are detected after deposition and grow together upon irradiation. The Trans-Gauche conformer is characterized for the first time. In para-hydrogen due to a weaker cage effect additional H2CO and HCO fragments are seen. Calculations of the potential energy surfaces of S0, S1, and T1 states--to analyse the torsional deformations which are involved in the isomerization process--and a kinetic analysis are presented to investigate the different relaxation pathways of GA. Fragmentation of GA under UV irradiation through the CO+CH3OH molecular channel is a minor process, as in the gas phase.

NMR characterization of chemically synthesized branched α-dextrin model compounds

1H and 13C NMR chemical shifts were accurately determined by consistent referencing for an extensive set of chemically synthesized branched α-glucan model compounds. The model compounds include anomerically fixed and reducing oligosaccharides ranging in size from isomaltose to a doubly branched decasaccharide. Both the 13C1 chemical shift and the 13C6 chemical shifts in α-(1→6) glycosidic bonds are strongly dependent on the chemical structure in the vicinity of the branch point, especially on the addition of glucopyranosyl units towards the non-reducing end of the backbone chain. The conformational sampling at the branch point of the branched α-glucan model compounds was experimentally probed with homo-nuclear scalar couplings. Substitution at O6 consistently increases the fraction of C6–O6 trans conformations, but to a lesser extent, if the attachment occurs at the reducing end residue. Increasingly complex structures in the vicinity of the branch point increase the population of the gauche–trans conformation of the C5–C6 bond. This population change is found to correlate with the 13C6 chemical shift.

Flexible Bis(imidazole) Mediated Assembly of Silver(I)–Organic Frameworks with Ethynide and Trifluoroacetate Ligands

A new family of 10 organosilver(I) complexes, namely, [(AgC≡CPh)2(AgO2CCF3)4(cis-1,2-bix)(CH3OH)]·2CH3OH (1,2-bix = 1,2-bis(imidazol-1-ylmethyl)benzene, 1A), [(AgC≡CC6H4Me-2)2(AgO2CCF3)4(cis-1,3-bix)]·5.25H2O (1,3-bix = 1,3-bis(imidazol-1-ylmethyl)benzene, 1B), [(AgC≡CPh)3(AgO2CCF3)6(trans-1,4-bix)(CH3OH)3]·2CH3OH (1,4-bix = 1,4-bis(imidazol-1-ylmethyl)benzene, 2A), [(AgC≡CC6H4Me-4)3(AgO2CCF3)6(trans-1,4-bix)(CH3OH)3]·2CH3OH (2B), [(AgC≡CPh)(AgO2CCF3)3(trans-1,3-bix)(H2O)]·0.5H2O (3A), [(AgC≡CC6H4Me-4)(AgO2CCF3)3(trans-1,3-bix)(H2O)] (3B), [(AgC≡CC6H4Me-4)(AgO2CCF3)3(bbi)(H2O)] (bbi = 1,1′-(1,4-butanediyl)bis(imidazole), 3C), [(AgC≡CC6H4tBu-4)(AgO2CCF3)3(trans-1,4-bix)] (3D), [(AgC≡CPh)2(AgO2CCF3)4(bbi)(H2O)]·2H2O (4), and [(AgC≡CtBu)2(AgO2CCF3)4(bbi)] (5), have been synthesized employing a variable combination of ethynide, trifluoroacetate, and bridging bis(imidazole) ligands. In both 1A and 1B, the flexible 1,2-bix or 1,3-bix ligands in cis-conformations are alternatively attached on both sides of an infinite cationic silver(I) chain, and neighboring organosilver(I) chains are further interconnected by intermolecular hydrogen bonds to generate a three-dimensional supramolecular architecture. In structural analogues 2A and 2B, pairs of silver(I) chains are linked via the trans-1,4-bix ligands to yield infinite ladders, which are further joined together by hydrogen bonds to afford a three-dimensional supramolecular network. In the isostructural series 3A–3D, centrosymmetric (PhC2)2Ag8 aggregates are connected by trifluoroacetate groups to give an infinite chain, and such chains are then bridged by bis(imidazole) ligands to generate a coordination layer. Furthermore, adjacent layers are linked by hydrogen bonds to form a three-dimensional supramolecular network. In 4, infinite silver(I)–phenylethynide chains constructed by Ag6 aggregates are bridged by bbi ligands in a gauche–trans–gauche conformation to yield a three-dimensional coordination framework. In contrast, infinite silver(I)-tert-butylethynide chains based on Ag8 and Ag6 aggregates in 5 are linked by bbi ligands exhibiting different trans–trans–trans and gauche–trans–gauche conformations to generate a three-dimensional coordination network. Finally, the roles played by various bis(imidazole) ligands and ethynides bearing different substituents in the framework assembly are discussed in detail.

Conformation and Dynamics at a Flexible Glycosidic Linkage Revealed by NMR Spectroscopy and Molecular Dynamics Simulations: Analysis of β-l-Fucp-(1→6)-α-d-Glcp-OMe in Water Solution

The intrinsic flexibility of carbohydrates facilitates different 3D structures in response to altered environments. At glycosidic (1→6)-linkages, three torsion angles are variable, and herein the conformation and dynamics of β-L-Fucp-(1→6)-α-D-Glcp-OMe are investigated using a combination of NMR spectroscopy and molecular dynamics (MD) simulations. The disaccharide shows evidence of conformational averaging for the ψ and ω torsion angles, best explained by a four-state conformational distribution. Notably, there is a significant population of conformations having ψ = 85° (clinal) in addition to those having ψ = 180° (antiperiplanar). Moderate differences in (13)C R1 relaxation rates are found to be best explained by axially symmetric tumbling in combination with minor differences in librational motion for the two residues, whereas the isomerization motions are occurring too slowly to be contributing significantly to the observed relaxation rates. The MD simulation was found to give a reasonably good agreement with experiment, especially with respect to diffusive properties, among which the rotational anisotropy, D∥/D⊥, is found to be 2.35. The force field employed showed too narrow ω torsion angles in the gauche-trans and gauche-gauche states as well as overestimating the population of the gauche-trans conformer. This information can subsequently be used in directing parameter developments and emphasizes the need for refinement of force fields for (1→6)-linked carbohydrates.