A MAS NMR investigation of aluminosilicate, silicophosphate, and aluminosilicophosphate gels and the evolution of crystalline structures on heating the gels

Gels of various composition containing SiO2, Al2O3, and P2O5 have been investigated by employing high resolution magic-angle-spinning (MAS) 27Al, 29Si, and 31P NMR spectroscopy. Changes occurring in the NMR spectra as the gels are progressively heated have been examined to understand the nature of structural changes occurring during the crystallization of the gels. 27Al resonance is sensitive to changes in the coordination number even when the Al concentration is as low as 1 mol%. As the percentage of Al increases, the hydroxyl groups tend to be located on the Al sites while Si remains as SiO4/2 (Q4). Mullite is the major phase formed at higher temperature in the aluminosilicate gels. In the case of the silicophosphate gels, Si is present in the form of Q4 and Q3 species. There is a change in the coordination of Si from four to six as the gel is heated. The formation of six-coordinated Si is facilitated even at lower temperatures (~673 K) when the P2O5 content is high. The phosphorus atoms present as orthophosphoric acid units in the xerogels change over to metaphosphate-like units as the gel is heated to higher temperatures. In aluminosilicophosphates, Si is present as Q4 and Q3 species while P is present as metaphosphate units; Al in these gels seems to be inducted into the tetrahedral network positions.

Differences in hydration and association of helical Boc-Val-Ala-Leu-Aib-Val-Ala-Leu-(Val-Ala-Leu-Aib)2-OMe. xH2O in two crystalline polymorphs

The 15-residue apolar peptide, Boc-Val-Ala-Leu-Aib-Val-Ala-Leu-(Val-Ala-Leu-Aib)h2a-sO Mebeen crystallized from 2-propanol-water (form I). The crystal parameters for I are as follows:C74H133N15018*2H20s,p ace group P21, a = 9.185 (6) A, b = 47.410 (3) A, c = 10.325 (9) A, @ = 91.47(2)O, 2 = 2, R = 6.3% for 4532 reflections observed >3aQ, resolution 0.94 A. The structure isalmost completely a-helical with eleven 5-1 hydrogen bonds and one 441 hydrogen bond nearthe N-terminus. The structure has been compared with a polymorph (form 11) obtained frommethanol-water (Karle, I. L.; Flippen-Anderson, J. L.; Uma, K.; Sukumar, M.; Balaram, P., J. An.Chem. SOC19. 90,112,9350-9356). The two forms differ in the extent of hydration; form I contains two water molecules in the head-to-tail region of helical columns, while form I1 is more extensively solvated, with the equivalent of 7.5 water molecules. The three-dimensional packing of helices is completely parallel in I and antiparallel in 11.

High-frequency capacitance-voltage characteristics of amorphous (undoped)/crystalline silicon heterostructures

A numerical procedure is presented for calculating high-frequency capacitance variation with bias in amorphous (undoped)/crystalline silicon heterojunction. The results of the model calculations using this procedure have been reported, for different p silicon substrates. These have been compared with the corresponding capacitance variations in the other limiting case, in which the heterostructure acts like an MIS structure. The effect of interface states on the capacitance characteristics has also been studied. In the second part, we report the results of 1 MHz capacitance measurements on various amorphous (undoped)/crystalline silicon heterostructures.

Quasicrystalline and related crystalline phases in a rapidly solidified 2024-2Li aluminium alloy

The formation and decomposition of quasicrystalline and crystalline phases in as-rapidly solidified and annealed commercial AISI 2024 aluminum alloy containing 2 wt% Li have been investigated by detailed transmission electron microscopy, including a combination of bright field and dark field imaging, selected area diffraction pattern analysis and energy dispersive X-ray microanalysis. The microstructure of as-melt spun 2024-2Li consists of alpha-Al cells, containing small coherent delta' precipitates, and particles or a continuous network of the icosahedral phase at the cell boundaries. After annealing at 300-degrees-C, the intercellular particles of the icosahedral phase coarsen progressively and assume a more faceted shape; after annealing at 400-degrees-C, particles of the decagonal and crystalline O phases precipitate heterogeneously on preexisting particles of the icosahedral phase; and after annealling at 500-degrees-C, the icosahedral and decagonal phases dissolve completely, and small particles of the crystalline O phase remain together with newly precipitated plates of the T1 phase. The icosahedral phase in melt spun and melt spun/annealed 2024-2Li belongs to the Al6CuLi3 class of icosahedral phases, with a quasilattice constant of 0.51 nm, a stoichiometry of (Al, Si)6(Cu, Mn, Fe) (Li, Mg)3 and an average composition of Al-24.1 at.% Cu-6.4 at.% Mg-1.7 at.% Si-0.3 at.% Mn-0.5 at.% Fe as-melt spun and Al-21.9 at.% Cu-6.3 at.% Mg-1.0 at.% Si-0.5 at.% Fe as-heat-treated. The decagonal phase in melt spun/annealed 2024-2Li belongs to the Al4Mn class of decagonal phases, with a periodicity of 1.23 nm along the 10-fold symmetry axis, a stoichiometry of Al3(Cu, Mn, Fe) and an average composition of Al-10.3 at.% Cu-13.8 at.% Mn-2.3 at.% Fe. The crystalline O phase in melt spun/annealed 2024-2Li has an orthorhombic structure with lattice parameters of a = 2.24 nm, b = 2.35 nm and c = 1.23 nm, a stoichiometry of Al3(Cu, Mn, Fe) and an average composition of Al-11.0 at.% Cu-14.8 at.% Mn-3.9 at.% Fe. Detailed analysis of selected area diffraction patterns shows a close similarity between the icosahedral, decagonal and crystalline O phases in melt spun and melt spun/annealed 2024-2Li. In particular, the decagonal phase and crystalline O phases have a similar composition, and exhibit an orientation relationship which can be expressed as: [GRAPHICS] suggesting that the orthorhombic O phase is an approximant structure for the decagonal phase.

Quasicrystals and their crystalline homologues in the Al-Mn-Cu ternary alloys

Electron diffraction and high-resolution electron microscopy have been employed to differentiate among icosahedral, decagonal and crystalline particles that occur in as-cast and rapidly solidified Al-Mn-Cu alloys. The resemblance between decagonal quasicrystals and crystals in their electron diffraction patterns is striking. The crystalline structure is based on the orthorhombic 'Al3Mn' structure, but also a new monoclinic phase called 'X' has been discovered and described here. The present observations are also closely related to the orthorhombic structures in Al60Mn11Ni4. The occurrence of fine-scale twinning and fragmentation into domains explains the complex diffraction effects.

X-ray studies on crystalline complexes involving amino acids and peptides XIX. Effects of change in chirality in the complexes of succinic acid with dl- and l-arginine

Crystals of dl-arginine hemisuccinate dihydrate (I)(monoclinic; P21/c; a = 5.292, b = 16.296, c = 15.203 Å; α= 92.89°; Z = 4) and l-arginine hemisuccinate hemisuccinic acid monohydrate (II) (triclinic; P1; a = 5.099; b = 10.222, c = 14.626 Å; α= 77.31, β= 89.46, γ= 78.42°; Z = 2) were grown under identical conditions from aqueous solutions of the components in molar proportions. The structures were solved by direct methods and refined to R = 0.068 for 2585 observed reflections in the case of (I) and R = 0.036 for 2154 observed reflections in the case of (11). Two of the three crystallographically independent arginine molecules in the complexes have conformations different from those observed so far in the crystal structures containing arginine. The succinic acid molecules and the succinate ions in the structures are centrosymmetric and planar. The crystal structure of (II) is highly pseudosymmetric. Arginine-succinate interactions in both the complexes involve specific guanidyl-carboxylate interactions. The basic elements of aggregation in both the structures are ribbons made up of alternating arginine dimers and succinate ions. However, the ribbons pack in different ways in the two structures. (II) presents an interesting case in which two ionisation states of the same molecule coexist in a crystal. The two complexes provide a good example of the effect of change in chirality on stoichiometry, conformation, aggregation, and ionisation state in the solid state.

X-ray studies on crystalline complexes involving amino acids and peptides. XXI. Structure of a (1:1) complex between L-phenylalanine and D-valine

CsHllNO2.C9HilNO2, Mr = 282.3, P1, a = 5.245 (1), b = 5.424 (1), c = 14.414 (2) A, a = 97.86 (1), fl = 93-69 (2), y = 70-48 (2) °, V= 356 A 3, Z = 1, O m = 1-32 (2), Dx = 1.32 g cm-3, h(Mo Ka) = 0-7107 A, g = 5-9 cm-1, F(000) = 158, T= 298 K, R=0.035 for 1518 observed reflections with I>2tr(I). The molecules aggregate in double layers, one ayer made up of L-phenylalanine molecules and the other of D-valine molecules. Each double layer is stabilized by interactions involving main-chain atoms of both types of molecules. The interactions include hydrogen bonds which give rise to two head-to-tail sequences. The arrangement of molecules in the complex is almost the same as that in the structure of DL-valine (and DL-leucine and DL-isoleucine) except for the change in the side chain of L molecules. The molecules in crystals containing an equal number of L and O hydrophobic amino-acid molecules thus appear to aggregate in a similar fashion, irrespective of the precise details of the side chain.

X-ray studies on crystalline complexes involving amino acids and peptides. XXV. Structures of DL-proline hemisuccinic acid and glycyl-L-histidinium semisuccinate monohydrate and a comparative study of amino-acid and peptide complexes of succinic acid

DL-Proline hemisuccinic acid, C5H9NO2.1/2C4H6O4, M(r) = 174.2, P2(1/c) a = 5.254 (1), b = 17.480 (1), c = 10.230 (i) angstrom, beta = 119.60 (6)-degrees Z = 4, D(m) = 1.41 (4), D(x) = 1.42 g cm-3, R = 0.045 for 973 observed reflections. Glycyl-L-histidinium semisuccinate monohydrate, C8H13N4O3+.C4H5O4-.H2O, M(r) = 348.4, P2(1), a = 4.864 (1), b = 17.071 (2), c = 9.397 (1) angstrom, beta = 90.58-degrees, Z = 2, D(m) = 1.45 (1), D(x) = 1.48 g cm-3, R = 0.027 for 1610 observed reflections. Normal amino-acid and dipeptide aggregation patterns are preserved in the structures in spite of the presence of succinic acid/semisuccinate ions. In both the structures, the amino-acid/dipeptide layers stack in such a way that the succinic acid molecules/semisuccinate ions are enclosed in voids created during stacking. Substantial variability in the ionization state and the stoichiometry is observed in amino-acid and peptide complexes of succinic acid. Succinic acid molecules and succinate ions appear to prefer a planar centro-symmetric conformation with the two carboxyl (carboxylate) groups trans with respect to the central C=C bond. Considerable variation is seen in the departure from and modification of normal amino-acid aggregation patterns produced by the presence of succinic acid. Some of the complexes can be described as inclusion compounds with the amino acid/dipeptide as the 'host' and succinic acid/semisuccinate/succinate as the 'guest'. The effects of change in chirality, though very substantial, are not the same in different pairs of complexes involving DL and L isomers of the same amino acid.

Structural Relationships in 2,3-Bis-n-decyloxyanthracene and 12-Hydroxystearic Acid Molecular Gels and Aerogels Processed in Supercritical CO2

Supercritical carbon dioxide is used to prepare aerogels of two reference molecular organogelators, 2,3-bis-n-decyloxyanthracene (DDOA) (luminescent molecule) and 12-hydroxystearic acid (HSA). Electron microscopy reveals the fibrillar morphology of the aggregates generated by the protocol. SAXS and SANS measurements show that DDOA aerogels are crystalline materials exhibiting three morphs: (1) arrangements of the crystalline solid (2D p6m), (2) a second hexagonal morph slightly more compact, and (3) a packing specific of the fibers in the gel. Aggregates specific of the aerogel (volume fraction being typically phi approximate to 0.60) are developed over larger distances (similar to 1000 angstrom) and bear fewer defaults and residual strains than aggregates in the crystalline and gel phases. Porod, Scherrer and Debye-Bueche analyses of the scattering data have been performed. The first five diffraction peaks show small variations in position and intensity assigned to the variation of the number of fibers and their degree of vicinity within hexagonal bundles of the related SAFIN according to the Oster model. Conclusions are supported by the guidelines offered by the analysis of the situation in HSA aerogels for which the diffraction pattern can be described by two coexisting lamellar-like arrangements. The porosity of the aerogel, as measured by its specific surface extracted from the scattering invariant analysis, is only 1.8 times less than that of the swollen gel and is characteristic of a very porous material.

Evidence for O-H.cntdot..cntdot..cntdot.C and N-H.cntdot..cntdot..cntdot.C hydrogen bonding in crystalline alkynes, alkenes, and aromatics

Attempts have been made to understand the nature and significance of hydrogen bonds of the type X-H-C (X = 0, N) . These unusual interactions have been discussed recently. Crystallographic studies on 17a-ethynylandrosta- 2,4-dieno[2,3-d]dihydroxazol1-7 8-01 (donazole) provide direct evidence of such an 0-H.0-C interaction. Ab initio computations, IR spectroscopy, and database studies show that these hydrogen bonds, while uncommon, are energetically and structurally significant.

Novel photocrosslinkable liquid-crystalline polymers: poly[bis(benzylidene)] esters

A new class of photo-cross-linkable main-chain liquid crystalline polymers (PMCLCPs) containing bis(benzylidene)cycloallranone groups have been synthesized and studied for their liquid crystalline and photochemical properties. The bis(benzylidene)cycloalkanone group in the chain functions both as a mesogen and as a photoreactive center. All of the polymers exhibit a nematic mesophase. Two kinds of photoreactions, namely, photoisomerization and photo-cross-linking, operate in these polymers. Above Tu at the initial stages of irradiation, photoisomerization predominates the cross-linking, which resulta in the disruption of the chromophore aggregates. Below T8, because of the restricted mobility of the chains, only cross-linking takes place. Studies on the model compound, bis(benzylidene)cyclopentanone, confii the above observations and demonstrate further that the cross-linking proceeds by the 2r + 2r cycloaddition reaction of the bis(benzylidene)cycloallranone moieties. The cross-linking rate decreases with increase in the size of the cycloalkanone ring. Heating the solution cast polymer fii results in the ordered aggregation of the chromophores just above TI and also at the crystal to crystal transition temperature, which facilitates the phobcross-linking reactions. In the isotropic phase, the random orientation of the chromophores drastically curtails the cross-linking rata

Synthesis and characterization of single-crystalline alpha-MoO3 nanofibers for enhanced Li-ion intercalation applications

High quality, single-crystalline alpha-MoO3 nanofibers are synthesized by rapid hydrothermal method using a polymeric nitrosyl-complex of molybdenum(II) as molybdenum source without employing catalysts, surfactants, or templates. The possible reaction pathway is decomposition and oxidation of the complex to the polymolybdate and then surface condensation on the energetically favorable 001] direction in the initially formed nuclei of solid alpha-MoO3 under hydrothermal conditions. Highly crystalline alpha-MoO3 nanofibers have grown along 001] with lengths up to several micrometres and widths ranging between 280 and 320 nm. The alpha-MoO3 nanofibers exhibit desirable electrochemical properties such as high capacity reversibility as a cathode material of a Li-ion battery.

Influence of water and thermal history on ion transport in lithium salt-succinonitrile plastic crystalline electrolytes

Important issues of water and thermal history affecting ion transport in a representative plastic crystalline lithium salt electrolyte: succinonitrile (SN)-lithium perchlorate (LiClO4) are discussed here. Ionic conductivity of electrolytes with high lithium salt amounts (similar to 1 M) in SN at a particular temperature is known to be influenced both by the trans-gauche isomerism and ion association (solvation), the two most important intrinsic parameters of the plastic solvent. In the present study both water and thermal history influence SN and result in enhancement of ionic conductivity of 1 M LiClO4-SN electrolyte. Systematic observations reveal that the presence of water in varying amounts promote ion-pair dissociation in the electrolyte. While trace amounts (approximate to 1-15 ppm) do not affect the trans-gauche isomerism of SN, the presence of water in large amounts (approximate to 5500 ppm) submerges the plasticity of SN. Subjugating the electrolyte to different thermal protocol resulted in enhancement of trans concentration only. This is an interesting observation as it demonstrates a simple and effective procedure involving utilization of an optimized set of external parameters to decouple solvation from trans-gauche isomerism. Observations from the ionic conductivity of various samples were accounted by changes in signature isomer and ion-association bands in the mid-IR regime and also from plastic to normal crystal transition temperature peak obtained from thermal studies. (C) 2010 Elsevier B.V. All rights reserved.

A crosslinked ``polymer-gel'' rechargeable lithium-ion battery electrolyte from free radical polymerization using nonionic plastic crystalline electrolyte medium

A cross-linked polymer-gel soft matter electrolyte with superior electrochemical, thermal and mechanical properties obtained from free radical polymerization of vinyl monomers in a semi-solid organic nonionic plastic crystalline electrolyte for application in rechargeable lithium-ion batteries is discussed here.

Dielectric Relaxation Spectroscopy for Evaluation of the Influence of Solvent Dynamics on Ion Transport in Succinonitrile-Salt Plastic Crystalline Electrolytes

Influence of succinonitrile (SN) dynamics on ion transport in SN-lithium perchlorate (LiClO4) electrolytes is discussed here via dielectric relaxation spectroscopy. Dielectric relaxation spectroscopy (similar to 2 x 10(-3) Hz to 3 MHz) of SN and SN-LiClO4 was studied as a function of salt content (up to 7 mol % or 1 M) and temperature (-20 to +60 degrees C). Analyses of real and imaginary parts of permittivity convincingly reveal the influence Of trans gauche isomerism and solvent-salt association (solvation) effects on ion transport. The relaxation processes are highly dependent on the salt concentration and temperature. While pristine SN display only intrinsic dynamics (i.e., trans-gauche isomerism) which enhances with an increase in temperature, SN-LiClO4 electrolytes especially at high salt concentrations (similar to 0.04-1 M) show salt-induced relaxation processes. In the concentrated electrolytes, the intrinsic dynamics was observed to be a function of salt content, becoming faster with an increase in salt concentration. Deconvolution of the imaginary part of the permittivity spectra using Havriliak-Negami (HN) function show a relaxation process corresponding to the above phenomena. The permittivity data analyzed using HN and Kohlrausch-Williams-Watta (KWW) functions show non-Debye relaxation processes and enhancement in the trans phase (enhanced solvent dynamics) as a function of salt concentration and temperature.