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The chemistry of actinide-nitrides has witnessed significant advances in the last ten years with a large focus on uranium and a few breakthroughs with thorium. Following the early discovery of the first terminal and bridging nitride complexes, various synthetic routes to uranium nitrides have since been identified, although the range of ligands capable of stabilizing uranium nitrides still remains scarce. In particular, both terminal- and bridging-nitrides possess attractive advantages for potential reactivity, especially in light of the recent development of uranium complexes for dinitrogen reduction and functionalization. The first molecular thorium bridged-nitride complexes have also been recently identified, anticipating the possibility of expanding nitride chemistry not only to low-valent thorium, but also to the transuranic elements.

A set of guiding principles for the development of a standard for FAIR management of spectroscopic data are outlined and discussed. The principles form the basis for future recommendations of IUPAC Project 2019-031-1-024 specifying a detailed data model and metadata schema for describing the contents of an “IUPAC FAIRData Collection” and the organization of digital objects within that collection. Foremost among the recommendations will be a specification for an “IUPAC FAIRData Finding Aid” that describes the collection in such a way as to optimize the findability, accessibility, interoperability, and reusability of its contents. Results of an analysis of data provided by an American Chemical Society Publications pilot study are discussed in relation to potential workflows that might be used in implementing the “IUPAC FAIRSpec” standard based on these principles.

Thirty years after the release of the first commercial lithium-ion battery, capacity fading due to complex ageing mechanisms remains one of the major concerns in lithium-ion battery research. Lithium-ion battery cathodes age due to phenomena as transition metal dissolution, electrolyte oxidation and volume expansions.[1] To suppress these effects, a protective coating can be applied to the cathode’s surface to avoid direct contact with the liquid electrolyte. Many studies exist in literature, showing the protective effect of conformal and pinhole-free Atomical Layer Deposited (ALD) coatings. However, the inorganic coatings deposited by ALD are rigid and will crack upon volume expansion of the cathode.[2] Molecular Layer Deposition (MLD) offers the same benefits as ALD but can be used to deposit hybrid inorganic/organic flexible films that can accommodate potential volume expansions of the cathode. To our knowledge, apart from ‘metalcones’ i.e. MLD films grown using a metal containing precursor and an alcohol, MLD films remain to be explored as protective and flexible coatings for lithium-ion batteries.[3] In this work, hybrid MLD titanium carboxylate thin films are deposited using tetrakis(dimethylamido)titanium (TDMAT) and various dicarboxylic acid precursors: oxalic acid, malonic acid, succinic acid, glutaric acid and 3,6-dioxaoctanedioic acid. The latter containing two ethylene oxide units per molecule, potentially increasing the lithium-ion conductivity.[4] The growth of the titanium carboxylate MLD processes is studied using in situ ellipsometry at a substrate temperature of 100 °C and 160 °C. Only the TDMAT/oxalic acid process is found to display good saturation behavior, while a parasitic CVD component is present during the TDMAT pulse for the other processes. The structure of the as-deposited films is physically characterized using Fourier Transform IR spectroscopy (FTIR) and X-Ray Photoelectron Spectroscopy (XPS), confirming the successful deposition of titanium carboxylate films. The films are found to be stable in air up to 50 days as shown by FTIR. This is in contrast to many metalcone MLD films which are considered to be air sensitive as the organic backbone degrades upon air exposure. In addition, FTIR, X-Ray Reflectivity (XRR) and X-Ray Fluorescence (XRF) measurements show that the titanium carboxylate films remain intact upon immersion into a solution of 1 M LiClO4 in propylene carbonate, the liquid electrolyte used for electrochemical characterization. The electrochemical properties of a 5 nm TDMAT/oxalic acid, TDMAT/3,6-dioxaoctanedioic acid and TDMAT/glycerol film (conventional titanicone film [5]) are tested on top of three ideal electrode systems: anatase TiO2, TiN and LiMnO2 (LMO). The titanium carboxylate films are observed to have little to no effect on the lithium-ion kinetics of the TiO2 electrode system compared to the uncoated electrode. This is in contrast to the titanicone film displaying a detrimental effect on the kinetics. All films are observed to effectively suppress electrolyte oxidation when exposing the TiN electrode system to elevated potentials. On the LMO electrode an activation step is necessary for all films, after which a good lithium-ion mobility through the titanium carboxylate films is observed without the severe irreversible reactions detected in the potential profile for the titanicone films. Overall, the explorative tests on thin film electrodes in this work indicate that the electrochemical properties of the titanium carboxylate films seem promising candidates as protective and flexible coating of lithium-ion battery cathodes. [1] Vetter, J., Novák, P., Wagner, M. R., Veit, C., Möller, K. C., Besenhard, J. O., ... & Hammouche, A. (2005). Ageing mechanisms in lithium-ion batteries. Journal of power sources, 147(1-2), 269-281. [2] Ban, C., & George, S. M. (2016). Molecular layer deposition for surface modification of lithium‐ion battery electrodes. Advanced Materials Interfaces, 3(21), 1600762. [3] Zhao, Y., Zhang, L., Liu, J., Adair, K., Zhao, F., Sun, Y., ... & Sun, X. (2021). Atomic/molecular layer deposition for energy storage and conversion. Chemical Society Reviews, 50(6), 3889-3956. [4] Xue, Z., He, D., & Xie, X. (2015). Poly (ethylene oxide)-based electrolytes for lithium-ion batteries. Journal of Materials Chemistry A, 3(38), 19218-19253. [5] Van de Kerckhove, K., Mattelaer, F., Deduytsche, D., Vereecken, P. M., Dendooven, J., & Detavernier, C. (2016). Molecular layer deposition of “titanicone”, a titanium-based hybrid material, as an electrode for lithium-ion batteries. Dalton Transactions, 45(3), 1176-1184.

While recent high-profile assassination attempts have once again brought nerve agents (NAs) into the spotlight, the current portfolio of NA sensors lack a sufficient combination of high performance and field-deployability. Here, we report a novel optical sensor for the detection of gaseous NAs with a potential to fill this gap. The technique is based on Fourier transform spectroscopy with a supercontinuum (SC) light source and cantilever-enhanced photoacoustic detection providing fast multi-species gas sensing with high sensitivity and selectivity in a sample volume of 7 ml, which becomes advantageous when analysing limited NA samples in the field. We study the fundamental C–H stretch bands of four known NA simulants and achieve detection limits of 64–530 ppb in one minute and recovery times of a few minutes. In the near future, the technique has significant potential to improve through the development of more powerful SC sources further in the mid-infrared region. publishedVersion

We report here a systematic photoelectron spectroscopy (PES) and theoretical study of divalent transition metal (TM) EDTA complexes [EDTA·TM(ii)]2- (TM = V-Zn), along with the Ca(ii) species for comparison. Gaseous TM dianions (TM = Ca, Mn, Co, Ni, Cu and Zn) were successfully generated via electrospray ionization, and their PE spectra, with 157, 193, and 266 nm photons, were obtained at 20 K. The spectrum of each TM complex shows an extra peak at the lowest electron binding energy (eBE), compared to that of [EDTA·Ca(ii)]2-. DFT calculations indicate a hexacoordinated metal-EDTA binding motif for all complexes, from which the vertical detachment energies (VDEs) are calculated and these agree well with the experimental values. The calculations further predict negative or very small VDEs for TM(ii) = V, Cr, and Fe, providing a rational explanation for why these three dianionic species are not observed in the gas phase. Direct spectral comparison, electron spin density differences, and MO analyses indicate that the least bound electrons are derived from TM d electrons with appreciable ligand contributions, in contrast to [EDTA·Ca(ii)]2-, in which the detachment is entirely derived from the ligand. The extent of ligand modulation, i.e. non-innocence of EDTA ligands in the oxidation process, is found to vary across the 3rd row of TMs. Comparing the gas-phase VDEs of [EDTA·TM(ii)]2- with the 3rd ionization potentials of TMs and solution phase oxidation potentials reveals intrinsic correlations among these three quantities, with deviations being largely modulated by the ligand participation. The detailed microscopic information about the intrinsic electronic structures and bonding motifs of these complexes obtained in this work will help better understand the rich redox chemistries of these ubiquitous species under diverse environments. The present work, along with our previous studies, indicates that PES coupled with electrospray ionization is a unique ion spectroscopic tool that not only provides intrinsic electronic structure and bonding information about redox species, but also can predict the related electron transfer chemistries with quantitative capability. ispartof: FARADAY DISCUSSIONS vol:217 issue:0 pages:383-395 ispartof: location:England status: published

The added value of supervised Machine Learning (ML) methods to determine the Absolute Configuration (AC) of compounds from their Vibrational Circular Dichroism (VCD) spectra was explored. Among all ML methods considered, Random Forest (RF) and Feedforward Neural Network (FNN) yield the best performance for identification of the AC. At its best, FNN allows near-perfect AC determination, with accuracy of prediction up to 0.995, while RF combines good predictive accuracy (up to 0.940) with the ability to identify the spectral areas important for the identification of the AC. No loss in performance of either model is observed as long as the spectral sampling interval used does not exceed the spectral bandwidth. Increasing the sampling interval proves to be the best method to lower the dimensionality of the input data, thereby decreasing the computational cost associated with the training of the models.

Dr. Kletz is one the pioneers in the process safety area, known widely for his work on inherent safety design and loss prevention. He worked 38 years in Imperial Chemical Industries, and became a fulltime researcher only after his retirement. He published more than 200 papers and 15 books during his retirement. The intellectual basis analysis presented in this article shows that he frequently cited his books in his articles, indicating that his industrial experience was very influential to his scholarly contributions. Lawley, H.G. was one of the researchers whose work had most influence on Kletz's research. Among Dr. Kletz's publications, the article ‘What You Don't Have, Can't Leak’ has the highest impact, while his most influential book is ‘Process plants: A handbook for inherently safer design’. The references co-citation network is divided in two clearly connected components: his earlier work related to infra-red spectra, and his later work addressing process safety related topics, including inherent safety and hazard and accident analysis. Both his work and that of his followers is rooted in a similar intellectual basis within process safety research, in which particularly Dr. Kletz's earlier work forms an influential original body of knowledge rooted in his industrial experience. His career is a prime example of how process safety research has been strongly influenced by knowledge from industrial practice, illustrating that a continued strong connection between industry and academia can lead to very fruitful outcomes. It is hoped that the presented analysis can inspire especially young graduates with academic interests to first embark on an industrial career to gain industrial experience before aiming to contribute to academic process safety knowledge.

A solvometallurgical process for the separation of indium(iii) and zinc(ii) from ethylene glycol solutions using the ionic liquid extractants Cyphos IL 101 and Aliquat 336 in an aromatic diluent has been investigated. The speciation of indium(iii) in the two immiscible organic phases was investigated by Raman spectroscopy, infrared spectroscopy, EXAFS and 115In NMR spectroscopy. At low LiCl concentrations in ethylene glycol, the bridging (InCl3)2(EG)3 or mononuclear (InCl3)(EG)2 complex is proposed. At higher lithium chloride concentrations, the first coordination sphere changes to two oxygen atoms from one bidentate ethylene glycol ligand and four chloride anions ([In(EG)Cl4]-). In the less polar phase, indium(iii) is present as a tetrahedral [InCl4]- complex independent of the LiCl concentration. After the number of theoretical stages had been determined using a McCabe-Thiele diagram for extraction by Cyphos IL 101, the extraction and scrubbing processes were performed in lab-scale mixer-settlers to test the feasibility of working in continuous mode. Indium(iii) was extracted quantitatively in four stages, with 19% co-extraction of zinc(ii). The co-extracted zinc(ii) was scrubbed selectively in six stages using an indium(iii) scrub solution. Indium(iii) was recovered from the loaded less polar organic phase as indium(iii) hydroxide (98.5%) by precipitation stripping with an aqueous NaOH solution. ispartof: RSC ADVANCES vol:10 issue:41 pages:24595-24612 ispartof: location:England status: published

The reaction mechanism of the recently reported Me3AuPMe3-H-2 plasma gold ALD process was investigated using in situ characterization techniques in a pump-type ALD system. In situ RAIRS and in vacuo XPS measurements confirm that the CH3 and PMe3 ligands remain on the gold surface after chemisorption of the precursor, causing self-limiting adsorption. Remaining surface groups are removed by the H-2 plasma in the form of CH4 and likely as PHxMey groups, allowing chemisorption of new precursor molecules during the next exposure. The decomposition behaviour of the Me3AuPMe3 precursor on a Au surface is also presented and linked to the stability of the precursor ligands that govern the self-limiting growth during ALD. Desorption of the CH3 ligands occurs at all substrate temperatures during evacuation to high vacuum, occurring faster at higher temperatures. The PMe3 ligand is found to be less stable on a gold surface at higher substrate temperatures and is accompanied by an increase in precusor decomposition on a gold surface, indicating that the temperature dependent stability of the precursor ligands is an important factor to ensure self-limiting precursor adsorption during ALD. Remarkably, precursor decomposition does not occur on a SiO2 surface, in situ transmission absorption infrared experiments indicate that nucleation on a SiO2 surface occurs on Si-OH groups. Finally, we comment on the use of different co-reactants during PE-ALD of Au and we report on different PE-ALD growth with the reported O-2 plasma and H2O process in pump-type versus flow-type ALD systems.

This paper investigates the effect of KOH and NaOH on C-S-H structure and solubility. Both KOH and NaOH have a similar effect, they increase pH values and silicon concentrations, and decrease calcium concentrations. At higher alkali hydroxide concentrations, more portlandite precipitates, while amorphous silica dissolves. This increases the Ca/SiC-S-H at low Ca/Sitarget but lowers the maximum Ca/SiC-S-H from 1.5 to 1.2 in 1 M KOH/NaOH. The amount of alkalis bound in C-S-H increases with increasing alkali hydroxide concentrations and is higher at low Ca/SiC-S-H. KOH/NaOH lead to a structural rearrangement in C-S-H, increasing the interlayer distance, number of layers stacked in c direction and shortening the silica chains. The mean chain lengths (MCL) estimated from FTIR and Raman spectroscopy agree well with the trends from 29Si NMR. Comparison with the independently developed CASH+ thermodynamic model showed a good agreement between the observed and modelled changes, including the shortening of the MCL.

We compare mid-IR and ALMA far-IR images of 12 nearby Seyferts selected from GATOS. The mid-IR unresolved emission contributes more than 60% of the nuclear emission in most galaxies. By contrast, the ALMA 870micron continuum emission is mostly resolved and typically along the torus equatorial direction (Paper I, Garcia-Burillo et al. 2021). The Eddington ratios and nuclear hydrogen column densities NH of half the sample are favorable to launching polar and/or equatorial dusty winds, according to simulations. Six show mid-IR extended emission in the polar direction as traced by the NLR and perpendicular to the ALMA emission. In a few, the nuclear NH might be too high to uplift large quantities of dusty material along the polar direction. Five galaxies have low NH and/or Eddington ratios and thus polar dusty winds are not likely. We generate new CAT3D-WIND disk-wind model images. At low wind-to-disk cloud ratios the far-IR model images have disk- and ring-like morphologies. The X-shape associated with dusty winds is seen better in the far-IR at intermediate-high inclinations for the extended-wind configurations. In most models, the mid-IR emission comes from the inner part of the disk/cone. Extended bi-conical and one-sided polar mid-IR emission is seen in extended-wind configurations and high wind-to-disk cloud ratios. When convolved to our resolution, the model images reproduce qualitative aspects of the observed morphologies. Low-intermediate wind-to-disk ratios are required to account for the large fractions of unresolved mid-IR emission. This work and Paper I provide observational support for the torus+wind scenario. The wind component is more relevant at high Eddington ratios and/or AGN luminosities, and polar dust emission is predicted at NH of up to $10^{24}$cm$^{-2}$. The torus/disk component, on the other hand, prevails at low luminosities and/or Eddington ratios. (Abridged), 27 pages, 27 figures. Accepted for publication in A&A

An integrated study involving sedimentology, mineral chemistry and spectroscopy highlights a distinctive compositional evolution of Cretaceous glauconite within the Ukra Hill Member. Glauconite occurs at the top part of transgressive systems tract deposits built on a marine shelf. The concentration of glauconite steadily increases towards the maximum flooding surface, maximizing around 50%, and sharply falls at the onset of progradation. Unlike most Phanerozoic examples, Ukra glauconite forms by the variable degree of replacement of quartz, feldspar and mica grains. XRD, FEG-SEM and spectroscopy of glauconite pellets indicate an 'evolved' stage of maturation. Mossbauer spectroscopy reflects a minor substitution of Al3+-Fe3+ (total) in tetrahedral sites and significant substitution of the same in octahedral sites. A consistently high value of 1(20 as well as Fe2O3 contradicts the two popular theories, 'layer lattice' and 'verdissement', and support replacement origin of glauconite in a high a(si+) and high a(K+) pore water environment. Incipiently formed glauconite records a marginal increase in K2O content accompanied by release of Al2O3 and SiO2 to form evolved glauconite pellets; those forming within quartz grains involve an addition of Fe2O3 (total) content during maturation. The minimal increase in K2O content of incipiently formed glauconite, best exhibited by those formed within quartz grains is possibly related to stratigraphic condensation. Compositional evolution like this is exhibited by Precambrian glauconites involving abiotic substrates, but is unusual for the Phanerozoic. Original K2O and Fe2O3 (total) content of glauconites is reduced around peripheries and fractures during diagenesis, adding to compositional variability. (C) 2017 Elsevier Ltd. All rights reserved.

We present ground and excited state frequency calculations of the recently discovered extremely red-shifted chlorophyll f. We discuss the experimentally available vibrational mode assignments of chlorophyll f and chlorophyll a which are characterised by particularly large downshifts of 131-keto mode in the excited state. The accuracy of excited state frequencies and their displacements are evaluated by the construction of Franck&ndash, Condon (FC) and Herzberg&ndash, Teller (HT) progressions at the CAM-B3LYP/6-31G(d) level. Results show that while CAM-B3LYP results are improved relative to B3LYP calculations, the displacements and downshifts of high-frequency modes are underestimated still, and that the progressions calculated for low temperature are dominated by low-frequency modes rather than fingerprint modes that are Resonant Raman active.

International audience; We present a detailed analysis of the X-ray absorption near-edge structure (XANES) data on the Fe K-edge of CO Myoglobin based on a combined procedure of Molecular Dynamics (MD) calculations and MXAN (Minuit XANes) data analysis that we call D-MXAN. The ability of performing quantitative XANES data analysis allows us to refine classical force field MD parameters, thus obtaining a reliable tool for the atomic investigation of this important model system for biological macromolecules. The iterative procedure here applied corrects the greatest part of the structural discrepancy between classical MD sampling and experimental determinations. Our procedure, moreover, is able to discriminate between different heme conformational basins visited during the MD simulation, thus demonstrating the necessity of a sampling on the order of tens of nanoseconds, even for an application such X-ray absorption spectroscopy data analysis. © 2018 Author(s).

Using reflection-absorption infrared spectroscopy (RAIRS), we show that solids displaying spontaneous dipole orientation possess quite general non-local and non-linear characteristics, exemplified through their internal electric fields. The most graphic illustration of this, uncovered originally through electron beam studies, may be found in films of cis-methyl formate (cis-MF), for which data demonstrated the counter-intuitive property that the degree of dipole order in the film does not monotonically decrease as the temperature of deposition rises, but rather increases sharply above similar to 77 K. Here we show how RAIRS provides independent evidence to support this conclusion. These new data confirm (i) that the behaviour of spontelectrics is governed by an expression for the degree of dipole orientation, which is continuous in temperature, but with a discontinuity in the derivative, and (ii) that the temperature of deposition associated with this discontinuity matches the temperature above which dipole order switches from the expected reduction with temperature to an increase with temperature.

In the valorisation of lignin, the application of catalytic hydrogen transfer reactions (e.g. in catalytic upstream biorefining or lignin-first biorefining) has brought a renewed interest in the fundamental understanding of hydrogen-transfer processes in the defunctionalisation of lignin-derived phenolics. In this report, we address fundamental questions underlining the distinct reactivity patterns of positional isomers of guaiacol towards H-transfer reactions in the presence of RANEY® Ni and 2-PrOH (solvent and H-donor). We studied the relationship between reactivity patterns of 2-, 3- and 4-methoxyphenols and their interactions at the liquid–solid interface of RANEY® Ni as probed by attenuated total reflection infrared (ATR-IR) spectroscopy. Regarding the reactivity patterns, 2-methoxyphenol or guaiacol is predominantly converted into cyclohexanol through a sequence of reactions including demethoxylation of 2-methoxyphenol to phenol followed by hydrogenation of phenol to cyclohexanol. By contrast, for the conversion of the two non-lignin related positional isomers, the corresponding 3- and 4-methoxycyclohexanols are the major reaction products. The ATR-IR spectra of the liquid–solid interface of RANEY® Ni revealed that the adsorbed 2-methoxyphenol assumes a parallel orientation to the catalyst surface, which allows a strong interaction between the methoxy C–O bond and the surface. Conversely, the adsorption of 3- or 4-methoxyphenol leads to a tilted surface complex in which the methoxy C–O bond establishes no interaction with the catalyst. These observations are also corroborated by a smaller activation entropy found for the conversion of 2-methoxyphenol relative to those of the other two positional isomers.

International audience; The soil chromophyte alga Xanthonema (X.) debile contains only non-carbonyl carotenoids and Chl-a. X. debile has an antenna system denoted Xanthophyte light-harvesting complex (XLH) that contains the carotenoids diadinoxanthin, heteroxanthin, and vaucheriaxanthin. The XLH pigment stoichiometry was calculated by chromatographic techniques and the pigment-binding structure studied by resonance Raman spectroscopy. The pigment ratio obtained by HPLC was found to be close to 8:1:2:1 Chl-a:heteroxanthin:diadinoxanthin:vaucheriaxanthin. The resonance Raman spectra suggest the presence of 8-10 Chl-a, all of which are 5-coordinated to the central Mg, with 1-3 Chl-a possessing a macrocycle distorted from the relaxed conformation. The three populations of carotenoids are in the all-trans configuration. Vaucheriaxanthin absorbs around 500-530nm, diadinoxanthin at 494nm and heteroxanthin at 487nm at 4.5K. The effective conjugation length of heteroxanthin and diadinoxanthin has been determined as 9.4 in both cases; the environment polarizability of the heteroxanthin and diadinoxanthin binding pockets is 0.270 and 0.305, respectively.

The nebular-epoch spectrum of the rapidly declining, "transitional" type Ia supernova (SN) 2007on showed double emission peaks, which have been interpreted as indicating that the SN was the result of the direct collision of two white dwarfs. The spectrum can be reproduced using two distinct emission components, one red-shifted and one blue shifted. These components are similar in mass but have slightly different degrees of ionization. They recede from one another at a line-of-sight speed larger than the sum of the combined expansion velocities of their emitting cores, thereby acting as two independent nebulae. While this configuration appears to be consistent with the scenario of two white dwarfs colliding, it may also indicate an off-centre delayed detonation explosion of a near Chandrasekhar-mass white dwarf. In either case, broad emission line widths and a rapidly evolving light curve can be expected for the bolometric luminosity of the SN. This is the case for both SNe 2007on and 2011iv, also a transitional SN Ia which exploded in the same elliptical galaxy, NGC 1404. Although SN 2011iv does not show double-peaked emission line profiles, the width of its emission lines is such that a two-component model yields somewhat better results than a single-component model. Most of the mass ejected is in one component, however, which suggests that SN 2011iv was the result of the off-centre ignition of a Chandrasekhar-mass white dwarf., Comment: Accepted for publication in MNRAS

Lanthanides are extracted to basic nitrate-based extractants, like trihexyl(tetradecyl)phosphonium nitrate, as pentanitrato lanthanide complexes., A speciation study was carried out for lanthanide complexes formed in the organic phase after solvent extraction with quaternary ammonium and phosphonium nitrate extractants. These extractants are liquid at room temperature and were applied in their undiluted form. A comparison was made between the quaternary compound trihexyl(tetradecyl)phosphonium nitrate, the nitrate form of the commercial extractant Cyphos IL 101, and Aliquat 336 nitrate, the nitrate form of the commercial trialkylmethylammonium chloride extractant Aliquat 336 (alkyl = mixture of C8 and C10 chains). The structures of the lanthanide complexes across the entire lanthanide series (with the exception of promethium) were determined by a combination of solvent extraction techniques, FTIR, NMR, high-resolution steady-state luminescence spectroscopy, luminescence life time measurements, elemental analysis and EXAFS spectroscopy. The results suggest that the lanthanide ions form an anionic nitrate complex in the organic phase by coordinating with five bidentate nitrate ligands. Charge neutralization is provided by two counter cations of the extractant present in the outer coordination sphere of the complex. Furthermore, it is suggested that the pentanitrato complex is the sole lanthanide species that is formed in significant concentrations in the organic phase.

One-step synthesis using only physical tools is an appealing “green” method for the realization of technological materials. High-pressure conditions are particularly suitable in the attainment of extended supramolecular networks and in combination with high-temperature are effective in selecting specific reaction pathways to increase product quality. Here we show how pressures below 3 GPa and temperatures on the order of 420 K are effective for the synthesis, from urea crystal phase IV, of 2D graphitic carbon nitride oxide with enhanced crystalline quality. Angle-dispersive X-ray diffraction and Fourier transform IR spectroscopy show that the reaction becomes less selective at higher pressure with the formation of melamine and ammonium carbamate as byproducts. An anomalous positive slope is shown by the P–T instability boundary, likely arising from unfavorable hydrogen bonding with respect to the topochemical path, making urea an interesting case study for gaining insight into the role of hydrogen bonding in solid-state reactivity.

Crystalline ice formation requires water molecules to be sufficiently mobile to find and settle on the thermodynamically most stable site. Upon cooling, however, diffusion and rearrangement become increasingly kinetically difficult. Water ice grown by the condensation of water vapor in laboratory is thus generally assumed to be in a metastable amorphous form below 100 K. Here, we demonstrate the possibility of crystalline ice formation at extremely low temperature using a water/neon matrix (1/1000, 30 000 monolayers) prepared at 6 K, which is subsequently warmed to 11–12 K. In situ infrared spectroscopy revealed the assembly of the dispersed water molecules, forming crystalline ice I during the sublimation of the neon matrix for 40–250 seconds. This finding indicates that the high mobility of the water molecules during matrix sublimation can overcome the kinetic barrier to form crystals even at extremely low temperature.

The molecular structure, vibrational spectra and photochemistry of 5-methylhydantoin (C4H6N2O2; 5-MH) were studied by matrix isolation infrared spectroscopy and theoretical calculations at the DFT(B3LYP)/6-311++G(d,p) theory level. The natural bond orbital (NBO) analysis approach was used to study in detail the electronic structure of the minimum energy structure of 5-MH, namely the specific characteristics of the sigma and pi electronic systems of the molecule and the stabilizing orbital interactions. UV irradiation of 5-MH isolated in argon matrix resulted in its photofragmentation through a single photochemical pathway, yielding isocyanic acid, ethanimine, and carbon monoxide, thus following a pattern already observed before for the parent hydantoin and 1-methylhydantoin molecules. The investigation of the thermal properties of 5-MH was undertaken by differential scanning calorimetry (DSC), polarized light thermal microscopy (PLTM) and Raman spectroscopy. Four different polymorphs of 5-MH were identified. The crystal structure of one of the polymorphs, for which it was possible to grow up suitable crystals, was determined by X-ray diffraction (XRD). Two of the additional polymorphs were characterized by powder XRD, which confirmed the molecules pack in different crystallographic arrangements.

The spontelectric state of matter is exemplified by the presence of static, spontaneous electric fields extending throughout thin films of dipolar solids. The spontelectric state was discovered using a low energy electron beam technique, using the ASTRID storage ring at Aarhus University. Following a resume of the characteristics and of a model for the spontelectric effect, a description is given of the counter-intuitive behaviour of fields in films of methyl formate as a function of deposition temperature, T. It is found that films for T ≤ 77.5 K show the expected decrease in the field with increasing T but, for T ≥ 77.5 K, an increase in the field for higher T is revealed. Analysis of these results illustrates the non-linear and non-local characteristics of the spontelectric state. Recently it has been shown that Reflection-Absorption Infrared Spectroscopy (RAIRS) provides a new and independent technique for the detection of the spontelectric effect, through the observation of vibrational Stark shifts in spectra of films. Stark shifts for nitrous oxide are demonstrated to be in harmony with electric fields measured using the electron beam technique. The method is then applied to carbon monoxide, showing that this material displays the spontelectric effect between deposition temperatures of 20 K and 26 K.

We present a search for metal absorption line systems at the highest redshifts to date using a deep (30h) VLT/X-Shooter spectrum of the z = 7.084 quasi-stellar object (QSO) ULAS J1120+0641. We detect seven intervening systems at z > 5.5, with the highest-redshift system being a C IV absorber at z = 6.51. We find tentative evidence that the mass density of C IV remains flat or declines with redshift at z < 6, while the number density of C II systems remains relatively flat over 5 < z < 7. These trends are broadly consistent with models of chemical enrichment by star formation-driven winds that include a softening of the ultraviolet background towards higher redshifts. We find a larger number of weak ( W_rest < 0.3A ) Mg II systems over 5.9 < z < 7.0 than predicted by a power-law fit to the number density of stronger systems. This is consistent with trends in the number density of weak Mg II systems at z = 2.5, and suggests that the mechanisms that create these absorbers are already in place at z = 7. Finally, we investigate the associated narrow Si IV, C IV, and N V absorbers located near the QSO redshift, and find that at least one component shows evidence of partial covering of the continuum source., 18 pages, 23 figures, accepted for publication in MNRAS

The electric field experienced by an acid molecule in the acid-water cluster depends on its local environment comprising of surrounding water molecules. A critical field of about 193 and 163 MV cm(-1) is required for the dissociation of HCl and HBr, respectively, and is associated with the arrangement of water molecules around the acid. The critical field required for dissociation of isolated HCl and HBr is 510 and 462 MV cm(-1), respectively. Hence the solvation of the proton and the halide anion by water molecules substantially lowers the critical electric field by about 300 MV cm(-1), relative to vacuum.

This work describes a mid-infrared (MIR) metabolic profiling study of 2nd trimester amniotic fluid in relation to selected prenatal disorders, with results focusing on fetal malformations (FM), preterm delivery (PTD) and premature rupture of membranes (PROM), the latter two conditions occurring later in pregnancy. Partial least squares-discriminant analysis (PLS-DA) models were obtained for FM and pre-PTD subject groups, supported by Monte Carlo Cross Validation (MCCV), and identified specific MIR profile changes. For pre-PROM subjects, minor changes were noted. MIR interpretation was assisted by intra(MIR/MIR) and inter- (MIR/NMR) domain statistical correlation analysis, the results unveiling possible biomarker MIR signatures for FM and pre-PTD subjects. Biofluid MIR metabolic profiling holds enticing possibilities as a low cost, easy to use, rapid method and the results presented have shown its sensitivity to clinically diagnosed conditions such as FM, and to the pre-clinical stages of PTD. Specific improvement needs are discussed, namely regarding sample numbers and experimental reproducibility. (C) 2012 Elsevier B.V. All rights reserved.

This study focuses on changes in the structure of ionomer membranes, provided by the 3M Fuel Cells Component Group, as a function of the equivalent weight (EW) and the relationship between the structure and the properties of the membrane. Wide-angle X-ray diffraction results showed evidence of both non-crystalline and crystalline ordered hydrophobic regions in all the EW membranes except the 700 EW membrane. The spectral changes evident in the vibrational spectra of the 3M membranes can be associated with two major phenomena: (1) dissociation of the proton from the sulfonic acid groups even in the presence of small amounts of water; and (2) changes in the conformation or the degree of crystallinity of the poly(tetrafluoroethylene) hydrophobic domains both as a function of EW and membrane water content. All the membranes, regardless of EW, are thermally stable up to 360 °C. The wet membranes have conductivities between 7 and 20 mS/cm at 125 °C. In this condition, the conductivity values follow VTF behavior, which suggests that the proton migration occurs via proton exchange processes between delocalization bodies (DBs) that are facilitated by the dynamics of the host polymer. The conductivity along the interface between the hydrophobic and hydrophilic domains makes a larger contribution in the smaller EW membranes likely due to the existence of a greater number of interfaces in the membrane. The larger crystalline domains present in the higher EW membranes provide percolation pathways for charge migration between DBs, which reduces the probability of charge transfer along the interface. Therefore, at higher EWs although there is charge migration along the interface within the hydrophobic-hydrophilic domains, the exchange of protons between different DBs is likely the rate-limiting step of the overall conduction process.

The reactions of coronene dehydrogenation and fusion upon heat treatment in the temperature range of 500-700 degrees C were studied using XRD, TEM, Raman, IR, and NEXAFS spectroscopy. The formation of a coronene dimer (dicoronylene) was observed at temperatures 530-550 degrees C; dicoronylene can easily be separated using sublimation with a temperature gradient. An insoluble and not sublimable black precipitate was found to form at higher temperatures. Analysis of the data shows that dimerization of coronene is followed at 550-600 degrees C by oligomerization into larger molecules. Above 600 degrees C amorphization of the material and formation of graphitic nanoparticles was observed. Coronene fusion by annealing is proposed as a road to synthesis of larger polycyclic aromatic hydrocarbons and nanographenes.

Hydrazine and two linear diamines, H2N-(CH2)n-NH2 (n = 2 and 6), were reacted with (hexadecylamine/stearate)-capped CdSe nanoparticles (7.5 nm diameter) to form multilayers on ITO glass via layer-by-layer alternation. The new materials were investigated by cyclic voltammetry (CV), UV-vis and FTIR spectroscopies, and photoconductivity. FTIR analysis of multilayer growth showed the complete removal of both L (hexadecylamine) and X (stearate) caps; the latter occurred via complexation of the external cadmium layer. Bulk CdSe/hydrazine polymer, obtained from treatment of a CdSe nanocrystal (CdSe-NC) dispersion with excess hydrazine, included massive amounts of hydrazine in a N2H4/CdSe molar ratio of approximately 24. On the contrary, CV analysis showed that hydrazine covers the NC surface of multilayers with approximately 2x10-9 mol cm-2; specifically, the N2H4/CdSe molar ratio was much lower (ca. 0.5). FTIR analysis of bulk CdSe/diamine polymers showed the same NC surface coverage, (1-2)X10-9 mol cm-2, of the CdSe/hydrazine multilayers. The shortest hydrazine linker results in the highest photocurrent values. Diamines display lower photoconductivity values, decreasing as the N-N distance is increased.

Electronic excitation spectra of the S(1)← S(0) transition obtained by resonance-enhanced two-photon ionization (REMPI) are analysed for phenol-Ar(n) (PhOH-Ar(n)) clusters with n≤ 4. An additivity rule has been established for the S(1) origin shifts upon sequential complexation at various π binding sites, which has allowed for the identification of two less stable isomers not recognized previously, namely the (2/0) isomer for n = 2 and the (2/1) isomer for n = 3. Infrared (IR) spectra of neutral PhOH-Ar(n) and cationic PhOH(+)-Ar(n) clusters are recorded in the vicinity of the OH and CH stretch fundamentals (ν(OH), ν(CH)) in their S(0) and D(0) ground electronic states using IR ion dip spectroscopy. The small monotonic spectral redshifts Δν(OH) of about -1 cm(-1) per Ar atom observed for neutral PhOH-Ar(n) are consistent with π-bonded ligands. In contrast, the IR spectra of the PhOH(+)-Ar(n) cations generated by resonant photoionization of the neutral precursor display the signature of H-bonded isomers, suggesting that ionization triggers an isomerization reaction, in which one of the π-bonded Ar ligands moves to the more attractive OH site. The dynamics of this isomerization reaction is probed for PhOH(+)-Ar(3) by picosecond time-resolved IR spectroscopy. Ionization of the (3/0) isomer of PhOH(+)-Ar(3)(3π) with three π-bonded Ar ligands on the same side of the aromatic ring induces a π→ H switching reaction toward the PhOH(+)-Ar(3)(H/2π) isomer with a time constant faster than 3 ps. Fast intracluster vibrational energy redistribution prevents any H →π back reaction.

Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich. This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively. The dynamics of the intermolecular motion of the phenol+–Kr cation generated by photoionization of the neutral π-structure is probed by picosecond time-resolved infrared spectroscopy. The spectrum at zero delay displays only the free OH stretch band of the π-structure. The appearance of the hydrogen-bonded OH stretch band of the H-structure after a few ps is due to ionization-induced π → H site switching. Spectra at long delay (>20 ns) show that the Kr atom delocalizes from one π-site of the aromatic ring to the opposite π-site via the OH-site, like a pendular motion in the classical picture.

A large-size 1-naphthol cluster, (1-NpOH)(n), with n ≤ 30 was prepared by using a high-pressure pulsed valve. The electronic and vibrational transitions of (1-NpOH)(n) with n = 3-9 were measured by resonant two-photon ionization (R2PI) and ion-detected IR dip spectroscopies. The S(1) ← S(0) R2PI spectrum shows partially resolved structures around the origin band in the (1-NpOH)(n) cluster with n = 3-8. The (1-NpOH)(3) and the (1-NpOH)(6) clusters show relatively sharp origin bands. The structure of (1-NpOH)(3) was determined by comparison of the IR dip spectrum with the simulated one by DFT calculation, while those of (1-NpOH)(n) (n ≥ 4) were discussed in terms of topological geometries of a hydrogen-bonded network. Those analyses suggest that (i) the (1-NpOH)(3) cluster has the cyclic structure where three 1-NpOH monomers are linked by both the hydrogen-bonding and the π···C-H interaction between naphthyl rings and (ii) the (1-NpOH)(n) cluster with n ≥ 4 is built up by attaching the 1-NpOH monomers to the (1-NpOH)(3) core.

In this study, in which the group vibrations of 3-aminophenylacetic acid were investigated by electronic structure calculations based on Density Functional Theory (DFT), the possible stable conformers of the molecule were searched through a relaxed "potential energy surface scan" carried out at B3LYP/6-31G(d) level of theory. The corresponding equilibrium geometrical and vibrational spectral data for each of the determined stable conformers and for their ipossible dimer structures were obtained through "geometry optimisation" and "frequency" calculations carried out at B3LYP/6-31G(d) and B3LYP/6-311G++(d,p) levels of theory. The obtained results confirmed that anharmonic wavenumbers calculated at B3LYP/6-311G++(d,p) level generally quite well agree with the experimental wavenumbers, however, harmonic wavenumbers calculated at both levels of theory need an efficient refinement for a satisfactory agreement with experiment. In particular, the harmonic wavenumbers, IR and Raman intensities refined within Scaled Quantum Mechanical Force Field (SQM FF) methodology constituted the primary data set in the interpretatiori of the experimental FT-IR, FT-Raman and dispersive Raman spectra of 3-aminophenylacetic acid. By the help of these refined spectral data, the effects of conformation and intermolecular hydrogen bonding on the fundamental bands observed in the experimental spectra could be correctly predicted. (C) 2015 Elsevier B.V. All rights reserved.

The reactivity of palladium acetate inside a poly(4-vinylpyridine-co-divinylbenzene) polymer is strongly influenced by the establishment of interaction between the Pd precursor and the pyridyl functional group in the polymer. Diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and simultaneous X-ray absorption near edge structure (XANES) and small angle X-ray scattering (SAXS) techniques have been applied to monitor the reactivity of palladium acetate in the presence of H-2 and CO as a function of temperature. H-2 reduces palladium acetate to Pd nanoparticles and acetic acid. The pyridyl groups in the polymer play a vital role both in stabilizing the formed acetic acid, thus allowing its detection by means of DRIFTS, and the final Pd nanoparticles, which are extremely small and mono-dispersed. On the contrary, CO does not reduce palladium acetate. Rather, it forms Pd2+ carbonyl adducts, which favor the detachment of the acetate ligands and their thermal degradation. These adducts are well observable by means of SAXS because they cause an important local change of the electronic density.

The reactions of L-enantiopure alpha-amino acids (aaH) with Na2MoO4 led to the high-yield isolation of Mo(VI) complexes of general formula Mo2O4(OH)4(aaH). A similar outcome was achieved by using (NH4)6Mo7O24 in the place of Na2MoO4. Solid-state IR and NMR spectroscopy indicated the presence of cis-MoO2 units linked by a zwitterionic amino acid ligand, via a bidentate bridging coordination through the carboxylate group. Thus possible dinuclear and polynuclear structures are proposed on the basis of DFT calculations.

Structural calculations by means of the density functional method have been performed on tetraoxaporphyrin dication and on isoelectronic diprotonated porphyrin as well as on the sulfur and carbon analogues of porphyrin. A detailed study of the stable conformations of these compounds is reported starting with the most symmetrical conformations and lowering the symmetry along the vibrational coordinates with imaginary frequency. The calculated geometries are related to experimental structures available from X-ray diffraction studies. The Raman spectra of tetraoxaporphyrin dication exciting with micro-Raman instrumentation at 785 nm and of diprotonated porphyrin in near-resonance conditions with the Soret band have been measured. The correlation between frequencies calculated with the DF/B3-LYP/cc-pVDZ procedure for porphyrin, diprotonated porphyrin, and tetraoxaporphyrin dication has allowed for making a vibrational assignment for the latter two systems in excellent agreement with experiment using a single frequency scale factor.

Four potato cellulose synthase (CesA) homologs (StCesA1, 2, 3 and 4) were isolated by screening a cDNA library made from developing tubers. Based on sequence comparisons and the fact that all four potato cDNAs were isolated from this single cDNA-library, all four StCesA clones are likely to play a role in primary cell wall biosynthesis. Several constructs were generated to modulate cellulose levels in potato plants in which the granule-bound starch synthase promoter was used to target the modification to the tubers. The StCesA3 was used for up- and down-regulation of the cellulose levels by sense (SE-StCesA3) and antisense (AS-StCesA3) expression of the complete cDNA. Additionally, the class-specific regions (CSR) of all four potato cellulose synthase genes were used for specific down-regulation (antisense) of the corresponding CesA genes (csr1, 2, 3 and 4). None of the transformants showed an overt developmental phenotype. Sections of tubers were screened for altered cell wall structure by Fourier Transform Infrared microspectroscopy (FTIR) and exploratory Principal Component Analysis (PCA), and those plants discriminating from WT plants were analysed for cellulose content and monosaccharide composition. Several transgenic lines were obtained with mainly decreased levels of cellulose. These results show that the cellulose content in potato tubers can be reduced down to 40% of the WT level without affecting normal plant development, and that constructs based on the CSR alone are specific and sufficient to down-regulate cellulose biosynthesis. (C) 2004 Elsevier Ltd. All rights reserved.

Titan's middle atmosphere is currently experiencing a rapid change of season after northern spring arrived in 2009. A large cloud was observed for the first time above Titan's southern pole in May 2012, at an altitude of 300 km. This altitude previously showed a temperature maximum and condensation was not expected for any of Titan's atmospheric gases. Here we show that this cloud is composed of micron-sized hydrogen cyanide (HCN) ice particles. The presence of HCN particles at this altitude, together with new temperature determinations from mid-infrared observations, indicate a very dramatic cooling of Titan's atmosphere inside the winter polar vortex in early 2012. Such a cooling is completely contrary to previously measured high-altitude warming in the polar vortex, and temperatures are a hundred degrees colder than predicted by circulation models. Besides elucidating the nature of Titan's mysterious polar cloud, these results thus show that post-equinox cooling at the winter pole is much more efficient than previously thought., Published in Nature on 2 October 2014. This is the author version, before final editing by Nature

International audience; We present scaling laws for absolute cross sections for non-statistical fragmentation in collisions between Polycyclic Aromatic Hydrocarbons (PAH/PAH(+)) and hydrogen or helium atoms with kinetic energies ranging from 50 eV to 10 keV. Further, we calculate the total fragmentation cross sections (including statistical fragmentation) for 110 eV PAH/PAH(+) + He collisions, and show that they compare well with experimental results. We demonstrate that non-statistical fragmentation becomes dominant for large PAHs and that it yields highly reactive fragments forming strong covalent bonds with atoms (H and N) and molecules (C6H5). Thus nonstatistical fragmentation may be an effective initial step in the formation of, e. g., Polycyclic Aromatic Nitrogen Heterocycles (PANHs). This relates to recent discussions on the evolution of PAHNs in space and the reactivities of defect graphene structures.

The reaction of cobalt(II) chloride hexahydrate and pyrazine in a reduced amount of water under hydrothermal conditions affords [CoCl(2)pyz](n), which crystallises in an orthorhombic unit cell (a = 12.0014, b = 7.1040, c = 3.5380 angstrom), space group Cmmm. Fourier transform infrared spectroscopy confirms the coordination of pyrazine to Co(II) in an octahedral geometry. This compound is thermally stable in air up to 320 degrees C and may also be obtained by the single-step decomposition of [CoCl2(pyz)(2)](n) at 190 degrees C, with an activation energy of 121 kJ mol(-1). [CoCl(2)pyz](n) contains Co(II) chains bridged by two chloride ions making an angle of 92.21 degrees, leading to orthogonal (d-p) orbitals and to one-dimensional ferromagnetic chains. In contrast, in [CoCl2(pyz)(2)](n) only pyrazine bridges the Co(II) ions, setting them apart and resulting in a purely paramagnetic system. Because the simple contact with a pyrazine vapour or aqueous pyrazine reintroduces this molecule into [CoCl(2)pyz](n), while heating [CoCl2(pyz)(2)](n) removes pyrazine affording [CoCl(2)pyz](n), the magnetic behaviour may be reversibly switched between the two states.

In this study we have examined 42 [(L)M(CO)(n)](+/-/0) complexes (M = Ni and Au), including neutral ligands, such as phosphines and carbenes, and anionic ones. For each complex, the carbonyl stretching frequency (nu(CO)) and the amount of charge donated from the ligand to the metal (CT) have been computed on the basis of DFT calculations. For nickel complexes, the two observables nicely correlate with each other, as expected from the theory underlying the Tolman electronic parameter. On the contrary, for gold complexes a more complex pattern can be observed, with an apparent differentiation between phosphine ligands and carbon-based ones. Such differences have been explained analyzing the AuL bond in terms of Dewar-Chatt-Duncanson bonding constituents (sigma donation and pi back-donation). Our analysis demonstrates that in linear gold(I) complexes, nu(CO) depends only on the metal-to-ligand pi back-donation.

Protolysis of alkylaluminum compounds with silsesquioxanes is an efficient procedure to synthesize both Lewis and Bronsted acidic aluminosilsesquioxanes. Treatment of AlEt3 with (c-C5H9)(7)Si7O9(OH)(3) and (c-C5H9)(7)Si7O9(OSiMe3)(OH)(2) gives the corresponding Lewis acidic aluminosilsesquioxanes, {[ (c-C5H9)(7)Si7O12]Al}(n) (1) and [ (c-C5H9)(7)Si7O11(OSiMe3)]AlEt . NEt3 (2). By allowing AlEt3 to react with two equivalents of (C-C5H9)(7)Si7O9(OSiMe3)(OH)(2), the Bronsted acidic aluminosilsesquioxane [(c-C5H9)(7)Si7O11(OSiMe3)]Al[(c-C5H9)(7)Si7O10(OSiMe3)(OH)] (3) is selectively formed. H-1 NMR and IR spectroscopy and density functional theory (DFT) calculations show that complex 3 contains a strong intramolecular hydrogen bond. Although the high strength of this hydrogen bond reduces the Bronsted acidity of 3 substantially, 3 can easily be deprotonated by amines to yield the corresponding ammonium salts {[(cC(3)H(9))(7)Si7O11(OSiMe3)](2)Al}-X+ (X = Et3NH 4a, PhN(H)Me-2 4b, C5H5NH 4c). The X-ray crystal structure of 4a demonstrates that the ammonium cation is bonded to the aluminosilsesquioxane anion by a hydrogen bond. The corresponding lithium salt {[(c-C5H9)(7)Si7O11(OSiMe3)](2)Al}(-){Li . 2THF}(+) (5) could best be prepared by protolysis of (c-C5W9)(7)Si7O9(OSiMe3)(OH)(2) with half an equivalent of LiAlH4.

Protolysis of alkylaluminum compounds with silsesquioxanes is an efficient procedure to synthesize both Lewis and Bronsted acidic aluminosilsesquioxanes. Treatment of AlEt3 with (c-C5H9)(7)Si7O9(OH)(3) and (c-C5H9)(7)Si7O9(OSiMe3)(OH)(2) gives the corresponding Lewis acidic aluminosilsesquioxanes, {[ (c-C5H9)(7)Si7O12]Al}(n) (1) and [ (c-C5H9)(7)Si7O11(OSiMe3)]AlEt . NEt3 (2). By allowing AlEt3 to react with two equivalents of (C-C5H9)(7)Si7O9(OSiMe3)(OH)(2), the Bronsted acidic aluminosilsesquioxane [(c-C5H9)(7)Si7O11(OSiMe3)]Al[(c-C5H9)(7)Si7O10(OSiMe3)(OH)] (3) is selectively formed. H-1 NMR and IR spectroscopy and density functional theory (DFT) calculations show that complex 3 contains a strong intramolecular hydrogen bond. Although the high strength of this hydrogen bond reduces the Bronsted acidity of 3 substantially, 3 can easily be deprotonated by amines to yield the corresponding ammonium salts {[(cC(3)H(9))(7)Si7O11(OSiMe3)](2)Al}-X+ (X = Et3NH 4a, PhN(H)Me-2 4b, C5H5NH 4c). The X-ray crystal structure of 4a demonstrates that the ammonium cation is bonded to the aluminosilsesquioxane anion by a hydrogen bond. The corresponding lithium salt {[(c-C5H9)(7)Si7O11(OSiMe3)](2)Al}(-){Li . 2THF}(+) (5) could best be prepared by protolysis of (c-C5W9)(7)Si7O9(OSiMe3)(OH)(2) with half an equivalent of LiAlH4.

Yilmaz, Veysel/0000-0002-2849-3332 WOS: 000318209100017 PubMed: 23466323 A new palladium(II) complex, [Pd(ppeieo)(inap)]center dot DMSO (ppeieo = (1E,2E)-phenyl-[(1-phenylethyl)imino]-ethanal oxime and imp = isonitrosoacetophenone) has been synthesized and characterized by elemental analysis, UV-vis, IR, NMR. X-ray diffraction analysis of the DMSO solvate of the complex shows that the palladium(II) ion is coordinated in a distorted square-planar geometry by ppeieo and map, which is formed during the hydrolysis of ppeieo. DFT (B3LYP/LANL2DZ) calculations on the complex have been carried out to correlate geometry and spectroscopic properties such as electronic, vibrational and NMR chemical shifts. The complete vibrational frequency assignments were made and the calculation results were applied to simulate infrared spectra of the title compound which shows good agreement with observed spectra. The calculated HOMO and LUMO energies show that several transitions including the pi -> pi* and charge transfer occur within the molecule. The chemical shifts reasonably correspond to the calculated spectra. (c) 2013 Elsevier B.V. All rights reserved. Uludag UniversityUludag University This work is a part of a Research Project OUAP(F)-2012/12. We thank Uludag University for the financial support given to the project.

Astronomy and Astrophysics 553 (2013): A5 reproduced with permission from Astronomy and Astrophysics, Context. We have analysed far-infrared spectra of 32 circumstellar disks around Herbig Ae/Be and T Tauri stars obtained within the Herschel key programme Dust, Ice and Gas in Time (DIGIT). The spectra were taken with the Photodetector Array Camera and Spectrometer (PACS) on board the Herschel Space Observatory. In this paper we focus on the detection and analysis of the 69 μm emission band of the crystalline silicate forsterite. Aims. This work aims at providing an overview of the 69 μm forsterite bands present in the DIGIT sample. We use characteristics of the emission band (peak position and FWHM) to derive the dust temperature and to constrain the iron content of the crystalline silicates. With this information, constraints can be placed on the spatial distribution of the forsterite in the disk and the formation history of the crystalline grains. Methods. The 69 μm forsterite emission feature is analysed in terms of position and shape to derive the temperature and composition of the dust by comparison to laboratory spectra of that band. The PACS spectra are combined with existing Spitzer IRS spectra and we compare the presence and strength of the 69 μm band to the forsterite bands at shorter wavelengths. Results. A total of 32 disk sources have been observed. Out of these 32, 8 sources show a 69 μm emission feature that can be attributed to forsterite. With the exception of the T Tauri star AS 205, all of the detections are for disks associated with Herbig Ae/Be stars. Most of the forsterite grains that give rise to the 69 μm bands are found to be warm (∼100-200 K) and iron-poor (less than ∼2% iron). AB Aur is the only source where the emission cannot be fitted with iron-free forsterite requiring approximately 3-4% of iron. Conclusions. Our findings support the hypothesis that the forsterite grains form through an equilibrium condensation process at high temperatures. The large width of the emission band in some sources may indicate the presence of forsterite reservoirs at different temperatures. The connection between the strength of the 69 and 33 μm bands shows that at least part of the emission in these two bands originates fom the same dust grains. We further find that any model that can explain the PACS and the Spitzer IRS observations must take the effects of a wavelength dependent optical depth into account. We find weak indications of a correlation of the detection rate of the 69 μm band with the spectral type of the host stars in our sample. However, the sample size is too small to obtain a definitive result

Experimental IR and Raman spectra of solid acetazolamide have been analysed by computing the molecular structures and vibrational spectra of monomer and dimer forms and water clusters of acetazolamide. The possible stable conformers of free acetazolamide molecule in the ground state were obtained by scanning the potential energy surface through the dihedral angles, D1(1S-2C-6S-9N), D2(4N-5C-12N-14C), and D3(5C-12N-14C-16C). The final geometry parameters for the obtained stable conformers were determined by means of geometry optimization, carried out at DFT/B3LYP/6-31G++(d,p) theory level. Afterwards the possible dimer forms of the molecule and acetazolamide-H2O clusters were formed and their energetically preferred conformations were investigated using the same method and the same level of theory. The effect of BSSE on the structure and energy of acetazolamide dimer has been investigated. The assignment of the vibrational modes was performed based on the potential energy distribution of the vibrational modes, calculated by using GAR2PED program. The experimental vibrational wavenumbers of solid acetazolamide are found to be in better agreement with the calculated wavenumbers of dimer form of acetazolamide than those of its monomeric form. NBO analysis has been performed on both monomer and dimer geometries.