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531.
Elucidation of the absolute configuration of rhizopine by chiral supercritical fluid chromatography and vibrational circular dichroism 下载免费PDF全文
Alain Krief Melissa Dunkle Masoud Bahar Patrick Bultinck Wouter Herrebout Pat Sandra 《Journal of separation science》2015,38(14):2545-2550
The absolute configuration of rhizopine, an opine‐like natural product present in nitrogen‐fixing nodules of alfalfa infected by rhizobia, is elucidated using a combination of state‐of‐the‐art analytical and semi‐preparative supercritical fluid chromatography and vibrational circular dichroism spectroscopy. A synthetic peracetylated racemate was fractionated into its enantiomers and subjected to absolute configuration analysis revealing that natural rhizopine exists as a single enantiomer. The stereochemistry of non‐derivatized natural rhizopine corresponds to (1R,2S,3R,4R,5S,6R)‐4‐amino‐6‐methoxycyclohexane‐1,2,3,5‐tetraol. 相似文献
532.
Tuning the Halogen/Hydrogen Bond Competition: A Spectroscopic and Conceptual DFT Study of Some Model Complexes Involving CHF2I 下载免费PDF全文
Dr. Nick Nagels Yannick Geboes Dr. Balazs Pinter Prof. Dr. Frank De Proft Prof. Dr. Wouter A. Herrebout 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(27):8433-8443
Insight into the key factors driving the competition of halogen and hydrogen bonds is obtained by studying the affinity of the Lewis bases trimethylamine (TMA), dimethyl ether (DME), and methyl fluoride (MF) towards difluoroiodomethane (CHF2I). Analysis of the infrared and Raman spectra of solutions in liquid krypton containing mixtures of TMA and CHF2I and of DME and CHF2I reveals that for these Lewis bases hydrogen and halogen‐bonded complexes appear simultaneously. In contrast, only a hydrogen‐bonded complex is formed for the mixtures of CHF2I and MF. The complexation enthalpies for the C?H ??? Y hydrogen‐bonded complexes with TMA, DME, and MF are determined to be ?14.7(2), ?10.5(5) and ?5.1(6) kJ mol?1, respectively. The values for the C?I ??? Y halogen‐bonded isomers are ?19.0(3) kJ mol?1 for TMA and ?9.9(8) kJ mol?1 for DME. Generalization of the observed trends suggests that, at least for the bases studied here, softer Lewis bases such as TMA favor halogen bonding, whereas harder bases such as MF show a substantial preference for hydrogen bonding. 相似文献
533.
Dr. Wouter Marchal Dr. Dries De Sloovere Prof. Dr. Michael Daenen Prof. Dr. Marlies K. Van Bael Prof. Dr. An Hardy 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(42):9070-9083
Solution-based (multi)metal oxide synthesis has been carried out employing a large diversity of precursor routes. The selection of an appropriate synthesis strategy is frequently dictated by the resulting material properties, although this choice should also be based on green chemistry principles, atom economy considerations and energy efficiency. In order to limit the required energy budget to convert the chemical precursor to the target oxide material, various approaches were recently reported. This Review summarizes some frequently encountered low-temperature routes, critically assessing their application window and advantages. More specifically, auto-combustion synthesis, UV-assisted decomposition routes, sol–gel network adjustments and precursor complex design concepts are discussed. It is expected that this toolbox of low-temperature strategies may assist further progress in the field, stimulating novel applications, such as flexible electronics or organic–oxide hybrid materials, which are very sensitive to the temperature requirements. 相似文献
534.
Kuppens T Herrebout W van der Veken B Bultinck P 《The journal of physical chemistry. A》2006,110(34):10191-10200
Carboxylic acids are known for their strong intermolecular associations. With chiral carboxylic acids, this behavior can be studied using vibrational circular dichroism (VCD). Tetrahydrofuran-2-carboxylic acid 1, a chiral building block for beta-lactam antibiotics, is studied by emphasizing the effect of the dimerization. Experimental results indicate that for solutions of 1 in CDCl3 and CS2, a complex equilibrium exists between the monomers and dimers. B3LYP/aug-cc-pVTZ calculations are performed on both monomer and dimer structures. To simulate IR and VCD spectra, populations for monomer and dimers were approximated using a semiquantitative model. A good agreement between experimental and simulated spectra is obtained by taking into account both the monomeric and the dimeric structures, weighted using the experimentally determined populations. 相似文献
535.
The combination of capillary electrophoresis (CE) and electrospray ionization-mass spectrometry (ESI-MS) via a triaxial interface was studied as a potential means for the characterization of intact proteins. To evaluate the possibility to use a nonvolatile electrolyte for CE, the effect of sodium phosphate and ammonium borate on the MS signal of the proteins insulin, myoglobin, and bovine serum albumin (BSA) was investigated by employing infusion experiments, and compared to the effect of ammonium formate and formic acid. The study shows that with formic acid (50 mM, pH 2.4) the most intense protein signals were obtained, while the use of sodium phosphate buffer (5 and 10 mM, pH 7.5) almost completely diminished the MS response. Ammonium formate and ammonium borate (up to 100 mM, pH 8.5) also caused protein ion suppression, but especially with the borate buffer significant MS intensity remained. MS analysis of myoglobin revealed the loss of the heme group when an acidic CE electrolyte was used. Using a background electrolyte containing 25 mM ammonium borate (pH 8.5), it is demonstrated that a CE separation of a protein test mixture can be monitored with ESI-MS without degrading the MS performance allowing molecular weight determinations of the separated compounds. In the presence of borate, detection limits were estimated to be 5-10 microM (ca. 100 fmol injected). The usefulness of the CE-MS system employing a borate buffer is indicated by the analysis of a stored sample of BSA revealing several degradation products. A sample of placental alkaline phosphatase (PLAP), a potential therapeutic agent, was also analyzed by CE-MS indicating the presence of a protein impurity. Probably due to insufficient ionization of the PLAP (a complex glycoprotein), no MS signals of the intact protein were observed. 相似文献
536.
Seyednejad H Ji W Schuurman W Dhert WJ Malda J Yang F Jansen JA van Nostrum C Vermonden T Hennink WE 《Macromolecular bioscience》2011,11(12):1684-1692
Scaffolds based on a novel functionalized polyester, pHMGCL, are electrospun and characterized morphologically and physically. In vitro degradation studies of pHMGCL films show considerable mass loss and molecular weight reduction within 70 weeks. Scaffolds composed of fibers with uniform diameter (≈ 900 nm) and with melting temperatures higher than body temperature are prepared. As an indication for the feasibility of this material for regenerative medicine approaches, articular chondrocytes are seeded onto electrospun pHMGCL scaffolds. Chondrocytes attach to the fibers and re-differentiate as demonstrated by the production of GAG and collagen type II within four weeks of in vitro culture. Hydrophilic pHMGCL scaffolds may thus be useful for tissue engineering applications. 相似文献
537.
Dom JJ van der Veken BJ Michielsen B Jacobs S Xue Z Hesse S Loritz HM Suhm MA Herrebout WA 《Physical chemistry chemical physics : PCCP》2011,13(31):14142-14152
A vibrational assignment of the anaesthetic sevoflurane, (CF(3))(2)CHOCH(2)F, is proposed and its interaction with the aromatic model compound benzene is studied using vibrational spectroscopy of supersonic jet expansions and of cryosolutions in liquid xenon. Ab initio calculations, at the MP2/cc-pVDZ and MP2/aug-cc-pVDZ levels, predict two isomers for the 1?:?1 complex, one in which the near-cis, gauche conformer of sevoflurane is hydrogen bonded through its isopropyl-hydrogen atom, the other in which the same conformer is bonded through a bifurcated hydrogen bond with the fluoromethyl hydrogen atoms. From the experiments it is shown that the two isomers are formed, however with a strong population dominance of the isopropyl-bonded species, both in the jet and liquid phase spectra. The experimental complexation enthalpy in liquid xenon, ΔH(o)(LXe), of this species equals -10.9(2) kJ mol(-1), as derived from the temperature dependent behaviour of the cryosolution spectra. Theoretical complexation enthalpies in liquid xenon were obtained by combining the complete basis set extrapolated complexation energies at the MP2/aug-cc-pVXZ (X = D,T) level with corrections derived from statistical thermodynamics and Monte Carlo Free Energy Perturbation calculations, resulting in a complexation enthalpy of -11.2(3) kJ mol(-1) for the isopropyl-bonded complex, in very good agreement with the experimental value, and of -11.4(4) kJ mol(-1), for the fluoromethyl-bonded complex. The Monte Carlo calculations show that the solvation entropy of the isopropyl-bonded species is considerably higher than that of the fluoromethyl-bonded complex, which assists in explaining its dominance in the liquid phase spectra. 相似文献
538.
539.
Visser WF Verhoeven-Duif NM Ophoff R Bakker S Klomp LW Berger R de Koning TJ 《Journal of chromatography. A》2011,1218(40):7130-7136
D-Amino acids are increasingly being recognized as important signaling molecules in mammals, including humans. D-Serine and D-aspartate are believed to act as signaling molecules in the central nervous system. Interestingly, several other D-amino acids also occur in human plasma, but very little is currently known regarding their function and origin. Abnormal levels of D-amino acids have been implicated in the pathogenesis of different diseases, including schizophrenia and amyotrophic lateral sclerosis (ALS), indicating that D-amino acid levels hold potential as diagnostic markers. Research into the biological functions of D-amino acids is hindered, however, by the lack of sufficiently sensitive, high-throughput analytical methods. In particular, the interference of large amounts of L-amino acids in biological samples and the low concentrations of D-amino acids are challenging. In this paper, we compared 7 different chiral derivatization agents for the analysis of D-amino acids and show that the chiral reagent (S)-NIFE offers outstanding performance in terms of sensitivity and enantioselectivity. An UPLC-MS/MS based method for the quantification of D-amino acids human biological fluids was then developed using (S)-NIFE. Baseline separation (R(s)>2.45) was achieved for the isomers of all 19 chiral proteinogenic amino acids. The limit of detection was <1 nM for all amino acids except d-alanine (1.98 nM), d-methionine (1.18 nM) and d-asparagine (5.15 nM). For measurements in human plasma, cerebrospinal fluid and urine, the accuracy ranged between 85% and 107%. The intra-assay and inter-assay were both <16% RSD for these three different matrices. Importantly, the method does not suffer from spontaneous racemization during sample preparation and derivatization. Using the described method, D-amino acid levels in human cerebrospinal fluid, plasma and urine were measured. 相似文献
540.
In this article we introduce a novel polymer platform based on off-stoichiometry thiol-enes (OSTEs), aiming to bridge the gap between research prototyping and commercial production of microfluidic devices. The polymers are based on the versatile UV-curable thiol-ene chemistry but takes advantage of off-stoichiometry ratios to enable important features for a prototyping system, such as one-step surface modifications, tuneable mechanical properties and leakage free sealing through direct UV-bonding. The platform exhibits many similarities with PDMS, such as rapid prototyping and uncomplicated processing but can at the same time mirror the mechanical and chemical properties of both PDMS as well as commercial grade thermoplastics. The OSTE-prepolymer can be cast using standard SU-8 on silicon masters and a table-top UV-lamp, the surface modifications are precisely grafted using a stencil mask and the bonding requires only a single UV-exposure. To illustrate the potential of the material we demonstrate key concepts important in microfluidic chip fabrication such as patterned surface modifications for hydrophobic stops, pneumatic valves using UV-lamination of stiff and rubbery materials as well as micromachining of chip-to-world connectors in the OSTE-materials. 相似文献