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951.
In this communication we present the application of a new method, which enables one to acquire 3D NMR spectra in a reasonable time and preserves high resolution in indirectly detected domains. The new method is based on random distribution of time domain data points followed by Quaternion FT with respect to two time variables in one step.The experimental examples include three-dimensional spectra of strychnine in CDCl3, TOCSY-HSQC, COSY-HMBC, and the new technique proposed here: heteronuclear single quantum multiple bond correlation (HSQMBC). The obtained spectra are compared to those recorded at the same time employing the conventional acquisition scheme. We show that high-quality 3D spectra of organic compounds can be obtained in reasonable experimental time and that they are of great interest in cases when direct analysis of 2D spectra is difficult. 相似文献
952.
The synthesised complex cis-[Cr(C2O4)(AaraNH2)(OH2)(OSO2)]− anion with SO
3
2−
as a ligand in the inner coordination sphere, where AaraNH2 denotes methyl 3-amino-2,3-dideoxy-α-d-arabino-hexopyranoside, was hydrolysed in the presence of acid at H+ concentrations from 0.01 to 2.7 m (HClO4). The reaction kinetics was studied with the stopped-flow spectrophotometric (u.v.–vis.) technique at temperatures of 5,
10, 15, 18 and 20 °C. This hydrolysis turned out to be a single-step process. Determined for this reaction were the rate constant
k
1 for the removal of SO2 from the coordination sphere of the cis-[Cr(C2O4)(AaraNH2)(OH2)(OSO2)]− ion and the constant pK
1 of the protonation of this species in the reaction preceding the hydrolysis. The final product of this reaction – a new complex
of CrIII, cis-[Cr(C2O4)(AaraNH2)(OH2)2]+, was obtained. A mechanism for the acid hydrolysis reaction is put forward based on the analysis of the rate constants obtained. 相似文献
953.
Dominska M Mazur M Greenough KP Koan MM Krysiński PG Blanchard GJ 《Bioelectrochemistry (Amsterdam, Netherlands)》2007,70(2):421-434
We have investigated the local organization intrinsic to a variety of interfacial structures, by both electrochemical and spectroscopic means. Our focus has been on the design and construction of biomimetic interfaces, where a lipid bilayer or a hybrid bilayer membrane can be bound to an interface. The goal of this work is ultimately to create an interface on a transducer surface that can support an enzyme in its active form. To this point, we have examined the extent of organization that is achievable in monolayers that will be used to bind bilayer structures to a transducer surface. Our electrochemical data point to the important role of the substrate surface in determining adlayer organization. We have also investigated the fluidity and structural heterogeneity of lipid bilayers using time-resolved and steady state fluorescence spectroscopy. Our data point to the highly interactive nature of lipid bilayer constituents, where perturbations introduced to one region have significant consequences on other regions of the bilayer. Such information is directly relevant to the existence and properties of lipid raft structures in both model and biological bilayers. 相似文献
954.
Mazur M Krysiński P Michota-Kamińska A Bukowska J Rogalski J Blanchard GJ 《Bioelectrochemistry (Amsterdam, Netherlands)》2007,71(1):15-22
In this paper we present a simple method allowing for stable laccase immobilization on various conducting surfaces that retains the activity of the enzyme. The strategy for laccase immobilization presented in this paper relies on Zr(4+) ion coordination chemistry that involves -COO- terminal groups present on the protein. Using a host of techniques, including surface plasmon resonance (SPR), quartz crystal microbalance (QCM) gravimetry, atomic force microscopy (AFM), surface enhanced Raman scattering (SERS), resonance Raman scattering (RR) and electrochemical techniques, we show that laccase bound to a surface coordinatively through zirconium phosphonate/carboxylate (ZPC) functionalities forms a stable enzymatic layer with the enzyme retaining its activity to a significant extent. 相似文献
955.
Dobrochna Matkowska Maciej Gola Marcin ?nie?ek Piotr Cmoch Krzysztof Staliński 《Journal of organometallic chemistry》2007,692(10):2036-2045
A series of triorganotin hydrides and diorganotin dihydrides containing the optically active 2-(4-isopropyl-2-oxazolinyl)-5-phenyl ligand have been characterized by means of the multinuclear low-temperature NMR investigations, the results of which are discussed. In the corresponding organotin hydrides values of the 1J(1H-117/119Sn) couplings appeared to be temperature dependent, supporting an axial/equatorial position of the hydrogen attached to the tin. 相似文献
956.
A Single Methylene Group in Oligoalkylamine‐Based Cationic Polymers and Lipids Promotes Enhanced mRNA Delivery 下载免费PDF全文
Anita Jarzębińska Dr. Tamara Pasewald Jana Lambrecht Olga Mykhaylyk Linda Kümmerling Dr. Philipp Beck Dr. Günther Hasenpusch Priv.‐Doz. Dr. Carsten Rudolph Prof. Dr. Christian Plank Dr. Christian Dohmen 《Angewandte Chemie (International ed. in English)》2016,55(33):9591-9595
The development of chemically modified mRNA holds great promise as a new class of biologic therapeutics. However, the intracellular delivery and endosomal escape of mRNA encapsulated in nanoparticles has not been systematically investigated. Here, we synthesized a diverse set of cationic polymers and lipids from a series of oligoalkylamines and subsequently characterized their mRNA delivery capability. Notably, a structure with an alternating alkyl chain length between amines showed the highest transfection efficiency, which was linked to a high buffering capacity in a narrow range of pH 6.2 to 6.5. Variation in only one methylene group resulted in enhanced mRNA delivery to both the murine liver as well as porcine lungs after systemic or aerosol administration, respectively. These findings reveal a novel fundamental structure–activity relationship for the delivery of mRNA that is independent of the class of mRNA carrier and define a promising new path of exploration in the field of mRNA therapeutics. 相似文献
957.
The total phenolics and flavonoids, rutin, early, advanced and final Maillard reaction products, and antioxidative capacity determined against 2,2′-azinobis-(3-ethylbenzothiazoline-6-sulfonate) radical cation and superoxide anion radicals were used for the characterization of the quality of novel rye-buckwheat ginger cakes enriched with rutin (quercetin rutinoside). The cakes were prepared substituting 30 % of rye flour by light buckwheat flour or flour from roasted buckwheat dehulled grains and employing a dough fermentation-like incubation step. Enrichment of ginger cakes with rutin showed protective effect on lysine blockage, improved antioxidant properties, inhibited the formation of furosine and free fluorescent compounds thus stimulating the Maillard reaction progress towards melanoidin formation. The loss of the nutritional quality of cakes enriched with rutin was related to the formation of fluorescent compounds linked to protein and carboxymethyllysine at an advanced stage of the Maillard reaction. It can be concluded that free fluorescence intermediatory compounds, carboxymethyllysine and browning are the best chemical markers for the characterization of the quality of this novel type of ginger cakes. This study also indicates that rye-buckwheat ginger cakes enriched with rutin can be recommended for wider consumption since daily consumption of 250 g of these cakes may have a prophylactic or therapeutic effect corresponding to typical pharmacological drugs with rutin as the active component. 相似文献
958.
Dr. Joice Thomas Dr. Liliana Dobrzańska Prof. Luc Van Meervelt Prof. Mario Alfredo Quevedo Prof. Krzysztof Woźniak Marcin Stachowicz Prof. Mario Smet Prof. Wouter Maes Prof. Wim Dehaen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(3):979-987
A synthetic route towards homodiselenacalix[4]arene macrocycles is presented, based on the dynamic covalent chemistry of diselenides. The calixarene inner rim is decorated with either alkoxy or tert‐butyl ester groups. Single‐crystal X‐ray analysis of two THF solvates with methoxy and ethoxy substituents reveals the high similarity of their molecular structures and alterations on the supramolecular level. In both crystal structures, solvent channels are present and differ in both shape and capacity. Furthermore, the methoxy‐substituted macrocycle undergoes a single‐crystal‐to‐single‐crystal transformation during which the molecular structure changes its conformation from 1,3‐alternate (loaded with THF/water) to 1,2‐alternate (apohost form). Molecular modelling techniques were applied to explore the conformational and energetic behaviour of the macrocycles. 相似文献
959.
960.
Tomasz Sierański 《Structural chemistry》2016,27(4):1107-1120
Extensive calculations of potential energy surfaces for parallel-displaced configurations of pyrrole–pyrrole systems have been carried out by the use of a dispersion-corrected density functional. System geometries associated with the energy minima have been found. The minimum interaction energy has been calculated as ?5.38 kcal/mol. However, bonding boundaries appeared to be relatively broad, and stacking interactions can be binding even for ring centroid distances larger than 6 Å. Though the contribution of the correlation energy to intermolecular interaction in pyrrole dimers appeared to be relatively small (around 1.6 smaller than it is in a benzene–benzene system), this system’s minimum interaction energy is lower than those calculated for benzene–benzene, benzene–pyridine and even pyridine–pyridine configurations. The calculation of the charges and energy decomposition analysis revealed that the specific charge distribution in a pyrrole molecule and its relatively high polarization are the significant source of the intermolecular interaction in pyrrole dimer systems. 相似文献