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991.
Sychrovský V Budesínský M Benda L Spirko V Vokacova Z Sebestík J Bour P 《The journal of physical chemistry. B》2008,112(6):1796-1805
The l-alanyl-l-alanine (AA) molecule behaves differently in acidic, neutral, and basic environments. Because of its molecular flexibility and strong interaction with the aqueous environment, its behavior has to be deduced from the NMR spectra indirectly, using statistical methods and comparison with ab initio predictions of geometric and spectral parameters. In this study, chemical shifts and indirect spin-spin coupling constants of the AA cation, anion, and zwitterion were measured and compared to values obtained by density functional computations for various conformers of the dipeptide. The accuracy and sensitivity of the quantum methods to the molecular charge was also tested on the (mono)-alanine molecule. Probable AA conformers could be identified at two-dimensional potential energy surfaces and verified by the comparison of the computed parameters with measured NMR data. The results indicate that, whereas the main-chain peptide conformations of the cationic (AA+) and zwitterionic (AAZW) forms are similar, the anion (AA-) adopts also another, approximately equally populated conformer in the aqueous solution. Additionally, the NH2 group can rotate in the two main chain conformations of the anionic form AA-. According to a vibrational quantum analysis of the two-dimensional energy surfaces, higher-energy conformers might exist for all three charged AA forms but cannot be detected directly by NMR spectroscopy because of their small populations and short lifetimes. In accord with previous studies, the NMR parameters, particularly the indirect nuclear spin-spin coupling constants, often provided an excellent probe of a local conformation. Generalization to peptides and proteins, however, has to take into account the environment, molecular charge, and flexibility of the peptide chain. 相似文献
992.
The main result of this work is a Dancer-type bifurcation result for the quasilinear elliptic problem
Here, Ω is a bounded domain in denotes the Dirichlet p-Laplacian on , and is a spectral parameter. Let μ1 denote the first (smallest) eigenvalue of −Δ
p
. Under some natural hypotheses on the perturbation function , we show that the trivial solution is a bifurcation point for problem (P) and, moreover, there are two distinct continua, and , consisting of nontrivial solutions to problem (P) which bifurcate from the set of trivial solutions at the bifurcation point (0, μ1). The continua and are either both unbounded in E, or else their intersection contains also a point other than (0, μ1). For the semilinear problem (P) (i.e., for p = 2) this is a classical result due to E. N. Dancer from 1974. We also provide an example of how the union looks like (for p > 2) in an interesting particular case.
Our proofs are based on very precise, local asymptotic analysis for λ near μ1 (for any 1 < p < ∞) which is combined with standard topological degree arguments from global bifurcation theory used in Dancer’s original
work.
Submitted: July 28, 2007. Accepted: November 8, 2007. 相似文献
((P)) |
993.
Several octasubstituted zinc azaphthalocyanines (ZnAzaPcs) of the tetrapyrazinoporphyrazine type have been synthesized as potential sensitizers for photodynamic therapy (PDT). Octasubstituted complexes, with thiophen-2-yl, thiophen-3-yl or benzo[b]thiophen-3-yl peripheral groups, were synthesized and characterized. Octa(thiophen-2-yl) ZnAzaPc is a better singlet oxygen producer and has a red shifted UV absorption Q-band compared to both thiophen-3-yl and benzo[b]thiophen-3-yl substituted ZnAzaPcs. Thus, the thiophen-2-yl substituent is better suited for our purpose. Unsymmetrically substituted ZnAzaPcs were synthesized by cyclotetramerisations of pyrazine-2,3-dicarbonitriles attached to one thiophen-2-yl group and one alkylsulfanyl, thiomorpholinyl or imide group. Constitutional isomers were detected by NMR spectroscopy for some of these complexes. Compared to unsubstituted ZnAzaPc, red shifted Q-bands were observed for all these complexes, due to the presence of thiophen-2-yl groups. The least promising complexes are ZnAzaPcs with thiomorpholine or imide peripheral substituents, i.e. where the peripheral substituents are attached to the macrocycle through nitrogen atoms. Low singlet oxygen quantum yields (ΦΔ) and also low fluorescence quantum yields (ΦF) were observed for these ZnAzaPcs. In the case of combined thiophen-2-yl and alkylsulfanyl substituents, the values of ΦΔ were the highest and reached values of approximately 0.69. 相似文献
994.
Kogan A Popov I Uvarov V Cohen S Aserin A Garti N 《Langmuir : the ACS journal of surfaces and colloids》2008,24(3):722-733
Crystallization of carbamazepine (CBZ), an antiepileptic drug, precipitated from confined spaces of nonionic microemulsions was investigated. The study was aimed to correlate the structure of the microemulsion [water-in-oil (W/O), bicontinuous, and oil-in-water (O/W)] with the crystalline structure and morphology of solid CBZ. The precipitated CBZ was studied by DSC, TGA, powder XRD, single-crystal XRD, SEM, and optical microscopy. The results suggest that the microstructure of the microemulsions influences the crystallization process and allows crystallizing polymorphs that exhibit different crystal structure and habits. W/O nanodroplets orient the crystallizing CBZ molecules to form a prismlike anhydrous polymorphic form with monoclinic unit cell and P21/n space group. Bicontinuous structures lead to platelike dihydrate crystals with orthorhombic unit cell and Cmca space group. The O/W nanodroplets cause the formation of needlelike dihydrate crystals with monoclinic unit cell and P21/c space group. The morphological features of solid CBZ remain predetermined by the basic symmetry and parameters of its unit cell. Precipitation of CBZ pseudopolymorphs from supersaturated microemulsion is discussed in terms of oriented attachment that provides perfect packing of numerous separately nucleated ordered nuclei of CBZ into microscale platelets and then into macroscopic crystals. Crystallization from microemulsion media enabling one to obtain the drug (CBZ) with predicted structure and morphology should be of great significance for pharmaceutical applications. 相似文献
995.
996.
Cígler P Král V Kozísek M Konvalinka J Mirsky VM 《Colloids and surfaces. B, Biointerfaces》2008,64(1):145-149
Adsorption of HIV protease onto surfaces that are usually considered to be protein-resistant was studied quantitatively using surface plasmon resonance. Adsorption onto gold surfaces functionalized by OH-terminated alkyl chains was much stronger than onto oligo(ethylene glycol)-terminated surfaces. Equilibrium and kinetic adsorption constants were determined. An anomalous mutual attraction between adsorbate molecules was observed, indicating the possibility of two-dimensional crystallization of HIV protease. These results are applicable for the design of sensors/biosensors for HIV protease resistance detection and for proper manipulation of this enzyme in laboratory devices. 相似文献
997.
Ng SH Tran N Bramnik KG Hibst H Novák P 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(35):11141-11148
Li(4)V(3)O(8) materials have been prepared by chemical lithiation by Li(2)S of spherical Li(1.1)V(3)O(8) precursor materials obtained by a spray-drying technique. The over-lithiated vanadates were characterised physically by using scanning electron microscopy (SEM) and X-ray diffraction (XRD), and electrochemically using galvanostatic charge-discharge and cyclic voltammetry measurements in both the half-cell (vs. Li metal) and full-cell (vs. graphite) systems. The Li(4)V(3)O(8) materials are stable in air for up to 5 h, with almost no capacity drop for the samples stored under air. However, prolonged exposure to air will severely change the composition of the Li(4)V(3)O(8) materials, resulting in both Li(1.1)V(3)O(8) and Li(2)CO(3). The electrochemical performance of these over-lithiated vanadates was found to be very sensitive to the conductive additive (carbon black) content in the cathode. When sufficient carbon black is added, the Li(4)V(3)O(8) cathode exhibits good cycling behaviour and excellent rate capabilities, matching those of the Li(1.1)V(3)O(8) precursor material, that is, retaining an average charge capacity of 205 mAh g(-1) at 2800 mA g(-1) (8C rate; 1C rate means full charge or discharge of a battery in one hour), when cycled in the potential range of 2.0-4.0 V versus Li metal. When applied in a non-optimised full cell system (vs. graphite), the Li(4)V(3)O(8) cathode showed promising cycling behaviour, retaining a charge capacity (Li(+) extraction) above 130 mAh g(-1) beyond 50 cycles, when cycled in the voltage range of 1.6-4.0 V, at a specific current of 117 mA g(-1) (C/3 rate). 相似文献
998.
Milko P Roithová J Tsierkezos N Schröder D 《Journal of the American Chemical Society》2008,130(23):7186-7187
An unprecedented red shift of more than 200 cm(-1) in the vibrational frequency of the C-O bond in the [Cu(PhO)Ln]+ complex (PhO = phenoxy), dependent on the number n of additional ligands L, is reported. Upon change of n from 1 to 2, the spin density is shifted from the aromatic ring to the oxygen and copper atoms, which is reflected in the bond order and thus vibrational frequency of the C-O bond. 相似文献
999.
In capillary electrophoresis (CE) dynamic coating agents are commonly used for manipulating or reversing electroosmotic flow (EOF) and suppressing adsorption of analytes by the silica surface. In this paper we review general aspects of dynamic coating in CE and discuss features and facts concerning formation of the EOF and determination of its magnitude. 相似文献
1000.
Ji?í Dybal Emanuel Makrlík Jan Budka Petr Vaňura 《Monatshefte für Chemie / Chemical Monthly》2008,275(2):1353-1355
Using DFT calculations, two of the most probable structures (A, B) of the tetraphenyl p-tert-butylcalix[4]arene tetraketone·H3O+ cationic complex species were derived. The hydroxonium ion H3O+, placed in the coordination cavity formed by the calix[4]arene lower-rim groups, is bound by strong hydrogen bonds to the
phenoxy oxygen atoms of the calix[4]arene ligand (structures A, B) and also to one carbonyl oxygen (structure B). 相似文献