[reaction: see text] A novel approach to alpha,alpha-disubstituted-beta-amino acids (beta(2,2)-amino acids) was employed in the synthesis of a series of 3-(pyrrolidin-1-yl)propionic acids possessing high affinity for the CCR5 receptor and potent anti-HIV activity. The rat pharmacokinetics for these new analogues featured higher bioavailabilities and lower rates of clearance as compared to cyclopentane 1. 相似文献
Films of titanate nanosheets (approx. 1.8-nm layer thickness and 200-nm size) having a lamellar structure can form electrolyte-filled semi-permeable channels containing tetrabutylammonium cations. By evaporation of a colloidal solution, persistent deposits are readily formed with approx. 10-μm thickness on a 6-μm-thick poly(ethylene-terephthalate) (PET) substrate with a 20-μm diameter microhole. When immersed in aqueous solution, the titanate nanosheets exhibit a p.z.c. of − 37 mV, consistent with the formation of a cation conducting (semi-permeable) deposit. With a sufficiently low ionic strength in the aqueous electrolyte, ionic current rectification is observed (cationic diode behaviour). Currents can be dissected into (i) electrolyte cation transport, (ii) electrolyte anion transport and (iii) water heterolysis causing additional proton transport. For all types of electrolyte cations, a water heterolysis mechanism is observed. For Ca2+ and Mg2+ions, water heterolysis causes ion current blocking, presumably due to localised hydroxide-induced precipitation processes. Aqueous NBu4+ is shown to ‘invert’ the diode effect (from cationic to anionic diode). Potential for applications in desalination and/or ion sensing are discussed.
Reaction of potassium dichromate with gamma-glutamylcysteine, N-acetylcysteine, and cysteine in aqueous solution resulted in the formation of 1:1 complexes of Cr(VI) with the cysteinyl thiolate ligand. The brownish red Cr(VI)-amino acid/peptide complexes exhibited differential stability in aqueous solutions at 4 degrees C and ionic strength = 1.5 M, decreasing in stability in the order: gamma-glutamylcysteine > N-acetylcysteine > cysteine. (1)H, (13)C, and (17)O NMR studies showed that the amino acids act as monodentate ligands and bind to Cr(VI) through the cysteinyl thiolate group, forming RS-Cr(VI)O(3)(-) complexes. No evidence was obtained for involvement of any other possible ligating groups, e.g., amine or carboxylate, of the amino acid/peptide in binding to Cr(VI). EPR studies showed that chromium(V) species at g = 1.973-4 were formed upon reaction of potassium dichromate with gamma-glutamylcysteine and N-acetylcysteine. Reaction of potassium dichromate or sodium dichromate with N-acetylcysteine and the methyl ester of N-acetylcysteine in N,N-dimethylformamide (DMF) also led to the formation of RS-Cr(VI)O(3)(-) complexes as determined by UV/vis, IR, and (1)H NMR spectroscopy. Thus, an early step in the reaction of Cr(VI) with cysteine and cysteine derviatives in aqueous and DMF solutions involves the formation of RS-CrO(3)(-) complexes. The Cr(VI)-thiolate complexes are more stable in DMF than in aqueous solution, and their stability towards reduction in aqueous solution follows the order cysteine < N-acetylcysteine < gamma-glutamylcysteine < glutathione. 相似文献
Pyrrolizidine alkaloids (PAs) and their N-oxides are found in several plant families throughout the world. PAs are potentially toxic to the liver and/or lungs in humans and may cause acute liver failure, cirrhosis, pneumonitis, or pulmonary hypertension. PAs are also carcinogenic to animals, and they have been linked to the development of hepatocellular and skin squamous cell carcinomas as well as liver angiosarcomas. According to experimental studies, the quantity of PAs in some herbal teas and dietary supplements is sufficient to be carcinogenic in exposed individuals. A method for the extraction and identification of PAs and their N-oxides in botanical materials and commercial comfrey-containing products has been developed using liquid chromatography electrospray ionization mass spectrometry. Following optimization of the extraction procedure and the chromatographic conditions, the method was applied to the analysis of 10 herbal remedies. All of the products that were labeled to contain comfrey were found to contain measurable quantities of PAs. 相似文献
The kinetics of pyridine exchange on trans-[MO2(py)4]+ have been followed by 1H-NMR in CD3NO2 for M = Re, Tc: k298S?1 = (5.5 ± 0.1) × 10?6, 0.04 ± 0.02; ΔH≠/kJmol?1 = 111 ± 3, 101 ± 9; ΔS≠/JK?1mol?1 = +28 ± 10, +68 ± 35. For the Rev complex, pyridine and oxygen exchanges have been measured simultaneously by 1H- and 17O-NMR in deuterated water: k298/s?1 = (8.6 ± 0.2) × 10?6 (py), (14.5 ± 0.3) × 10?6 (oxygen); ΔH≠/kJmol?1 = 111 ± 1, 91 ± 1; ΔS /JK?1mol?1 = +32 ± 3, ?32 ± 4. For both complexes, the rate law for pyridine exchange is first-order in complex and zero-order in pyridine; together with the activation parameter values, and the fact that the rate does not depend significantly on the nature of the solvent, this strongly implies the operation of a dissociative mechanism. The ratio of pyridine exchange rates for the Tc and Re complexes at room temperature is ca. 8000. The consequences of these observations for radiopharmaceutical synthesis are discussed. 相似文献
[reaction: see text] The palladium-catalyzed cyanation reaction is known to be sensitive to dissolved cyanide. Investigation into some causes of high levels of dissolved cyanide is presented here, along with a robust solution to this problem. 相似文献
YBaFe(2)O(5) has been synthesized by heating a nanoscale citrate precursor in a carefully controlled reducing environment. Successful synthesis of a single-phase sample can only be achieved in a narrow window of oxygen partial pressures and temperatures. YBaFe(2)O(5) adopts an oxygen-deficient perovskite-type structure, which contains double layers of corner sharing FeO(5) square pyramids separated by Y(3+) ions. At T(N) congruent with 430 K, tetragonal (P4/mmm) and paramagnetic YBaFe(2)O(5) orders antiferromagnetically (AFM) experiencing a slight orthorhombic distortion (Pmmm). Around this temperature, it can be characterized as a class-III mixed valence (MV) compound, where all iron atoms exist as equivalent MV Fe(2.5+) ions. The magnetic structure is characterized by AFM Fe-O-Fe superexchange coupling within the double layers and a ferromagnetic Fe-Fe direct-exchange coupling between neighboring double layers. Upon cooling below approximately 335 K, a premonitory charge ordering (2Fe(2.5+) --> Fe(2.5+delta) + Fe(2.5)(-delta)) into a class-II MV phase takes place. This transition is detected by differential scanning calorimetry, but powder diffraction techniques fail to detect any volume change or a long-range structural order. At approximately 308 K, a complete charge ordering (2Fe(2.5+) --> Fe(2+) + Fe(3+)) into a class-I MV compound takes place. This charge localization triggers a number of changes in the crystal, magnetic, and electronic structure of YBaFe(2)O(5). The magnetic structure rearranges to a G-type AFM structure, where both the Fe-O-Fe superexchange and the Fe-Fe direct-exchange couplings are antiferromagnetic. The crystal structure rearranges (Pmma) to accommodate alternating chains of Fe(2+) and Fe(3+) running along b and an unexpectedly large cooperative Jahn-Teller distortion about the high-spin Fe(2+) ions. This order of charges does not fulfill the Anderson condition, and it rather corresponds to an ordering of doubly occupied Fe(2+) d(xz) orbitals. Comparisons with YBaMn(2)O(5) and YBaCo(2)O(5) are made to highlight the impact of changing the d-electron count. 相似文献
The temperature-dependent self-assembly of the single-chain bolaamphiphile dotriacontan-1,1'-diyl-bis[2-(trimethylammonio)ethyl phosphate] (PC-C32-PC) was investigated by transmission electron microscopy (TEM), differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FT-IR), X-ray scattering, rheological measurements, and dynamic light scattering (DLS). At room temperature this compound, in which two phosphocholine headgroups are connected by a C(32) alkyl chain, proved to be capable of gelling water very efficiently by forming a dense network of nanofibers (Kohler et al. Angew. Chem., Int. Ed. 2004, 43, 245). A specific feature of this self-assembly process is that it is not driven by hydrogen bonds but solely by hydrophobic interactions of the long alkyl chains. The nanofibers have a thickness of roughly the molecular length and show a helical superstructure. A model for the molecular structure of the fibrils which considers the extreme constitution of the bolaamphiphile is proposed. Upon heating the suspensions three different phase transitions can be detected. Above 49 degrees C, the temperature of the main transition where the alkyl chains become "fluid", a clear low-viscosity solution is obtained due to a breakdown of the fibrils into smaller aggregates. Through mechanical stress the gel structure can be destroyed as well, indicating a low stability of these fibers. The gel formation is reversible, but as a drastic rearrangement of the molecules takes place, metastable states occur. 相似文献
Arylazide mediated photocrosslinking has been widely used to obtain structural constraints in biological systems, even though the reactive species generated upon photolysis in aqueous solution have not been well characterized. We establish a mechanistic framework for formation of adducts between photoactivated 3-hydroxyphenyl azide and RNA. Tethered to an internal site in an RNA duplex via a 2'-amido linkage, photolysis of the aryl azide yields a cross-strand cross-link. Analysis of the ability of reagents with diagnostic reactivities to intercept formation of this cross-strand cross-link supports the assignment that the photoactivated intermediate is the ketenimine or a ketenimine-derived ring expansion product. Neither the initially produced singlet nitrene nor the subsequently formed triplet nitrene contribute to cross-link formation. Argon matrix and time-resolved solution experiments show that photolysis of free 3-hydroxyphenyl azide releases (in 相似文献