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21.
22.
A fluorogenic renin substrate, N-CBO-L -prolyl-L -phenylalanyl-L -histidyl-L -leucyl-L -leucyl-L -valyl-L -tyrosyl-L -seryl-β-naphthylamide, has been synthesized. Upon incubation at pH 5,6 with renin and an excess of the auxiliary enzyme aminopeptidase M, it gives rise to β-naphthylamine at a rate related to the quantity of renin. 相似文献
23.
Colourless single crystals of the caffeine adduct of mercurous perchlorate dihydrate, [Hg2(Caf)2](ClO4)2(H2O)2, were grown from aqueous solutions of mercurous perchlorate and caffeine by isothermal evaporation at ambient temperature. The crystal structure (monoclinic, P21/n, Z = 4, a = 1628.0(2), b = 780.4(1), c = 2229.6(3) pm, β = 99.84(1)°, R1(all data) = 0.0894) contains [trans‐Caf‐Hg‐Hg‐Caf]2+ cations with a Hg‐Hg distance of 250.88(6) pm, Hg‐N (bond) distances of 214.4(6) and 215.1(6) pm and Hg‐Hg‐N angles of 176.9(2) and 165.1(2)°, respectively. These cations are attached via weak Hg‐O contacts to dimers which are further arranged to leave large channels into which one crystal water molecule is included. The second water molecule and the two perchlorate anions are weakly attracted to one Hg atom. 相似文献
24.
Ernst M Detken A Böckmann A Meier BH 《Journal of the American Chemical Society》2003,125(51):15807-15810
Proteins are not always available in amounts desirable for solid-state magic-angle spinning (MAS) nuclear-magnetic resonance (NMR) spectroscopy. To maximize the signal-to-noise ratio achievable with small samples, the filling factor must be optimized by using small-diameter MAS rotors. These rotors have the added benefit of allowing higher radio frequency field amplitudes during polarization transfer steps and during decoupling periods as well as allowing higher spinning frequencies. We demonstrate the advantages of relatively fast MAS (30 kHz using a 2.5 mm rotor) compared to MAS at 12 kHz for the 10.4 kDa model protein Crh with 93 residues and show that the signal-to-noise ratio in two-dimensional correlation spectra can be significantly improved by taking advantage of optimized pulse sequences available with rapid MAS. 相似文献
25.
This paper reports the preparation, properties, and structure of new SF5Br-fluoroolefin adducts. The extent and direction of SF5Br addition to fluoroolefins have been studied with seven fluoroolefins. Steric factors appear to be important for this addition. 相似文献
26.
Shengfei Jin Hang T. Dang Graham C. Haug Viet D. Nguyen Hadi D. Arman Oleg V. Larionov 《Chemical science》2020,11(34):9101
Construction of C–C bonds at the α-carbon is a challenging but synthetically indispensable approach to α-branched carbonyl motifs that are widely represented among drugs, natural products, and synthetic intermediates. Here, we describe a simple approach to generation of boron enolates in the absence of strong bases that allows for introduction of both α-alkyl and α-aryl groups in a reaction of readily accessible 1,2-dicarbonyls and organoboranes. Obviation of unselective, strongly basic and nucleophilic reagents permits carrying out the reaction in the presence of electrophiles that intercept the intermediate boron enolates, resulting in two new α-C–C bonds in a tricomponent process.α-Branched carboxylic acids and other carbonyls are readily accessed by a metal- and base-free deoxygenative α-alkylation and α-arylation of 1,2-dicarbonyls via boron enolates, resulting in a tricomponent coupling with unconventional electrophiles. 相似文献
27.
Julia Post Vanessa Kogel Anja Schaffrath Philipp Lohmann N. Jon Shah Karl-Josef Langen Dieter Willbold Antje Willuweit Janine Kutzsche 《Molecules (Basel, Switzerland)》2021,26(6)
Amyotrophic lateral sclerosis (ALS) is a progressive neurodegenerative disease characterised by selective neuronal death in the brain stem and spinal cord. The cause is unknown, but an increasing amount of evidence has firmly certified that neuroinflammation plays a key role in ALS pathogenesis. Neuroinflammation is a pathological hallmark of several neurodegenerative disorders and has been implicated as driver of disease progression. Here, we describe a treatment study demonstrating the therapeutic potential of a tandem version of the well-known all-d-peptide RD2 (RD2RD2) in a transgenic mouse model of ALS (SOD1*G93A). Mice were treated intraperitoneally for four weeks with RD2RD2 vs. placebo. SOD1*G93A mice were tested longitudinally during treatment in various behavioural and motor coordination tests. Brain and spinal cord samples were investigated immunohistochemically for gliosis and neurodegeneration. RD2RD2 treatment in SOD1*G93A mice resulted not only in a reduction of activated astrocytes and microglia in both the brain stem and lumbar spinal cord, but also in a rescue of neurons in the motor cortex. RD2RD2 treatment was able to slow progression of the disease phenotype, especially the motor deficits, to an extent that during the four weeks treatment duration, no significant progression was observed in any of the motor experiments. Based on the presented results, we conclude that RD2RD2 is a potential therapeutic candidate against ALS. 相似文献
28.
Watzke A Brunsveld L Durek T Alexandrov K Rak A Goody RS Waldmann H 《Organic & biomolecular chemistry》2005,3(7):1157-1164
Rab/Ypt guanosine triphosphatases (GTPases) represent a family of key membrane traffic regulators in eukaryotic cells. For their function Rab/Ypt proteins require double modification with two covalently bound geranylgeranyl lipid moieties at the C-terminus. Generally, prenylated proteins are very difficult to obtain by recombinant or enzymatic methods. We generated prenylated RabGTPases using a combination of chemical synthesis and protein engineering. This semi-synthesis depends largely on the availability of functionalized prenylated peptides corresponding to the proteins' native structure or modifications. We developed solution phase and solid phase strategies for the generation of peptides corresponding to the prenylated C-terminus of Rab7 GTPase in preparative amounts enabling us to crystallize the mono-prenylated Ypt1:RabGDI complex. The structure of the complex provides a structural basis for the ability of RabGDI to inhibit the release of nucleotide by Rab proteins and a molecular basis for understanding a RabGDI mutant that causes mental retardation in humans. 相似文献
29.
Giraud N Blackledge M Goldman M Böckmann A Lesage A Penin F Emsley L 《Journal of the American Chemical Society》2005,127(51):18190-18201
A detailed analysis of nitrogen-15 longitudinal relaxation times in microcrystalline proteins is presented. A theoretical model to quantitatively interpret relaxation times is developed in terms of motional amplitude and characteristic time scale. Different averaging schemes are examined in order to propose an analysis of relaxation curves that takes into account the specificity of MAS experiments. In particular, it is shown that magic angle spinning averages the relaxation rate experienced by a single spin over one rotor period, resulting in individual relaxation curves that are dependent on the orientation of their corresponding carousel with respect to the rotor axis. Powder averaging thus leads to a nonexponential behavior in the observed decay curves. We extract dynamic information from experimental decay curves, using a diffusion in a cone model. We apply this study to the analysis of spin-lattice relaxation rates of the microcrystalline protein Crh at two different fields and determine differential dynamic parameters for several residues in the protein. 相似文献
30.
Tolonen A Uusitalo J Hohtola A Jalonen J 《Rapid communications in mass spectrometry : RCM》2002,16(5):396-402
Hypericum perforatum L. (St. John's Wort) has long been known as a medicinal plant, and has been used for the treatment of depression and neuralgic disorders. Its main active constituents are believed to be a naphthodianthrone, hypericin, and a phloroglucinol, hyperforin. A sensitive high performance liquid chromatography (HPLC)/electrospray tandem mass spectrometric method for fast simultaneous determination of six major naphthodianthrones and phloroglucinols of Hypericum perforatum extract has been developed. The method, based on multiple dissociation reaction monitoring (MRM), allows the analysis of hypericin, protohypericin, pseudohypericin, protopseudo-hypericin, hyperforin and adhyperforin from the extract in less than 5 min. Good linearity over the range 0.1-1000 ng/mL for hyperforin and 2-500 ng/mL for hypericin was observed. Intra-assay accuracy and precision varied from 2 to 19% within these ranges. Lower levels of quantitation for hyperforin were 0.5 ng/mL and 2 ng/mL for hypericin. 相似文献