A practical synthetic route to 4′-alkylaristeromycin derivatives: 4′-methylaristeromycin

(−)-(1S,4R)-4-Hydroxy-2-cyclopenten-1-yl acetate provided a convenient entry point for a 16-step chiral preparation of 4′-methylaristeromycin. This procedure is adaptable to a number of carbocyclic nucleosides with a diversity of substitution at C-4′ and C-5′ and a variety of heterocyclic bases.     

Melting behavior of one-dimensional zirconium nanowire

In this paper, we analyze the melting behavior of zirconium nanowire using the results of a series of molecular dynamics simulations. Our calculation employs a well-fitted, tight-binding many-body potential for zirconium atoms. The melting point of the nanowire is predicted by the root-mean-square displacements for inner and outer shells. Our simulations predict two melting behaviors: one is the inner melting and the other is the outer melting. Our results reveal that the melting of nanowire starts from the inner shell atoms. The melting point of zirconium nanowire is lower than the bulk value (2125 K). Moreover, the melting point of the inner shell is lower than that of the outer shell. A coexistence of crystal and liquid units is observed in the melting process of nanowire. An investigation of local clusters is carried out to further analyze the melting mechanism of the nanowire. The presence of the local clusters 1331, 1321, 1211, etc. is an indication of disordered structures. The pair and angular correlation functions are also presented for the analysis of the melting behavior. It is not only the diffusion of single atom but the diffusion of clusters result in the occurrence of the melting.     

A reliable ab initio potential energy surface and vibrational states for the ground electronic state of HgH2(X1Sigma+g)

A three-dimensional global potential energy surface for the ground (X (1)Sigma(+)(g))electronic state of HgH(2) is constructed from more than 13,00 ab initio points. These points are generated using an internally contracted multireference configuration interaction method with the Davidson correction and a large basis set. Low-lying vibrational energy levels of HgH(2), HHgD, and HgD(2) calculated using the Lanczos algorithm are found to be in good agreement with the available experimental band origins. The majority of the vibrational energy levels up to 9000 cm(-1) are assigned with normal mode quantum numbers. Our results indicate a gradual transition for the stretching vibrations from the normal mode regime at low energies to the local mode regime near 9000 and 8000 cm(-1) for HgH(2) and HgD(2), respectively, as evidenced by a decreasing energy gap between the (0,0,n(3)) and (1,0,n(3)-1) vibrational states and bifurcation of the corresponding wave functions.     

电化学合成铜配合物的研究

采用金属铜为"牺牲"阳极,首次在无隔膜电解槽中,电化学溶解金属铜一步制备了纳米CuO前体Cu(OEt)2, Cu(OBu)2, Cu(acac)2, Cu(OEt)(acac), Cu(OBu)(acac) (acac为乙酰丙酮基).产物通过红外光谱(FT-IR)、拉曼光谱(Raman spectrum)进行表征.同时讨论了影响电合成铜醇盐及其配合物的关键因素.实验表明,防止阳极钝化,温度控制在30～50 ℃,采用有机胺溴化物为导电盐, 电极电位控制在0.8～1.2 V之间,可以提高电合成效率.实验同时表明Cu(acac)2, Cu(OEt)(acac), Cu(OBu)(acac)可作为制备含铜纳米材料前驱体.     

Immunosuppressive ent‐Kaurene Diterpenoids from Isodon serra

Three new enmein‐type ent‐kaurenoids, i.e., the two pairs 1 and 2 of 20‐epimers and the (20R)‐isomer 3 , besides the seven known diterpenoids 4 – 10 , were isolated from the aerial parts of Isodon serra. Their structures were elucidated by spectroscopic techniques and X‐ray diffraction. The immunosuppressive effect for T‐lymphocytes proliferation induced by Con A in BALB/c mouse was evaluated for the isolates 1 – 10 . They all displayed a remarkable inhibitory effect, with multi‐glycosides of Tripterygium wilfordii as positive reference substance (Table 3).     

A zwitterion of 1,5‐bis­(2‐hydroxy­benzamido)‐3‐aza­pentane: a two‐dimensional hydrogen‐bonding network involving dimers

The title compound, 2‐{N‐[2‐(2‐hydroxy­benzamido)ethyl­ammonio­ethyl]amino­carbon­yl}phenolate, C₁₈H₂₁N₃O₄, crystallizes in a zwitterionic form as a result of inter­molecular proton transfer and possesses a negatively charged phenolate group and a protonated amino group. The 2‐hydroxy­benzamide and 2‐(amino­carbonyl)­phenolate moieties attached to the two ends of the C—C—N—C—C backbone adopt a cis conformation in relation to this backbone. All N‐ and O‐bound H atoms are involved in hydrogen‐bond formation; the zwitterions are first linked into head‐to‐tail dimers, which are further organized into a two‐dimensional network parallel to the crystallographic bc plane.     

Lysine peroxycarbamates: free radical-promoted peptide cleavage

Strategies are reported that combine in one step a predictable chemical-based protein digestion with mass spectrometry. Lysine residue amino groups in peptides and proteins are modified by reaction with a peroxycarbonate derived from p-nitrophenol, and tert-butyl hydroperoxide. The peroxycarbonate reacts with lysine residues in peptides and proteins, and the resulting lysine peroxycarbamates undergo homolytic fragmentation under conditions of low-energy collision-induced dissociation (CID). Observed fragmentation of the peptides involves apparent free radical processes including Hofmann-L?ffler-type rearrangements that lead to peptide chain fragmentation. Strategies for directed cleavage of peptides by free radical promoted processes are feasible, and such strategies may well simplify schemes for protein analysis.     

Differential determination of arsenic (III) and total arsenic with L-cysteine as prereductant using a flow injection non-dispersive atomic absorption device

Speciation of arsenic in environmental samples gains increasingly importance, as the toxic effects of arsenic are related to its oxidation state. A method was developed for the determination of trace amounts of arsenic (III) and total arsenic by flow injection hydride generation coupled with an in-house made non-dispersive AAS device. The total arsenic is determined after prereduction of arsenic (V) to arsenic (III) with L-cysteine in a low concentration of hydrochloric, acetic or nitric acid. The conditions for the prereduction, hydride generation and atomization were systematically investigated. A quartz tube temperature of 800 degrees C was found to be optimum in view of peak shape and baseline stability. Pb(II), Ni(II), Fe(III), Cu(II), Ag(I), Al(III), Ga(II), Se(IV), Bi(III) were checked for interfering with the 2 microg/L As(V) signal. A serious signal depression was only observed for Se(IV) and Bi(III) at a 150-fold excess. With the above system, arsenic was determined at a sampling frequency of about 1/min with a detection limit (3sigma) of 0.01 microg/L using a 0.5 mL sample. The reagent blank was 0.001+/-0.0003 absorbance units and the standard deviation of 10 measurements of the 2 microg/l As signal was found to be 1.2%. Results obtained for standard reference materials and water samples are in good agreement with the certified values and those obtained by ICP-MS     

Studies of the electrochemical behavior of epinephrine at a homocysteine self-assembled electrode

The self-assembled electrode with the homocysteine monolayer (Hcy/Au) has been characterized by infrared spectroscopy and ac impedance spectroscopy in electrolyte. The Hcy/Au electrode is demonstrated to promote the electrochemical response of epinephrine (E) by cyclic voltammetry. A pair of well-defined redox waves was obtained and the calculated standard rate constant (k_s) is 2.1×10⁻² cm s⁻¹ at the self-assembled electrode. The reduction peak of E can be used to determine the concentration of E in presence of ascorbic acid (AA) owing to the Hcy/Au also promoting the electrochemical oxidation of AA.     

On-line Separation and Detection of Peptides by Capillary Electrophoresis / Electrospray FT-ICR-MS

Recently, capillary electrophoresis/electrospray ionization mass spectrometry (CE/ESI- MS) has been rapidly developed as a powerful analytical tool for charged species ranged from small molecules such as carboxylic acids1, phenolic compounds2, metal species3, tetramines4, herbicides5, drugs and drug metabolites6 to peptides and proteins7, 8. The ESI mode has proven to be sensitive, versatile and relatively easy to use in combination with CE. CE confers rapid analysis and efficient separ…