具有双螺旋链的新型二维无机-有机骨架晶体材料Ni(PDC)(H2O)2的合成与结构

本文报道由H2PDC合成的新型维层状无机-有机骨架晶体Ni(PDC)(H2O)2(H2PDC=吡啶-2,5-二羧酸), 该化合物的一层是由右手螺旋Ni—O—C链与左手螺旋Ni-pdc链组成, 而邻近的一层则是由左手螺旋Ni—O—C链与右手螺旋Ni-pdc链组成, 层与层之间通过氢键作用形成了三维超分子结构. 用ICP、TG、IR和X射线单晶衍射分析等手段对其结构进行表征.     

Surface-grafted polystyrene beads with comb-like poly(ethylene glycol) chains: preparation and biological application

We prepared surface-grafted polystyrene (PS) beads with comb-like poly(ethylene glycol) (PEG) chains. To accomplish this, conventional gel-type PS beads (35-75 microm) were treated with ozone gas to introduce hydroperoxide groups onto the surface. Using these hydroperoxide groups, poly(methyl methacrylate) (PMMA, Mn= 22,000-25,000) was grafted onto the surface of the PS beads. The ester groups of the grafted PMMA were reduced to hydroxyl groups with lithium aluminum hydride (LAH). After adding ethylene oxide (EO) to the hydroxyl groups, we obtained the PS-sg-PEG beads, which had a rugged surface and a diameter of 80-150 microm. We could obtain several kinds of the PS-sg-PEG beads by controlling the chain lengths of the grafted PMMA and the molecular weights of the PEG chains. The grafted PEG layer was about 30-50 microm thick, which was verified from the cross-sectioned views of the fluorescamine-labeled beads. These fluorescence images proved that the beads possessed a pellicular structure. Furthermore, we found that the surface-grafted PEG chains had the characteristic property of reducing non-specific protein adsorption on the beads.     

Influence of inhibitory compounds and minor sugars on xylitol production by <Emphasis Type="Italic">Debaryomyces hansenii</Emphasis>

To obtain in-depth information on the overall metabolic behavior of the new good xylitol producer Debaryomyces hansenii UFV-170, batch bioconversions were carried out using semisynthetic media with compositions simulating those of typical acidic hemicellulose hydrolysates of sugarcane bagasse. For this purpose, we used media containing glucose (4.3–6.5 g/L), xylose (60.1–92.1 g/L), or arabinose (5.9–9.2 g/L), or binary or ternary mixtures of them in either the presence or absence of typical inhibitors of acidic hydrolysates, such as furfural (1.0–5.0 g/L), hydroxymethylfurfural (0.01–0.30 g/L), acetic acid (0.5–3.0 g/L), and vanillin (0.5–3.0 g/L). D. hansenii exhibited a good tolerance to high sugar concentrations as well as to the presence of inhibiting compounds in the fermentation media. It was able to produce xylitol only from xylose, arabitol from arabinose, and no glucitol from glucose. Arabinose metabolization was incomplete, while ethanol was mainly produced from glucose and, to a lesser less extent, from xylose and arabinose. The results suggest potential application of this strain in xyloseto-xylitol bioconversion from complex xylose media from lignocellulosic materials.     

Synthesis and Crystal Structure of a 1D Chained Coordination Polymer Containing One-dimensional Egg-like Channels： {[Cu2（C2O4）2（inta）4]（inta）}n （inta = Isonicotinamide）

A new one-dimensional copper coordination polymer chain has been prepared and fully characterized by single-crystal X-ray diffraction,elemental analyses and IR spectroscopy. The compound {[Cu2(C2O4)2(inta)4](inta)}n1 crystallizes in the triclinic system,space group P1,with a=8.4722(5),b=10.9825(6),c=11.6128(6),α=104.8050(10),β=102.5740(10),γ= 109.6890(10)o,V=927.18(9)3,Mr=929.79,Z=1,Dc=1.665 g/cm3,F(000)=475,μ=1.231 mm-1,R=0.0453 and wR=0.1185 for 3290 observed reflections (I > 2σ(I)). Of the compound,the Cu center is octahedrally coordinated with oxalate acting as a tetra-dentate ligand coordinated to the copper atom and each inta serving as a terminal ligand by employing only one N-donor to coordinate with the Cu center. An infinite {Cu2(C2O4)2}∞ chain is formed along the c axis. Furthermore,the 1D chains are held together via extensive hydrogen-bonding interactions to generate a three-dimensional network with 1D channels (ca. 5.491×11.507) where inta molecules are filled.     

A facile access to ureido sugars. Synthesis of urea-bridged β-cyclodextrins

The preparation of a urea-bridged β-cyclodextrin dimer and of a 6-monodeoxy-6-mono[3-(β-d-glucopyranos-2-yl)ureido]-β-cyclodextrin has been developed, using triphosgene as the isocyanation agent in an aqueous two-phase system. Per-O-acetylated β-d-gluco and mannopyranosylamines and 2-amino-2-deoxy-α- and β-d-glucose were also transformed into the corresponding isocyanates and converted in situ into ureas by coupling with aromatic and aliphatic amines.     

Superbeads: immobilization in "sweet" chemistry

Enzymatic oligosaccharide synthesis using recombinant glycosyltransferases is able to overcome the difficulties associated with chemical methods. Nonetheless, sugar nucleotide regeneration cycles are necessary for the glycosylation. The multistep enzyme reaction can be efficiently carried out on superbeads that are prepared by immobilizing multienzyme mixtures on bead support through fused binding domains.     

Singular perturbed Markov chains and exact behaviors of simulated annealing processes

We study asymptotic properties of discrete and continuous time generalized simulated annealing processesX(·) by considering a class of singular perturbed Markov chains which are closely related to the large deviation of perturbed diffusion processes. Convergence ofX(t) in probability to a setS ₀ of desired states, e.g., the set of global minima, and in distribution to a probability concentrated onS ₀ are studied. The corresponding two critical constants denoted byd and withd are given explicitly. When the cooling schedule is of the formc/logt, X(t) converges weakly forc>0. Whether the weak limit depends onX(0) or concentrates onS ₀ is determined by the relation betweenc, d, and . Whenc>, the expression for the rate of convergence for each state is also derived.     

Synthesis and structure of a novel three-dimensional metal selenite containing multidirectional intersecting double helical chains: [Fe2(H2O)4(SeO3)2]

A novel three-dimensional metal selenite [Fe₂(H₂O)₄(SeO₃)₂] (1) has been hydrothermally synthesized and characterized by the elemental analyses, IR spectrum, TG analysis and the single crystal X-ray diffraction. Compound 1 crystallizes in the monoclinic system, space group P21/n, with a=6.5283(13) Å, b=8.8754(18) Å, c=7.6798(15) Å, (=98.82(3)β, V=439.71(15) Å3, and Z=2. Compounds 1 exhibits interesting three-dimensional structure constructed from {FeO₆} octahedra and {SeO₃} pyramids linked via the corner- and/or edge-sharing mode. The most interesting structural feature of compound 1 is that the existence of multidirectional intersecting double helical chains in one compound.     

Synthesis of thiol chelating resins and their adsorption properties toward heavy metal ions

A series of chelating resins, derived from a macroreticular styrene-divinylbenzene (2%) copolymer beads grafted with various poly(ethylene glycols) HO? (? CH₂? CH₂? O? )_n? H(n = 0, 4, 9, 13) and containing thiol groups as chelating functions, have been synthesized in a three-step reaction sequence. The structure of the functionalized resins was confirmed by IR spectrophotometry, elemental analysis, and differential scanning calorimetry. The complexation behavior of these thiol resins was investigated towards Hg(II), Cu(II), and Pb(II) ions in aqueous solution by a batch equilibration technique. The influence of pH on adsorption capacity was also examined. The adsorption values for metal ions' intake followed the order Hg(II) > Cu(II) > Pb(II). The affinity of these polymers towards Hg(II) ions was so high that the total mercury level in the liquid decreased from 20 ppm to below 10 ppb after 2 h of treatment. Polymers can be regenerated by washing with a solution of hydrochloric acid (6N) and 10% by weight of an aqueous solution of thiourea. © 1994 John Wiley & Sons, Inc.     

Syntheses and Crystal Structures of Two Metal Succinates Modified by Bipyridines

Two new metal succinates modified by rigid bipyridines, Cd(4, 4′‐bpy)(C₄H₄O₄)·1/4H₂O ( 1 ) and Cu(2, 2′‐bpy)(C₄H₄O₄)_0.5(NO₃)(H₂O) ( 2 ) (bpy = bipyridine), have been synthesized by hydrothermal reactions and structurally determined. Complex 1 crystallizes in the orthorhombic space group Cmca with the cell parameters a = 11.696(2), b = 15.554(2), c = 15.874(3) Å, α = β = γ = 90.00°, V = 2888(3) ų, Z = 8. Complex 2 crystallizes in the triclinic space group with a = 7.077(1), b = 9.838(2), c = 10.461(2) Å, α = 71.941(3)°, β = 73.078(3)°, γ = 74.502(3)°, V = 649.8(2) ų, Z = 2. In complex 1 , a 2‐D network was formed by Cd‐succinato bonding. The 2‐D networks are pillared by 4, 4′‐bpy ligands, forming a 3‐D grid framework. The 2‐fold interpenetration of the resulting 3‐D frameworks completes the molecular structure. In complex 2 , the Cu^II atom adopts a distorted octahedral in which the Cu^II atoms are bridged by two H₂O molecules into an infinite zigzag chain, [Cu₂(H₂O)₂(C₄H₄O₄)]_n. The neighboring chains are further linked by π‐π stacking interactions into a 2‐D network, and the interlayer hydrogen bonds lead to the final 3‐D crystal structure.