The elastic theory of a single DNA molecule

We study the elastic responses of double-(ds) and single-stranded (ss) DNA at external force fields. A double-strand-polymer elastic model is constructed and solved by path integral methods and Monte Carlo simulations to understand the entropic elasticity, cooperative extensibility, and supercoiling property of dsDNA. The good agreement with experiments indicates that short-ranged base-pair stacking interaction is crucial for the stability and the high deformability of dsDNA. Hairpin-coil transition in ssDNA is studied with generating function method. A threshold force is needed to pull the ssDNA hairpin patterns, stabilized by base pairing and base-pair stacking, into random coils. This phase transition is predicted to be of first order for stacking potential higher than some critical level, in accordance with experimental observations.     

高压下液态Ag-20 at%Ge合金的凝固及密排六方亚稳相的形成

 利用高压淬火方法，在液态Ag-20at%Ge合金的凝固过程中，对比液态急冷低四个数量级的冷却速率得到了单相密排六方结构亚稳相，其点阵参数为a=0.289 8 nm，c=0.470 8 nm，c/a=1.625。     

Precise synthesis of porphyrin array scaffolding polyisocyanides

Aryl isocyanides bearing free‐base and metallo‐porphyrins were prepared and polymerized with a Pd–Pt μ‐ethynediyl complex as the initiator to give polymers with narrow polydispersity indices. The molecular weights of the resulting polymers were precisely controlled by the initial feed ratio of the porphyrin monomer to the initiator. The UV–VIS spectra suggested that the porphyrin pendants are regularly arranged to form stacked columns. Metallo‐porphyrin polymers were also prepared by reacting free‐base porphyrin polymers with metal salts. The successive reactions of free‐base and zinc‐porphyrin monomers resulted in the formation of diblock polymers. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 585–595, 2006     

毛细管电泳中高盐样品在线富集的研究进展

在毛细管电泳分析过程中，简便高效的高盐样品处理技术对血清、尿液、海水和工业废水等样品的富集分析具有重要的意义。综述了在CE中高盐样品在线富集的若干种方法，包括乙腈法、瞬间等速电泳法、pH修饰法、动态pH联接法、胶束反应法和瞬间移动化学反应界面法，并简要地介绍它们的应用和研究进展。     

Synthesis and Crystal Structure of a Novel Layered Lead(Ⅱ) Carboxylate-sulfonate Compound Templated by 4,4''-Bipyridine

A new lead(Ⅱ) carboxylate-sulfonate has been hydrothermally synthesized and characterized by X-ray single-crystal and elemental analyses. It crystallizes in triclinic, space group P,(1) with a=8.1573(6), b=9.4663(7), c=12.7488(9) (A), α=89.2320(10), β=80.7380(10), γ=77.9760(10)°, Z=2, V=950.10(12) (A)3, Mr=599.57, Dc=2.096 g/cm3, μ=9.032 mm-1, F(000)=572, the final R=0.0412 and wR=0.1035. It has a 1D chain structure, and the Pb(Ⅱ) is six-coordinated. Two PbO6 polyhedra are interconnected via edge-sharing into a two-core unit. Such units are further interconnected by 3-sulfonato-benzoic acids into 1D chains which are linked by hydrogen bonds into a layer structure. The 4,4'-bipyridines are located at the interlayer space and link the layers into a supramolecular structure by π-π stacking interactions.     

钯(Ⅱ)-芳香氮碱-氨基酸三元配合物中的电子效应和芳环堆积作用

用pH-电位滴定法测定了Pd(L)(Aa)⁺三元配合物及相应的二元配合物,在25±0.5℃,30%的乙醇水溶液(体积分数),I=0.1(KNO₃)条件下的稳定常数及表征常数。其中L=邻菲罗啉(phen)、苯并咪唑邻菲罗啉(PIP)、邻菲罗啉-5,6-二酮(dophen)、2,9-二甲基邻菲罗啉(dmphen)和联吡啶3,3′-二羧酸(BDA);Aa为甘氨酸(gly)、苯丙氨酸(phe)、酪氨酸(tyr)、S-苄基-半胱氨酸(bcys)、谷氨酰胺(glu)和γ-谷氨酰-α-萘胺(gnapa)。从配合物配体间的电子效应和芳环堆积等观点对配合物的附加稳定性进行了讨论,并计算了电子效应和芳环堆积效应各自对三元配合物附加稳定性的贡献。     

Intramolecular dimers: a new design strategy for fluorescence-quenched probes

Fluorogenic probes dual-labeled with reporter and quencher dyes use a change in fluorescence to monitor biochemical events (e.g., substrate binding or enzyme digestion). Such events change the reporter-quencher distance, which affects fluorescence. Recently, it is has been shown that static quenching through intramolecular dimers is an important mechanism that can sometimes be more efficient than F?rster resonance energy transfer (FRET).     

Synthesis and Crystal Structure of a Novel Manganese Coordination Polymer： 2,5-Bis（4-pyridyl）-3,4-diaza-2,4-hexadiene

A new manganese coordination polymer 1, [Mn(H2O)4(L)]n(ClO4)2n·2nH2O·3nL (L = 2,5-bis(4-pyridyl)-3,4-diaza-2,4-hexadiene), has been synthesized and structurally characterized. The crystal structure was determined by single-crystal X-ray diffraction. The crystal is of monoclinic, space group Pn with a = 13.9176(8), b = 15.4754(9), c = 15.9670(9) , β = 99.5010(10)o, V = 3391.8(3) 3, Z = 2, C56H68Cl2MnN16O14 , Mr = 1315.10, Dc = 1.288 g/cm3, μ = 0.344 mm-1, F(000) = 1374, R = 0.0733 and wR = 0.2035. In the crystal the manganese atom is six-coordinated by two nitrogen atoms from 2,5-bis(4-pyridyl)-3,4-diaza-2,4-hexadiene and four oxygen atoms from water molecules, completing an octahedral geometry. The title complex exhibits a novel supramolecular layer architecture sustained by the concurrence of coordination bonds, hydrogen bonds, and π-π stacking interactions.     

(π)C—H···S, (allyl)C—H···C(π) and π···π intermolecular interactions: synthesis, characterization, and crystal structure of 2,2′-bipyridine bis(diallyldithiocarbamato)zinc(II)

A mixed-ligand Zn(II) complex formulated as [Zn(aldtc)₂(bipy)] (aldtc=diallyldithiocarbamate; bipy=2,2′-bipyridine) was synthesized and characterized by IR, ¹H and ¹³C NMR spectral measurements and X-ray crystallography. The crystal structure of this complex indicates that Zn has a distorted octahedral geometry. The Zn—N distances are invariant (2.168(2) Å), while those of the Zn—S are slightly different (2.5408(9) and 2.5440(9) Å). The N—Zn—N, S—Zn—S and N—Zn—S bond angles are in the range 75.35(13)–99.75(7)°, 70.48(3)–161.02(5)° and 95.26(7)–160.32(7)°, respectively. The crystal packing of the complex shows different motifs of supramolecularity resulting from both hydrophilic ((π)C—H···S) and hydrophobic ((allyl)C—H···C(π)) intermolecular interactions. These interactions result in a chain arrangement of molecules along crystallographic c axis and the chains are further connected via π···π stacking along with ((π)C—H···S along b axis leading to an overall crystal packing that can be regarded as layers of complexes along bc plane, which are held together through nonconventional hydrogen bonding and π···π stacking.     

配体分子结构对Pd(Ⅱ)-Phen-PCA体系堆积作用的影响

用pH电位滴定法测定了含l，10-邻菲咯啉(Phen)和羧酸(CA)配体的三元混配配合物Pd(Phen)(CA)体系的稳定常数，比较和讨论了各种三元混配配合物之间的稳定性差异．实验结果表明，在三元混配配合物Pd(Phen)(PCA)中(PCA为苯基羧酸)存在分子内芳环堆积作用，堆积程度依赖于苯基和配位的羧酸根之间的亚甲基数目，其中以2-苯乙酸和3-苯丙酸与邻菲咯啉为最佳堆积．