一种基于磁性纳米粒子PCR的高通量SNP分型方法

利用磁性纳米粒子PCR扩增(MNPs-PCR)和等位基因特异性双色荧光探针(Cy3, Cy5)杂交, 建立了一种单核苷酸多态性(SNP)分型的新方法. 应用该方法对9个样本MTHFR基因的C677T多态进行检测, 野生和突变型样本正错配信号比大于9.0, 杂合型正错配信号比接近1.0, 分型结果经测序验证. 此方法无须产物纯化、浓缩, 扫描分型结果快速、直观, 是一种操作简单、快速、高通量、高灵敏度的分型方法.     

改性聚苯乙烯微球的制备及其胶体晶体的组装

采用甲基丙烯酸改性的无皂乳液聚合方法制备了尺寸为210 nm、含羧基的聚苯乙烯(PS)微球，用红外光谱、透射电子显微镜和粒度分析仪对其形状和结构进行分析，结果表明，经甲基丙烯酸改性后得到了表面为高密度电荷的单分散性PS微球.用垂直沉积法快速制备出在较大范围(大于1 cm2)呈现很好有序性的密排结构聚苯乙烯胶体晶体薄膜，其在590 nm波长处存在光子带隙.在电子显微镜下，观察到这种胶体晶体是面心立方(fcc)密排结构.     

Synthesis, crystal structures and magnetic properties of Cu(II) compounds bridged by the terephthalate ligand and hydrogen bonds

A 3D network [Cu(tmen)(tp)(H₂O)₂]_n (1) (tmen = N,N,N′,N′-tetramethylethylenediamine; tp = terephthalate) and a 2D sheet [Cu(pyrazole)₂(tp)]_n (2), featuring 1D chains interwoven by hydrogen bonds, have been prepared and characterized by means of X-ray analyses and magnetic measurements. For 1, coordinative zigzag chains contain Cu(II) centers capped by the chelate ligand tmen, in which the tetragonal structure is elongated due to Jahn–Teller distortion. Coordinated water molecules are hydrogen-bonded to two free carboxylate oxygens of tp bridges, leading to the observed 3D structure. The use of the non-chelating capping ligand pyrazole produced the covalent-bonded 1D linear compound 2 with hydrogen bonds. A severe octahedral distortion of the Cu(II) center arises from a small bite angle (52.3(1)°) of two carboxylate oxygen atoms of tp, which are in turn hydrogen-bonded to the N–H groups of pyrazole ligands coordinated to Cu(II) atoms in neighboring chains. Magnetic data were fitted with the high-temperature series expansion for the Heisenberg chain spin Hamiltonian H = −J∑_iS_i · S_i + 1 together with consideration of the molecular field approximation (zJ′). Both compounds interestingly exhibit ferromagnetic interactions with g = 2.17, J = 4.08 cm⁻¹, zJ′ = −0.28 cm⁻¹ for 1 and g = 2.09, J = 1.47 cm⁻¹, zJ′ = −0.04 cm⁻¹ for 2. By taking into account structural parameters of distances between Cu atoms, it is reasonably assigned that the ferromagnetic couplings (J > 0) in these systems originate from the hydrogen bonds. The spin density of the d_x²-y² orbital on a Cu(II) atom in a chain is propagated and induced over the d_z² orbital of another Cu(II) atom in an adjacent chain. This orbital orthogonality gives rise to such interactions. The negative zJ′ term suggests that the tp bridges communicate only tiny antiferromagnetic interactions.     

A new oxamato-bridged heterotrinuclear NiCuNi complex with irregular spin state structure: Synthesis, spectroscopy, crystal structure and magnetism

A new oxamato-bridged Ni^IICu^IINi^II species, [Ni(tacn)(H₂O)]₂[μ-Cu(pba)](ClO₄)₂·6H₂O 1, (tacn=1,4,7-triazacyclononane; pba=1,3-propylenebis(oxamato)) has been synthesized and structurally as well as magnetically characterized. Complex 1 has a discrete trinuclear Ni^IICu^IINi^II structure: Two nickel(II) ions are bridged by [Cu(pba)]²⁻ anion, macrocyclic ligand tacn works as terminal ligand of the nickel(II) center. The magnetic data of compound 1 was analyzed by means of

leading to g_Cu=2.19, g_Ni=2.18, J=−112.8 cm⁻¹, D=±4.31 cm⁻¹. The parameters are compared with the similar complexes and the irregular spin state structure of complex 1 is also described here.     

Synthesis and properties of the Co7Se8−xSx and Ni7Se8−xSx solid solutions

We report the synthesis and elementary properties of the Co₇Se_8−xS_x (x=0-8) and Ni₇Se_8−xS_x (x=0-7) solid solutions. Both systems form a NiAs-type structure with metal vacancies. In general, the lattice parameters decrease with increasing x, but in the Ni₇Se_8−xS_x system c increases on going from x=5 to 7. Magnetic susceptibility measurements show that all samples exhibit temperature-independent paramagnetism from 25-250 K. Samples within the Co₇Se_8−xS_x system, as well as Ni₇Se₈ and Ni₇SeS₇, were found to be poor metals with resistivities of ∼0.20 and ∼0.06 mΩ cm at 300 K, respectively. The Sommerfeld constant (γ) was determined from specific heat measurements to be ∼13 mJ/mol_CoK² and ∼7 mJ/mol_NiK² for Co₇Se_8−xS_x and Ni₇Se_8−xS_x, respectively.     

Synthesis and characterization of a Ruddlesden-Popper compound: Sr3FeMoO7

A powder sample of Sr₃FeMoO₇ was synthesized by solid-state reaction in reduced atmosphere (5% H₂/Ar). At room temperature, Sr₃FeMoO₇ crystallizes in a typical Ruddlesden-Popper (n=2) structure in the space group I4/mmm, and . The structure refinement indicates that the Fe and Mo ions are randomly distributed in a single B-site with small fraction of B-site and oxygen vacancies. At low temperature, long-range magnetic interaction was observed. The antiferromagnetic magnetic interaction can be described with a large unit cell, and c_m=c_n, in the magnetic space group An′.     

Ternary rare-earth nickel arsenides R3Ni7As5 (R=La, Ce, Pr, Nd, Sm) with a new variant of the BaAl4-type: crystal structure and physical properties

The ternary rare-earth nickel arsenides R₃Ni₇As₅ (R=La, Ce, Pr, Nd, Sm) were prepared by arc melting the elemental components and subsequent annealing at T=1070 K. The crystal structure of Ce₃Ni₇As₅ was determined from single-crystal X-ray data: space group Pmmn, Z=2; a=1.24210(6), b=0.40797(2), c=0.96436(5) nm, R_F=0.037 (R_w=0.044); 596 independent reflections; 53 variable parameters. It is a new structure type, which belongs to the family of BaAl₄-related structures. The magnetic properties are as follows: La₃Ni₇As₅ is a Pauli-type paramagnet above 4.2 K, Pr₃Ni₇As₅ remains paramagnetic in the temperature range investigated and Nd₃Ni₇As₅ undergoes a ferromagnetic ordering at T_C=24 K. Sm₃Ni₇As₅ orders antiferromagnetically at a Néel temperature of T_N=18 K followed by a spin flip towards parallel spin-alignment below T_C=6 K. Ce₃Ni₇As₅ reveals a strong deflection of the linear temperature dependence of the inverse susceptibility due to an intermediate valence behavior. The temperature dependence of the electrical resistivities for the La, Pr, Nd, Sm containing samples corroborates with the metallic state of the non-magnetic (La) and the magnetically ordered compounds, whereas in case of Ce₃Ni₇As₅ the resistivity seems to be determined by an interplay of Kondo scattering and crystalline field effects. L_III X-ray absorption spectra confirm the demagnetization effects owing from valence fluctuations, the actual valence thereby changes from ν=3.10-3.14 at room temperature and 10 K, respectively.     

Synthesis and magnetic properties of μ-phenolato copper (Ⅱ) binuclear complexes with different exogenous bridges

The syntheses and magnetic properties are reported for a series of copper(Ⅱ) complexes prepared from a pentadentate binucleating ligand 2,6-diformyl-4-methylphenol di(benzoyl-hydrazone) (H3L). These complexes incorporate different exogenous ions (X-) into a bridging position to form copper(Ⅱ) binuclear complexes of the formula [Cu2(H2L)X]2+, where X-= Br-(1), Cl-(2), HO-(3), C2H5O-(4) and C3H3N2- (5). The complexes have been characterized with variable temperature magnetic susceptibility (4.2-300 K) and the observed data were fit to those from a modified Bleaney-Bowers equation by least-squares method, giving the exchange integral 2J = -6.2 cm-1 for 1, -76.4 cm-1 for 2, -241.9 cm-1 for 3, -231.1 cm-1 for 4 and -343.8 cm-1 for 5. This suggested that there is an antiferromagnetic interaction between the Cu(Ⅱ) ions and the sequence of the effect of some exogenous bridging ligands on magnetic coupling is corresponding to that in spectrochemical series.     

Co3{CH3C(NH3)(PO3H)(PO3)}2 {CH3C(NH3)(PO3H)2}2(H2O)4·2H2O: A cobalt 1-aminoethylidenediphosphonate with a layer structure

This paper describes the structure and magnetic properties of a novel cobalt 1-aminoethylidenediphosphonate compound, namely Co₃{CH₃C(NH₃)(PO₃H)(PO₃)}₂{CH₃C(NH₃)(PO₃H)₂}₂(H₂O)₄·2H₂O (1). The structure contains a trimer unit of Co₃{CH₃C(NH₃)(PO₃H)(PO₃)}₂ in which two equivalent phosphonate ligands chelate and bridge the three cobalt ions. Each trimer unit is further linked to its four equivalent neighbors through corner-sharing of CoO₆ octahedra and CPO₃ tetrahedra, forming a two-dimensional layer in the bc-plane which contains 12-membered rings. These layers are connected to each other by extensive hydrogen bonds. Magnetic studies show that weak antiferromagnetic interactions are mediated between the cobalt ions. Crystal data for 1: monoclinic, space group C2/c, a=27.727(4), b=7.1091(11), , β=118.488(3), , Z=2.     

Direct computation of second-order SCF properties of large molecules on workstation computers with an application to large carbon clusters

Summary The ab initio SCF computation of second-order properties of large molecules (with 50 atoms or more) on workstation computers is demonstrated for static dipole polarizabilities and nuclear magneting shieldings. The magnetic shieldings are calculated on the basis of gauge including atomic orbitals (GIAO). Algorithmic advances (semi-direct algorithms with efficient integral pre-screening, and use of a quadratically convergent functional for the polarizabilities) are presented together with an illustrative application to the fullerenes C₆₀ and C₇₀.