氩离子轰击还原三氧化钨纳米线薄膜的光电子能谱研究

利用X射线光电子能谱(XPS)及氩离子刻蚀技术,原位研究了氩离子轰击对三氧化钨纳米线薄膜的还原作用,钨的价态由+6价逐渐被还原为0价,并获得了具有多价态结构的氧化钨薄膜.通过对实验结果的分析,定性描述了氩离子轰击还原三氧化钨纳米线薄膜的原理,认为择优溅射在整个还原过程中起着关键作用.     

A new ent-labdane eiterpenoid lactone from Andrographis paniculata

A new ent-labdane diterpenoid lactone with a new natural product was isolated from Andrographis paniculata. Their structures were elucidated on the basis of spectral evidences including 2D NMR.     

1-(2-萘基)-3-甲基-5-吡唑啉酮衍生试剂的制备及其在高效液相色谱-质谱法测定糖类化合物中的应用

以1-(2-萘基)-3-甲基-5-吡唑啉酮(NMP)作为柱前衍生试剂,建立了简单、灵敏的糖类组分的反相高效液相色谱测定方法。NMP与糖在氨为催化剂的条件下,于70 ℃下反应可获得稳定的衍生产物。在Hypersil ODS 2反相色谱柱上,实现了8种单糖的基线分离。衍生物线性相关系数均大于0.9985,检出限为0.58～1.1 pmol。利用柱后在线串联质谱的电喷雾电离正离子模式监测,获得了各组分的质谱定性及裂解规律,特别是m/z 473的特征碎片离子可作为单糖NMP衍生物的判定依据。与1-苯基-3-甲基-5-吡唑啉酮(PMP)相比,NMP对糖的衍生化具有灵敏、简单、质谱裂解规律性强、重现性好等优点。该方法用于测定油菜花粉多糖中的单糖组成,结果令人满意。     

锰（Ⅲ）5,10,15-三（五氟苯基）-Corrole配合物的DFT计算

在6-31G*水平上采用DFT(UB3LYP)方法对锰(Ⅲ)5,10,15-三(五氟苯基)-corrole[(TPFC)MnⅢ]及其咪唑轴向配位加合物(TPFC)MnⅢ(Im)进行了几何结构全优化.计算结果表明,咪唑的配位作用不会改变其基态的高自旋(s=2)特性.(TPFC)MnⅢ与咪唑配位形成轴向加合物后,其中心金属Mn原子偏离平面结构,与corrole大环N4平均平面的距离达到0.02734 nm.NBO分析显示(TPFC)MnⅢ和(TPFc)MnⅢ(Im)中心金属锰的电子组态为(dxz)1(dyz)1(dz2)1(dx2-y2)1(dxy)0(TPFC)MnⅢ(Im)前线分子轨道能级明显上升,从其β-(LUMO+3)轨道可见咪唑配位N原子的py轨道与中心金属Mn原子撕道形成了d-pπ轨道.TD-DFT计算发现,(TPFC)MnⅢ和(TPFC)MnⅢ(Im)电子光谱Q带的"四轨"特征比B带明显;(TPFC)MnⅢ的CT带主要源自β-(HOMO-1)→β(LUMO+5)和β-HOMO→β-(LUMO+4)的跃迁,(TPFC)MnⅢ(Im)的CT带则主要源自β-(HOMO-1)→β-(LUMO+3)和β-HOMO→β-(LUMO+4)的跃迁.     

腺苷与人血清白蛋白间相互作用的荧光光谱及分子模型法研究

在模拟人体生理条件下,结合紫外光谱和分子对接模型运用荧光光谱研究了腺苷与人血清白蛋白(HSA)间的键合作用。腺苷有较强的能力猝灭人血清白蛋白的内源荧光,且根据Stern-Volmer方程判断出猝灭机制为静态猝灭。本文运用相应的荧光值和Vant’Hoff热力学方程求得了不同温度下的结合常数(K)以及一些热力学参数,如焓变(ΔH)和熵变(ΔS)。结果表明：键合过程中疏水作用力对新化合物的稳定性起主要作用,这与分子对接模型方法研究的结果基本一致。另外还研究了常见离子对结合常数的影响。     

Protein surface recognition of the novel tetra-carboxylphenyl calix[4]arene to cytochrome c

The interaction of the novel tetra-carboxylphenyl calix[4]arene （TCPC） with the bovine heart cytochrome c （Cc） was first investigated by fluorescence spectroscopy and molecular modeling methods. The formation of a stable 1：1 complex was monitored by fluorescence titration, and its binding constant is 1.916 ×10^7 L mol^-1. Molecular modeling reveals the recognition mechanism of TCPC to the Cc surface, that is, the electrostatic interaction drives TCPC to the Cc surface, and the van der Waals interaction orientates TCPC parallel to the cleft of Cc.     

Two novel 18-metallacrown-6 complexes: Synthesis,structural characterization and bioactivity

Two new macrocyclic hexanuclear metal(III) 18-metallacrowns-6, [Mn₆(acshz)₆(H₂O)₆] · 18H₂O (1) and [Fe₆(acshz)₆(CH₃OH)₆] · 6CH₃OH · 6H₂O (2), have been synthesized and characterized, where acshz³⁻ is N-acetyl-5-chlorosalicylhydrazidate. These crystal structures contain neutral 18-membered metallacrown rings consisting of six metal(III) ions and six acshz³⁻ ligands. The ring is formed by the succession of six structural moieties of the type [M(III)–N–N] through hydrazide N–N groups bridging the ring metal ions. The ligand enforces the metal ions to form the stereochemistry of a propeller configuration with alternate Λ/Δ or Δ/Λ forms. The largest diameters of the hexanuclear rings are about 6.97 Å at the entrance and 9.53 Å at the centre of the cavity for 1; and 7.94 and 10.24 Å for 2, respectively. The solution integrity and stability of the metallacrowns were confirmed using electrospray ionization ESI-MS and UV–Vis spectroscopy in methanol. Antibacterial screening data indicate the formation of the metallacrown 1 reduces the antimicrobial activity of the ligand H₃acshz hugely, while metallacrown 2 has strong antimicrobial activity against Bacillus subtilis (B. subtilis).     

微囊藻毒素-LR免疫亲和层析柱的研制和应用

用CNBr-activated Sepharose4B和微囊藻毒素-LR的单克隆抗体制备了免疫亲和层析柱,测得抗体偶联率在75.7%~94.1%之间。制得的免疫亲和层析柱最大柱容量在76~95ng之间,柱空白为0,回收率在90.8%~105.1%之间。柱子再生重复使用6次后,回收率不低于75%。建立了免疫亲和层析柱-高效液相色谱测定水样中的微囊藻毒素-LR的方法。该法检出限为5ng/L;线性定量范围为10~500ng/L。实验结果显示,免疫亲和层析柱特异性好,一次净化能除去绝大部分干扰物,净化效果明显优于现有的固相萃取柱。     

Mass analysis in islands of stability with linear quadrupoles with added octopole fields

Mass analysis with linear quadrupole mass filters is possible by forming "islands" in the stability diagram with auxiliary quadrupole excitation. In this work, computer simulations are used to calculate stability boundaries, island positions, and peak shapes and ion transmission for mass analysis with linear quadrupole mass filters that have added octopole fields of about 2 to 4%. Rod sets with exact geometries that have quadrupole and octopole fields only in the potential, and round rod sets, with multipoles up to N = 10 (the twenty pole term) included in the calculations, show the same stability boundaries, island positions, and peak shapes. With the DC voltage applied to the rods so that the Mathieu parameter a < 0, conventional mass analysis is possible without the use of an island. With the DC polarity reversed so that a > 0, the resolution and transmission are poor preventing conventional mass analysis. In principle, mass analysis in an island is possible with operation at either of two tips. Provided the correct island tip is chosen for mass analysis, peak shapes comparable to those with a > 0 and no excitation are possible, both with a > 0 and with a < 0. In the latter case, the use of an island of stability allows mass analysis when the added octopole otherwise prevents conventional mass analysis.     

非螯合物浊点萃取-石墨炉原子吸收法测定水中痕量铊(Ⅲ)

建立不需形成螯合物的浊点萃取-石墨炉原子吸收法测定水中铊Ⅲ的新方法。用浊点萃取技术富集水中铊Ⅲ,石墨炉原子吸收法测定。经考察,浊点萃取环境水体中铊Ⅲ的最优条件为pH12,90℃水浴2h,Triton X-114浓度2.0g/L;在优化后实验条件下,方法测定铊Ⅲ的检出限为0.018μg/L;相对标准偏差为8.89%~13.7%(C=0.1μg/L及1.0μg/L,n=7);加标回收率为98.0%~101%。本法适于水中痕量铊Ⅲ的测定。