十四-(2,6-O-烯丙基)-β-环糊精的合成研究与表征

利用β－环糊精的吡喃葡萄糖单元上2，3，6－位羟基氢的反应活性差异，选用合适的催化剂和修饰剂合成了十四，（2，6－O－烯丙基）－β－环糊精，研究了反应温度，反应时间、催化剂、修饰剂等对合成的影响，产物经元素分析，IR，1H，NMR，FAB－MS等表征。     

聚乙烯吡啶(PVP)催化合成O-酰化乳酸酯的研究

本文利用聚乙烯吡啶（ｐｏｌｙｖｉｎｙｌ ｐｙｒｉｄｉｎｅ）为催化剂，对乳酸酯进行Ｏ－酰化反应，对影响反应的诸因素进行了讨论，产物的收率为７０－８０％。     

乙烷部分氧化超细Fe－Mo－O催化剂的研究

采用溶胶-凝胶法制备了Fe－Mo－O催化剂，用XRD、TEM、BET、IR、TPR、TPD和微反等技术研究了催化剂晶体结构、表面构造、晶格氧活泼性、化学吸附和乙烷部分氧化反应性能。Fe－Mo－O复合氧化物催化剂是由超细微粒组成，微粒粒径约10 nm～20 nm，比表面积为48.1 m2/g。催化剂表面由Lewis碱位（Mo=O键的端氧和Fe－O－Mo键中的桥氧）及Lewis酸位构成。乙烷能以甲基中的H原子吸附在催化剂表面Lewis碱位Mo=O的端氧上形成分子吸附态，其部分氧化产物主要是C2H4和少量的CH3CHO。     

气相中苯二聚体离子结构的串联质谱研究

应用碰撞诱导解离技术研究了苯自身化学电离条件下和苯化学电离（甲苯为反应气）条件下离子－分子反应产物ｍ／ｚ１５５和１５６离子的碰撞诱导解离（ＣＩＤ）破裂特性，并与化学电离条件下质子化联苯生成ｍ／ｚ１５５离子的ＣＩＤ碎裂反应相比较，获得了苯离子１－分子反应产物ｍ／ｚ１５５和１５６离子的结构信息。     

4-[2-(9,10-二氰蒽)乙烯基]-N-甲基-N-十六烷基苯胺的合成及其吸收光谱行为的研究

通过还原、溴代、氰化、Wittig反应等七步反应设计合成了一新二元电子给体－受体（D－A）化合物：4－［2－（9，10－二氰蒽）乙烯基］－N－甲基－N－十六烷基苯胺（DCACMA，反式）并初步研究了其吸收光谱行为。研究表明，基态下DCACMA分子中电子给体与电子受体（CMA与DCA）间存在显著的电荷转移相互作用，在LB膜及簇集态（DMSO－H2O二元体系中）下，DCACMA分子呈H－型簇集排列。     

侧链键接腺嘌呤的高分子核酸类似物对N-磷酰化氨基酸偶联尿苷反应的模板效应

将高分子核酸类似物聚甲基丙烯酸－β-（N^7－腺嘌呤基）乙酯加入到尿苷与N－（O,O′－二异丙基）－磷酰化丙氨酸的反应体系之中,研究其对此反应体系的影响。结果表明,聚甲基丙烯酸－β－（N^7－腺嘌呤基）乙酯参与了尿苷与磷酰化丙氨酸间的相互作用,并促进了具有较高离子密度、较大的流体动力学体积的大分子量产物及UpU,UpUpU等寡核苷酸片断的生成,表现出明显的模板效应,不含腺嘌呤的对应高分子则无此模板效应,聚甲基丙烯酸－β－（N^7－腺嘌呤基）乙酯对尿苷与N－（O,O′－二异丙基）－磷酰化丙氨酸反应的模板效应并不是由于其高分子主链引起的,而应归因于其侧链所挂的腺嘌呤碱基的存在,此效应对不同的核苷具有一定的特异性。     

TiO2/SnO2复合光催化剂的制备及光催化降解敌敌畏

合成了直链醚－组氨酸Schiff碱（四甘醇醛缩双组氨酸Schiff碱）及其稀土配合物,以元素分析、红外光谱、热重、磁化率等确定配合物组成为Ln3(H2L)2(NO3)9(Ln=La,Nd,Gd,Er,Yb;L=C20H26N6O7),采用交叉极化结合魔角旋转技术（CP／MAS）和消除旋转边带技术（TOSS）,获得固体高分辨^13C NMR谱,见到－COO^-的^13C谱峰分裂等新信息。结合液体^1H NMR谱等,对L－组氨酸中咪唑基的配位进行了研究,以EPR波谱探讨了配合物的晶体场强等特性。观察到Er配合物对超氧阴离自由基的清除有一定效果。     

邻磺酸基苯偶氮若丹宁流动注射分光光度法测定钯(Ⅱ)

本文报道了应用邻磺酸基苯偶氮若丹宁（ｏ－ＳＢＡＲ）试剂流动注射分光光度法测定钯的新方法。以（１＋１）的磷酸溶液为载体,试剂ｏ－ＳＢＡＲ与钯（Ⅱ）在反应管内迅速反应生成桔红色的络合物,其最大吸收波长为５２１ｎｍ。大量的碱金属、碱土金属及常见有色金属离子不影响,除Ａｕ＾３＋和Ｒｕ＾３＋干扰外,其他贵金属离子也有一定的允许量。此方法进样频率为８１次／小时,测定钯（Ⅱ）的线性范围为０．１～４．０μｇ／ｍＬ     

6－S－（取代的三或四唑杂环基）－1，2：3，4－二－O－异亚丙基－α-D吡喃型半乳糖的合成研究

报道了6－O－对甲苯磺酰基－1，2：3，4－二－O－异亚丙基－α-D吡喃型半 乳糖（3）与取代的3－巯基三唑或5－巯基四唑4a-4c或5a-5f的亲核取代反应，合 成了9个6－S－（取代的三或四唑杂环基）－1，2：3，4－二－O－异亚丙基－α- D吡喃型半乳糖（6a-6i），通过元素分析，IR，NMR和MS确证了上述化合物的结构 ，并经分子模型计算进行了其构象分析。     

相转移催化合成O,O-二烷基(硫代)磷酰氯

以氢氧化钠的饱和溶液做缚酸剂，用三氯硫酸和相应的醇通过相转移催化反应合成O，O－二烷氧基（硫代）磷酰氯，在温和条件下得较好收率，产物经IR，1H NMR和GC－MS表征。     

Ligand Exchange Between Penta-Coordinated Phosphoryl Serine and Histidine Compounds

With the assistance of HPLC-ESI-MS/MS, the self-assembly products of serine and histidine penta-coordinated phosphorus compound were separated and identified. The expectative product was seryl-histidine dipeptide, but it was found that there was almost equimolar amount of histidyl-histidine dipeptide as well as seryl-histidine dipeptide. The mechanism was speculated that there was iigand exchange between penta-coordinated phosphoryl serine and histidine in the reaction process. As a result,two types of dipeptide were produced.     

Synthesis and Characterization of N-(O,O-Dialkyl Phosphoryl)-D-glucosamine

Using D-glucosamine hydrochloride as a starting material and alkylphosphite as the phosphorylating agent, a new analogue of glycosyl phosphate, namely N-(O, O-dialkyl phosphoryl)-D-glucosamine, was synthesized without hydroxyl protection by Atherton–Todd reaction. The structure of N-(O, O-dialkyl phosphoryl)-D-glucosamine was determined by FT-IR, ¹H NMR, ¹³C NMR, ³¹P NMR, and HR MS. This concise and convenient synthetic pathway provides a new approach for the preparation of N-phosphoryl glucosamine derivatives.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

ESI／MS of N-（O, O-Diisopropyl） Phosphoryl Aromatic Amino Acids and their Stability Investigation Using HPLC／UV／ESI／MS

The full scan ESI/MS and ESI/MS^2 of N-(O, O-diisopropyl) phosphoryl aromatic amino acids (DIPPAAAs), N-(O, O-diisopropyl) phosphoryl phenylalanine, N-(O, O-diisopropyl)phosphoryl tryptophan and N-(O, O-diisopropyl) phosphoryl tyrosine, were obtained. The specific ions for them were found. Their stability in the LC mobile phase was investigated using developed HPLC/UV/ESI/MS and the results demonstrated that the DIPPAAAs were stable in the mobile phase (5 mmol/L NH4Ac-MeCN (80:20,v/v, pH7.5) within 48 h.     

Intermolecular Phosphoryl Transfer Between Serine and Histidine Residues

A novel intermolecular phosphoryl transfer from O-trimethylsilyl-N-(O, O-diisopropyl)phosphoryl serine trimethylsilyl ester to N, N‘-bis(trimethylsilyl) histidine trimethylsilyl ester wasstudied through electrospray ionization mass spectrometry (ESI-MS). It was proposed that thetransfer reaction went through penta-coordinated phosphorus intermediate.     

Mechanisms and Kinetics of Radical Reaction of O（^1D,^3P） ＋ HCN System

The reaction of HCN with O（^1D, ^3p） radical has been investigated by density functional theory （DFT） and ab initio methods. The stationary points on the reaction paths （reactants, intermediates and products） were optimized at the （U）B3LYP/aug-cc-pVTZ level. Single-point calculations were performed at the （U）QCISD（T）/aug-cc-pVTZ level for the optimized structures and all the total energies were corrected by zero-point energy. It is shown that there exist three competing mechanisms of oxygen attacking nitrogen O→N, oxygen attacking carbon O→C and oxygen attacking hydrogen O→H. The rate constants were obtained via Eyring transition-state theory in the temperature range of 600～2000 K. The linear relationship between lnk and 1/T was presented. The results show that path 1 is the main reaction channel and the product of NCO ＋ H is predominant.     

丝组二肽对DNA的切割作用的研究

近20年来,人工核酸切割试剂的研究一直是生物化学中最为活跃的前沿领域之一,研究人工核酸切割试剂的主要目的是合成定点切割试剂,后者是一种重要的分子生物学工具,在疾病的基团治疗、反义PCR技术等领域中有着重要的应用价值。此外,人工核酸切割试剂还可以在足迹技术和核酸高级结构的研究中用作高分辨率的化学探针。     

Phosphoryl Complexes of Some Metal(II) Trifluoromethanesulfonates

Cobalt(II), nickel(II), copper(II), and zinc(II) trifluoromethanesulfonates form complexes with the phosphoryl ligands hexamethylphosphoric triamide, nonamethyl imidodiphosphoric tetramide, trimorpholinophosphine oxide, tributylphosphine oxide, and triphenylphosphine oxide. The compounds have been prepared by a substitution reaction using trialkyl orthoformates as dehydrating agents and were investigated with the aid of infrared and ligand-field spectroscopy. In all compounds the ligands coordinate via the phosphoryl oxygen atoms. In some complexes the trifluoromethanesulfonate anions are (semi-)coordinated to the metal ions. The coordination around the metal ions was found to be tetrahedral, square pyramidal, or octahedral depending on the particular combination of metal ion and ligand. In its coordination behaviour the CF₃SO₃^? ion resembles the perrhenate ion.     

A tandem mass spectrometric investigation of N-(3-ferrocenyl-2-naphthoyl) dipeptide ethyl esters and N-(6-ferrocenyl-2-naphthoyl) dipeptide ethyl esters

N‐(3‐Ferrocenyl‐2‐naphthoyl) dipeptide ethyl esters 1–4 and N‐(6‐ferrocenyl‐2‐naphthoyl) dipeptide ethyl esters 5–8 were prepared by coupling either 3‐ferrocenylnaphthalene‐2‐carboxylic acid or 6‐ferrocenylnaphthalene‐2‐carboxylic acid to the dipeptide ethyl esters GlyGly(OEt) (1, 5), AlaGly(OEt) (2, 6), GlyPhe(OEt) (3, 7) and GlyLeu(OEt) (4, 8), using the standard N‐(3‐dimethylaminopropyl)‐N'‐ethylcarbodiimide hydrochloride, 1‐hydroxybenzotriazole protocol. Electrospray ionization mass spectrometry (ESI‐MS) and laser desorption ionization mass spectrometry (LDI‐MS) were employed in conjunction with tandem mass spectrometry in the analysis of N‐(3‐ferrocenyl‐2‐naphthoyl) dipeptide ethyl esters 1–4 and N‐(6‐ferrocenyl‐2‐naphthoyl) dipeptide ethyl esters 5–8. Radical cations, [M]^+? and [M + H]⁺ species were both observed in the mass spectra. Intense sodium [M + Na]⁺ and potassium [M + K]⁺ adducts were also present. An important diagnostic ion at m/z [M–65]⁺ was observed in both the MS and MS/MS spectra of the N‐(3‐ferrocenyl‐2‐naphthoyl) dipeptide derivatives. Sequence‐specific ions were generally not observed in the MS/MS spectra of the N‐(3‐ferrocenyl‐2‐naphthoyl) series due to formation of the diagnostic [M–65]⁺ ion. Sequence‐specific ions were observed in the MS/MS spectra of the N‐(6‐ferrocenyl‐2‐naphthoyl) dipeptide esters with charge retention on the derivatized N‐terminal of the dipeptide. Both series of compounds could be successfully analyzed by MALDI without the use of a matrix (LDI). Copyright © 2011 John Wiley & Sons, Ltd.     

Peptide Bond Formation in the Protonated Serine Dimer Following Vacuum UV Photon-Induced Excitation

Possible routes for intra-cluster bond formation (ICBF) in protonated serine dimers have been studied. We found no evidence of ICBF following low energy collision-induced dissociation (in correspondence with previous works), however, we do observe clear evidence for ICBF following photon absorption in the 4.6–14 eV range. Moreover, the comparison of photon-induced dissociation measurements of the protonated serine dimer to those of a protonated serine dipeptide provides evidence that ICBF, in this case, involves peptide bond formation (PBF). The experimental results are supported by ab initio molecular dynamics and exploration of several excited state potential energy surfaces, unraveling a pathway for PBF following photon absorption. The combination of experiments and theory provides insight into the PBF mechanisms in clusters of amino acids, and reveals the importance of electronic excited states reached upon UV/VUV light excitation.     

尖晶石LiMn2O4前驱体的低热固相反应法合成机理及其结构与热分解过程研究

以氢氧化锂、醋酸锰和柠檬酸为原料,采用低热固相反应法制备了Li+与Mn2+摩尔比为1∶2的前驱体化合物LiMn2L(Ac)2.通过元素分析、红外光谱、质谱和热重/差热等测试方法对前驱体的组成、结构、合成反应机理及热分解过程进行了研究.结果表明,可在全固相条件下通过低热固相反应得到锂离子与锰离子达到分子级混合水平的前驱体,该前驱体在350℃下焙烧4h即可出现明显的尖晶石相LiMn2O4产物.