Two new acids from mangrove endophytic fungus (No. ZZF13)

Two new acids 1 and 2, together with a known compound, purpactin A (3), were isolated from endophytic fungus No. ZZF13. Their structures were elucidated on the basis of 1D, 2D NMR, and HREIMS spectra. Published in Khimiya Prirodnykh Soedinenii, No. 4, pp.336-337, July-August, 2008. Original articlesubmitted April 24, 2007.     

The Mitsunobu 1-O-esterification of 1-hydroxy-3-phenyl-1H-quinoxalin-2-one 4-oxide

1-Hydroxy-2-oxo-3-phenyl-1,2-dihydroquinoxaline 4-oxide under conditions of the Mitsunobu reaction reacts with alcohols giving the corresponding esters at the hydroxy group in position 1. Other representatives of hydroxamic acids such as 1,4-dihydroxyperhydroquinoxaline-2,3-dione and 1,4-dihydroxy-3,3,6,6-tetramethylpiperazine-2,5-dione undergo destruction under these conditions. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1240–1243, June, 2008.     

Stabilities and coordination modes of histidine in copper(II) mixed-ligand complexes with ethylenediamine,diethylenetriamine or N,N,N′,N″,N″-pentamethyldiethylenetriamine in aqueous solution

Solution equilibrium studies on the Cu(II)–polyamine–histidine ternary systems (polyamine: ethylenediamine (en), diethylenetriamine (dien), N,N,N′,N″,N″-pentamethyldiethylenetriamine (Me₅dien)) have been performed by pH-potentiometry, UV–Vis spectrophotometry and EPR methods. The obtained results suggest the formation of the mixed-ligand complexes with [Cu(A)(His)]⁺ stoichiometry in all studied systems. Additionally, in the systems with dien and Me₅dien protonated [Cu(A)(H–His)]²⁺ species also exists in acid solution. Our spectroscopic results indicate the tetragonal geometry for the [Cu(en)(His)]⁺, the geometry slightly deviated from square pyramidal for the [Cu(dien)(His)]⁺ and strongly deviated from square pyramidal towards trigonal bipyramidal for the [Cu(Me₅dien)(His)]⁺ species. The coordination modes in these mixed-ligand complexes are discussed.     

微波辐射下5-取代-2-硫代海因衍生物的合成

微波辐射下, 由硫氰酸铵与α-氨基酸通过两步反应合成了11种5-取代-2-硫代海因衍生物, 并用¹H NMR, IR和元素分析确证了中间产物和终产物的结构. 对比常规加热方法, 微波辐射具有反应时间短(4 min), 每步反应产率高(85%～93%)的优点. 同时对合成化合物2h的反应历程进行了讨论.     

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.     

固相萃取-高效液相色谱法测定蜂蜜中的有机酸

建立了固相萃取-高效液相色谱(SPE-HPLC)同时测定蜂蜜中5种有机酸(L-苹果酸、马来酸、琥珀酸、柠檬酸、D-苹果酸)含量的方法。蜂蜜经制样后过Bond Elutes SAX固相萃取(SPE)小柱净化,用C18-MS-II反相色谱柱(250 mm×4.6 mm, 5 μm)进行分离,流动相为2%偏磷酸溶液,流速为0.7 mL/min,检测波长为210 nm。在此条件下5种有机酸在相应的线性范围内其线性相关系数均大于0.9967;方法的回收率为86.0%～103.9%,相对标准偏差为5.7%～9.8%(n=6),检出限为0.06～9.4 mg/kg。所建立的方法可用于蜂蜜样品中有机酸的测定。     

手性氨基酸及其衍生物配体在酮不对称氢转移反应中的应用进展

前手性酮的不对称氢转移反应(ATH)是获得手性醇的重要方法.近年来氨基酸及其衍生物在金属Ru,Rh,Ir催化酮的ATH中的应用引起人们关注.就氨基酸、氨基酸酰胺、氨基酸硫代酰胺、氨基酸羟胺酸、氨基酸酰肼、氨基醇及氨基酸羟基酰胺等为配体的金属络合物在ATH中的催化性能进行了综述.     

长江三角洲地区污水厂污泥中全氟有机酸污染特征

对长江三角洲地区污泥的分析结果表明：脱水剩余污泥中总全氟有机酸（PFAs）的浓度范围为122-1098ng／g,其中三氟乙酸（TFA）和五氟丙酸（PFPrA,除S13未检出外）一般是污染水平最高的两种PFAs,分别为107-562ng／g和4．41-395ng／g,占总PFAs的12％-93％和0．7％-61％,这充分说明在以后的监测中需要将超短链PFAs纳入检测范围．尽管全氟辛酸（PFOA）和全氟辛磺酸（PFOS）的浓度一般低于超短链的TFA和PFPrA,甚至在某些情况下还会低于部分中长链PFCAs,但在绝大多数情况下它们依然是两种主要的PPAs类污染物,浓度分别为2．78-66．9ng／g和1．27-80．4ng／g,占总PFAs的0．7％-8．8％和1％-20％．一般而言,全氟羧酸（PFCAs）的检出率较高,可达92．3％-100％,但是对全氟烷基磺酸（PFSAs）而言,除PFOS的检出率为100％外,全氟丁磺酸（eFBS）和全氟己磺酸（PFHxS）的检出率较低,仅分别为15．4％和7．8％．此外,不同的污水处理工艺可能会严重影响污水处理过程中PFAs污染水平和归趋,造成这种现象的原因可能是不同工艺条件下污泥的吸附性能不同,也可能是不同处理工艺对其前体物的降解转换率不同．     

固定化D-氨基酸氧化酶催化DL-氨基酸去消旋化制备非天然L-氨基酸

在过氧化氢酶和氧气存在下,固定化D-氨基酸氧化酶(D-AAO)对映选择性催化DL-氨基酸中的D-对映体氧化脱氨为相应酮酸,L-对映体保留.研究了D-AAO的底物特异性并对反应条件进行了优化.结果表明:D-AAO具有较宽的底物谱,能够催化疏水性α-氨基酸的D-对映体氧化脱氨.在最优反应条件下,D-AAO催化DL-2-氨基丁酸、DL-2-氨基戊酸去消旋化,L-2-氨基丁酸、L-2-氨基戊酸的收率分别为48%和47%,ee分别为99.5%和99.8%.进一步地利用Pd-C/HCOONH4催化氧化脱氨过程中产生的亚氨基酸原位还原,有效提高了L-2-氨基丁酸、L-2-氨基戊酸的收率并保持高的光学纯度.