Biomimetic alcohol oxidations by an iron(III) porphyrin complex: relevance to cytochrome P-450 catalytic oxidation and involvement of the two-state radical rebound mechanism

The systematic oxidation reactions of a wide range of alcohols have been carried out by using an iron porphyrin complex in order to understand their relation to cytochrome P-450 enzymes and to have a practical application to organic synthesis. The iron porphyrin complex catalyzed efficiently alcohol oxidation to the respective carbonyl compound via a high-valent iron-oxo porphyrin intermediate ((Porp)Fe=O+). Several mechanistic studies such as isotope 18O labeling, deuterium isotope effect, linear free energy relationship, and ring-opening of radical clock substrate, have suggested that the alcohol is oxidized by a sequence of reactions involving an alpha-hydroxyalkyl radical intermediate and oxygen rebound to form the gem-diol, dehydration of which yields the carbonyl compounds. Moreover, it has been proposed that a two-state reactivity mechanism can also be adopted for alcohol oxidation reactions in iron porphyrin model systems as exhibited by P-450 enzymes.     

Synthesis and Luminescent Properties of an Acetylide-Bridged Dinuclear Platinum(II) Terpyridyl Complex

Introduction Luminescent coordinatively unsaturated platinum(II) complexes are appealing from photochemical and pho-tophysical perspective.1,2 In particular, platinum(II) ter-pyridyl complexes have attracted considerable attention due to their rich spectroscopic2a-d and biological proper-ties.2a,e-g However, the development of the photochem-istry of these complexes is limited by their short-lived MLCT excited state in solution at room temperature. The lack of emission originates from low-l…     

含1,3-亚丙基冠醚的合成

为了进一步研究亚丙基冠醚的络合行为,合成了三种含1,3-亚丙基冠醚,即2,3-苯并-1,4,7,11-四氧-环十三-2-烯(苯并-13-冠-4)(1)、2,3-苯并-1,4,8,11,14-五氧-环十七-2-烯(苯并-17-冠-5)(2)、2,3-苯并-1,4,7,10,14,17-六氧-环十九-2-烯(苯并-19-冠-6)(3)。通过元素分析、红外光谱、质谱、核磁共振谱和 X-衍射晶体结构分析,确证了它们的结构。     

微波等离子体光谱法测定碲的研究

微波等离子体原子发射光谱法(MIPAES)测定碲,前人已作过一些工作。本文利用我们建立的微量进样系统与MIPAES联用,对碲的测定进行了研究。实验中发现,加入适量的SnCl_2可降低检出限约一个数量级,Te_(214.3nm)的检出限为5 ng/mL,同时还研究了碱金属卤化物对碲的测定的影响。     

Micro construction of poly(epsilon-caprolactone)/poly(L-lactic acid) blend film by solution casting under microwave irradiation

The micro construction of poly(epsilon-caprolactone) (PCL) and poly(L-lactic acid) (PLLA) blend films fabricated by solution casting under microwave irradiation was investigated by selective enzymatic degradation and scanning electron microscopy (SEM). The results were totally different from the blends obtained by conventional methods. The blend was more homogeneous and the PCL continuous phase more compact as no spherulites and tiny zone separation were observed from the film surface and no PCL network was observed inside the film, and the degradation of a PCL plank by Pseudomonas lipase was significantly retarded. The distributed PLLA micro spheres were enlarged and amorphous. The thermal behavior of the blend by microwave heating revealed that PCL and PLLA underwent a melting process, which induced the variations of the PCL phase and PLLA spheres. The weight loss caused by degradation of the PCL/PLLA blend obtained by conventional methods (B50c) is greater than that of the blend obtained by microwave methods (B50m), which reflects the change in morphology from a loose PCL network (B50c) to a dense PCL plank (B50m).     

Structural Characterization of the Chiral Skeleton Cluster RuCoMo (Co)_8(μ_3-Se ) C_5H_4C (O) C_6H_4C (O)OCH_3

1INTRoDUCTIoNIntenseinterestintransition-metalclusterscontinuesbecausetheyrepresentpos-sibleconceptualbridgesbetweenhomogeneousandheterogeneouscatalystsmoreoveralsobecausetheyrepresentsyntheticchallenges.TheuseofelementsofGroup16ofthePeriodicTableassingleatomligandsforclustergrowthandstabilizationofthemetalcorearenowwellestablished[1i.ThereisanincreasinginterestintheuseofSe-bridgrdclusters,manyofthereactionsofSe2Fe2(CO),andSe2Fe,(CO),havebeenreported"';however,therehasbeenverylittlewor…     

Enantioselective total synthesis of (+)-gigantecin: exploiting the asymmetric glycolate aldol reaction

The enantioselective synthesis of the potent, selective, cytotoxic, annonaceous acetogenin, (+)-gigantecin, has been completed. An asymmetric glycolate aldol serves to establish the stereocenters at C13,14 and at C21,22. A Carreira asymmetric acetylide addition is used to establish the C17 stereocenter.     

LiCoO2/LiNiO2/LiMn2O4材料安全性能的研究

随着锂离子电池的大型化,对电池安全性能的研究显得更为重要。锂离子电池的安全性有不同的测试方法,如进行过充试验和短路试验。在这些安全性试验中,以及在滥用中出现的安全性的问题,大多是由于电池内部温度升高,进而触发了大量放热的副反应[1],引起电池发生爆炸。本文通过对AA     

Enhancive Synthesis of ‐lβ, 11‐Diol‐4‐en‐eudesmol

An enhancive synthesis of ?1β, 11‐diol‐4‐en‐eudesmol, starting from 2‐chloroacrylonitrile, is described. The effect of temperature on the Diels‐Alder reaction of 2‐chloroacrylonitrile with 2‐methylfuran and the condition of cationic cyclization of diene were discussed in detail.