Formation of (2E)-4-Hydroxy-2-nonenal and (2E)-4-Hydroxy-2-hexenal by Plant Enzymes: A Review Suggests a Role in the Physiology of Plants

It is demonstrated that (3Z)-nonenal (NON) and (3Z)-hexenal (HEX) are oxidized in a cascade by lipoxygenase (LOX) and hydroperoxide peroxygenase (HP peroxygenase) into (2E)-4-hydroxy-2- nonenal (HNE) and (2E)-4-hydroxy-2-hexenal (HHE), respectively. In turn, HNE inactivates LOX terminating the cascade. The hydroxy-alkenals produced serve to inhibit plant pathogens, which initiated the cascade. In addition to LOX, other unknown oxygenases may be involved in the cascade.

Synthesis Hexadecyl 3-{4-[2-Hydroxy-3(isopropylamino)propoxy] phenyl}propionate as Potential Ligand for Liposome Targeting to Ischemic Myocardium

Novel hexadecyl 3- { 4-[2-hydroxy-3（isopropylamino）propoxy]phenyl }propionate （HPP）was synthesized and its effect on delivery of liposomes into cultured cardiomyocytes was examined. The structure of HPP was characterized by IH NMR, 1R and MS. The amount of cardiomyocytes uptake of HPP-liposome was 3.9-fold higher than plain-liposome, and the increase was 6.2-fold when hypoxia happens. It indicated that HPP was a potential ligand for liposome targeting to ischemic myocardium.

Synthesis, Crystal Structure and Antitumor Activity of 4-(tert-butyl)-5-(1H-1,2,4-triazol-1-yl)-N-(2-hydroxy-3,5-diiodinebenzyl)-thiazol-2-amine

The title compound, 4-（tert-butyl）-5-（1 H- 1,2,4-triazol- 1 -yl）-N-（2-hydroxy-3,5-diio- dinebenzyl）thiazol-2-amine, was synthesized via the reduction of 4-（tert-butyl）-5-（1H-l,2,4- triazol-l-yl）-N-benzylidene-thiazol-2-amine with NaBH4, and its crystal structure was determined by single-crystal X-ray diffraction. The compound crystallizes in monoclinic system, space group P21/c with a = 7.91944（19）, b = 10.5250（3）, c = 24.4985（6） A, Z = 4, V = 2041.66（9） A3, Mr = 599.22, Dc = 1,949 Mg/m3, S = 1.120, p = 3.203 mm-1, F（000） = 1152, the final R = 0.0283 and wR = 0.0592 for 3490 observed reflections （I 〉 2σ（I））. X-ray analysis displays that the crystal water takes part in three intermolecular hydrogen bonds of O（2）-H（2A）…O（1）, O（2）-H（2B）…N（I） and N（5）-H（5）…O（2）, and an octatomic ring R^（8） is formed via intramolecular hydrogen bond of O（I）-H（IA）…N（4）. Furthermore, the I…I contacts are involved in stabilizing the overall three-dimensional network structure. The preliminary biological test shows the title compound has good antitumor activity with the IC50 value of 26 μM against the Hela cell line.

Highly efficient synthesis of(R)-1,3-butanediol via anti-Prelog reduction of 4-hydroxy-2-butanone with absolute stereoselectivity by a newly isolated Pichia kudriavzevii

(R)-1,3-butanediol is an important pharmaceutical intermediate, and the synthesis of(R)-1,3-butanediol using green biological methods has recently been of interest for industrial application. Here, a novel strain QC-1 that efficiently transforms 4-hydroxy-2-butanone to(R)-1,3-butanediol was isolated from soil samples. Based on morphological, physiological, and biochemical tests and 5.8 S-internal transcribed spacer sequencing, the strain was identified as Pichia kudriavzevii QC-1. The reaction conditions were optimized to 35 ℃, pH 8.0, rotation speed 200 rpm, and 6:5 mass ratio of glucose to 4-hydroxy-2-butanone. Evaluation of the effects of 4-hydroxy-2-butanone concentrations on yield and cell survival rate showed that 85.60 g·L^-1 product accumulated, with an enantiomeric excess of more than 99%, when 30 g·L^-14-hydroxy-2-butanone was added at 0, 10, and 30 h in a 3-L bioreactor. Thus, strain QC-1 showed excellent catalytic activity and stereoselectivity for the synthesis of(R)-1,3-butanediol from 4-hydroxy-2-butanone.

Synthesis and Crystal Structure of [2-Hydroxy-5-(4-hydroxy-3-phenyliminomethyl-benzyl)-benzylidene]-phenyl-amine

The title compound [2-hydroxy-5-（4-hydroxy-3-phenyliminomethyl-benzyl）-benzylidene]-phenyl-amine （C27H22N2O2, Mr = 406.47） was synthesized by 5,5′-methylene-bissalicylal- dehyde with aminobenezene, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group C2/c with a = 4.4026（6）, b = 1.501（13）, c = 0.95818（12） nm, β = 90.868（2）°, V= 4.2813（9） nm^3, Z= 8, Dc= 1.292 g/cm^3,μ = 0.010, F（000） = 1744, R = 0.0576 and wR = 0.1450 for 3766 observed reflections with I 〉 2σ（I）. X-ray analysis reveals that the molecule has a pair of intramolecular OH…N hydrogen bonds.

A New Chiral Synthesis of Naturally Occurring (-)-(S)-4-Hydroxy-2-pyrrolidinone

A new and convenient chiral synthesis of naturally occurring (-)-(S)-4-hydroxy-2-pyrrolidinone from (S)-malic acid was reported.

Enantioselective Hydrogenation of Ethyl 2-Oxo-4-phenylbutyrate on Cinchona-Platinum Catalysts

Enantioselective hydrogenation of ethyl 2-oxo-4-phenylbutyrate to ethyl （R）-2-hydroxy-4-phenyl- bu- tyrate on Pt/γ-Al2O3 modified by 10,11-dihydrocinchonidine was studied by investigating the influences of the amount of modifier, initial concentration of reactant, pressure and temperature on conversion and enantiometric excess in a stirred autoclave and the effects of the liquid velocity, gas velocity, modifier concentration and various catalytic beds in a trickle-bed reactor. The maximum optical yields were about 50% and 60% in the two types of reactors, respectively. It was assumed that the total hydrogenation rate included the reaction rates over the unmodified and modified active sites on platinum surface and a kinetic model, which fitted the experimental data well in autoclave, was obtained. A simplified plug-flow model was proposed to describe the bed average efficiency of trickle-bed reactor.

Synthesis and Crystal Structure of Tri(4-(3-hydroxy2-ethyl-4-pyridinone-1-yl)-aniline Condensation Salicylaldehydato) Monohydratotricopper(II)Dimethylformamide Monohydrate Solvate

The title complex [Cu3L3(H2O)]DMFH2O (H2L = 4-(3-hydroxy-2-ethyl-4- pyridinone-1-yl)-aniline condensation salicylaldehyde) was obtained. The single-crystal X-ray study shows that it is a trinuclear compound [Cu3(C20H15N2O3)3(H2O)]DMFH2O. The coordi- nation sphere about each copper ion in the complex consists of two oxygen atoms from hydroxylpyridinone moiety of one ligand and one oxygen and one nitrogen atoms from salicyladehyde Schiff-base moiety of another ligand arranged in a slightly distorted square planar geometry. Among the three copper ions, one (Cu(2)) is coordinated by the other oxygen atom of water molecule on the fifth coordinate position to form a distorted square pyramid geometry. The crystal is of monoclinic, space group P21/c with a = 12.9202(5), b = 27.197(1), c = 17.0116(7) ? b = 100.588(1), V = 5875.9(4) 3, Z = 4, C63H57N7O12Cu3, Mr = 1294.78, Dc = 1.464 g/cm3, m = 1.146 mm-1, F(000) = 2668, R = 0.0784 and wR = 0.1546 for 6926 observed reflections with I > 2s(I). The differences of coordinate bond lengths are observed between anhydrous and hydrous units: in the former unit, the average bond lengths are 1.978 ?for CuN (azomethine), 1.883 ?for CuO (phenolic) in Schiff-base moiety, 1.959 ?for CuO (keto), and 1.919 ?for CuO (hydroxy) in hydroxypyridinone moiety; while those in the latter are longer with the following corresponding values: 1.985(5), 1.908(5), 1.993(5) and 1.919(4) ? respectively. The Cu(2)O (water) bond length is 2.375(6) ?

Use of Ultrasound and Microwave Irradiation for Clean and Efficient Synthesis of 3,3’-(Arylmethylene)bis (2-hydroxynaphthalene-1,4-dione) Derivatives

Nine 3,3’-(arylmethylene)bis(2-hydroxynaphthalene-1,4-dione) derivatives were synthesized through the reaction between 2-hydroxy-1,4-naphthalen-1,4-dione and different aromatic alde-hydes in water applying ultrasonic irradiation for 5 min at room temperature and microwave irradiation for 15 min at 70°;C. Two of the nine derivatives, compounds 3-e and 3-i, obtained from 3-bromo-hydroxybenzaldehyde and 5-methylfuran-2-carbaldehyde, respectively, are previously unpublished. The structures of all compounds were established on the basis of their spectral data and mass analysis. The attractive features of this synthesis protocol include mild conditions, high atom-economy and excellent yields with the elimination of water as the only by-product.

A New Halogenated Biindole and A New Apo-carotenone from Green Alga Chaetomorpha basiretorsa Setchell

A new halogenated biindole and a new apo-carotenone have been isolated from the ethanolic extract of the green alga Chaetomorpha basiretorsa Sethcell. On the basis of chemical and spectroscopic methods including 2D NMR technique, their structures have been elucidated as 4,4′-dichloro-5,5′-dibromo-7,7′-dimethoxy-2,2′-bi-1H-indole and 1′S*,4′R*-8-(4′-hydroxy-2′,6′,6′- trimethylcyclohex-2-enyl)-6-methyloct-3E,5E,7E-trien-2-one, respectively.

A New Sesquiterpene-substituted Benzoic Acid from the Brown Alga Dictyopteris divaricata

A new sesquiterpene-substituted benzoic acid has been isolated from the brown Alga Dictyopteris divaricata Okam.. Its structure was elucidated as 3-[(2-hydroxy-2,5,5,8a-tetra- methyldecahydro-1-naphthalenyl)methyl]-4-hydroxybenzoic acid, named dictyvaric acid on the basis of spectroscopic methods including IR, HRFABMS, 1D and 2D NMR techniques.

Redesign of a short-chain dehydrogenase/reductase for asymmetric synthesis of ethyl (R)-2-hydroxy-4-phenylbutanoate based on per-residue free energy decomposition and sequence conservatism analysis

As an important building block for the synthesis of angiotensin-converting enzyme inhibitors,ethyl(R)-2-hy-droxyl-4-phenylbutanoate[(R)-HPBE]has attracted increasing attention.The key to industrial biosynthesis of(R)-HPBE is a biocatalyst that efficiently reduces ethyl 2-oxo-4-phenylbutanoate(OPBE)with high R-enantiose-lectivity.This paper proposed a strategy for identifying key residues involved in enantioselectivity control based on per-residue free energy decomposition and sequence conservatism analysis.Using this strategy,4 noncon-servative sites with high energy contribution to binding of OPBE were chosen as engineering targets,generating variant Mu27 with 99%conversion and 98%(R)ee value at substrate loading of up to 500 mmol/L.MD simu-lations suggested the higher stability and formation probability of Mu27-OPBEproR prereaction state as key rea-sons for the excellent R-enantioselectivity of Mu27 towards OPBE.The success in this study provides a viable approach for rational design of alcohol dehydrogenases with high enantioselectivity towards unnatural substrates.

Vlultifunctional immune responses of HMBPP-specific Jy2Vδ2 T cells in M. tuberculosis and other infections

Vy2Vδ2 T （also known as Vy9Vδ2 T） cells exist only in primates, and in humans represent a major yδ T-cell sub-population in the total population of circulating yδ T cells. Results from recent studies suggest that while （E）-4-hydroxy-3-methyl-but-2-enyl pyrophosphate （HMBPP） phosphoantigen from Mycobacterium tuberculosis （Mtb） and other microbes activates and expands primate Vy2Vδ2 T cells, the Vy2Vδ2 T-cell receptor （TCR） recognizes and binds to HMBPP on antigen-presenting cells （APC）. In response to HMBPP stimulus, Vy2V82 TCRs array to form signaling-related nanoclusters or nanodomains during the activation of Vy2V82 T cells. Primary infections with H MBPP-producing pathogens drive the evolution of multieffector functional responses in Vy2Vδ2 T cells, although Vy2V82 T cells display different patterns of responses during the acute and chronic phases of Mtb infection and in other infections. Expanded Vy2Vδ2 T cells in primary Mtb infection can exhibit a broader TCR repertoire and a greater clonal response than previously assumed, with different distribution patterns of Vδ,2Vδ2 T-cell clones in lymphoid and non-lymphoid compartments. Emerging in vivo data suggest that HMBPP activation of Vy2W2 T cells appears to impact other immune cells during infection.

A new pyrrolidone derivative from Pistacia chinensis

A new N-phenyl-pyrrolidone derivative had been isolated from Pistacia chinesis Bunge. Its structure was elucidated as 4-hydroxy-5-（2-oxo-1-pyrrolidinyl）-benzoic acid, named pistaciamide on the basis of the 1D-NMR, DEPT, HMQC and HMBC spectroscopic techniques. 2007 Xi Kui Liu. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

A New Chromone Derivative from Stellera chamaejasme L

A new chromone derivative, 3-[1- (2, 4, 6-trihydroxyphenyl) 3-di-(4-hydroxyphenyl) 1-propanone-2-yl] 5,7-dihydroxy-8-di(4-hydroxyphenyl)methyl-4H-1-benzopyran-4-one, named as isomohsenone was isolated from the roots of Stellera chamaejasme L. together with known chamaechromone. Its structure was determined by the analysis of MS and NMR data, especially 2D NMR spectra.

A New Bisxanthone from Hypericum japonicum Thunb.ex Murray

A new bisxanthone, named bijaponicaxanthone C, was isolated from the whole plant of Hypericum japonicum. The structure was elucidated as 6-[1’’,5’’,6’’-trihydroxy-2’’’-(β-hydroxy-β- methylethyl)-2’’’,3’’’-dihydrofuran(5’’’,4’’’,3’’,4’’)xanthone-3’’’-oxyl]-1,3,5-trihydroxy-4-isoprenylxant- hone (1) on the basis of the spectral and chemical evidences.

New flavan and unusual chalcone glycosides from Drypetes parvifolia

Two new compounds 7-hydroxy-5-O-（β-D-glucopyranoside） flavan （1） and （Z）-4＇,6＇-dihydroxy-2＇-O-（β-D-glucopyranoside） chalcone （2）, along with eight known compounds, were isolated from the stem bark of Drypetes parvifolia （Euphorbiaceae）. Their structures were established on the basis of spectroscopic analysis and chemical evidence.

A new phenolic compound from Crinum asiaticum L.

A new phenolic compound was isolated from the ethanol extract of the bulbs of Crinum asiaticum L.var.sinicum Baker.Its structure was defined as 1-（2-hydroxy-4-hydroxymethyl）phenyl-6-O-caffeoyl-β-D-gluco-pyranoside on the basis of spectroscopic evidences.

A Phenolic Glucoside from Alangium plantanifolium

A novel phenolic glucoside was isolated from stem barks of Alangium plantanifolium, its structure was elucidated to be 1-O-[2-(1-hydroxy-6-oxocyclohex-2-ene-1-carboxymethyl) -phenyl]-4, 6-O-[(S)-4, 4', 5, 5', 6, 6'-hexahydroxydi-phenoyl]-beta -D-glucopyranose 1 by spectroscopic methods including 2D NMR techniques.

海洋真菌Penicillium sp. SCS-KFD16次级代谢产物研究

目的研究海洋真菌Penicilliumsp.SCS-KFD16的次级代谢产物。方法采用正向硅胶、ODS和半制备HPLC等方法对海洋真菌Penicillium sp.SCS-KFD16的发酵代谢产物进行分离纯化,采用MS和NMR等波谱方法对代谢产物进行结构鉴定,分别采用DPPH法、Ellman比色法和PNPG法对化合物的自由基清除能力、乙酰胆碱酯酶抑制活性及α-葡萄糖苷酶抑制活性进行测试。结果从海洋文蛤来源真菌Penicillium sp.SCS-KFD16的发酵产物醋酸乙酯部分中分离了6个化合物,分别鉴定为2-(4-hydroxy-2-methoxybenzyl)-5-methoxyphenol(1)、penicillide(2)、bioxanthracene 2(3)、6-ethyl-2,4-dihydroxy-3-methylbenzaldehyde(4)、4-羟基苯乙醇(5)和2-(4-hydroxyphenethyl) acetate(6)。结论化合物1为新化合物,命名为青霉双酚;化合物2～6具有一定的DPPH自由基清除活性,化合物4抑制α-葡萄糖苷酶活性的IC50为24.4μmol/L。