Reduction of 4-nitrophenol catalyzed by nitroreductase

The reduction of 4-nitrophenol catalyzed by nitroreductase in the presence of NADH was investigated in this paper.4-Amino- phenol and 4-bydroxylamino-phenol were found in the reductive products.The relationship between reaction time and the reductive ratio were studied.The similar reducing ratios of 4-nitrophenol were obtained under aerobic and anaerobic conditions.The results indicated that an oxygen-insensitive reaction was proceeded in the reduction of 4-nitrophenol and nitroreductase was an oxygen- insensitive enzyme.The reductive products of 4-nitrophenol were determined by HPLC and MS.     

Polymerization of 4—Vinylpyridine by Lanthanide Coordination Catalyst

Polyvinylpyridines are an important class of polymers that exhibit interesting properties due to the presence of the nitrogen atom in the pyridine ring. The weakly basic nitrogen atom makes possible a variety of reactions on vinylpyridine polymers, e.g. reaction with acids, quaternization and complexation of metals. In addition, these polymers are mainly attractive in applications as polyelectrolytes, polymeric reagents etc. Few papers about polymerization of 4-vinylpyridine (4-Vpy) with co…     

Asymmetric Dihydroxylation of Allylamine Catalyzed by Wool-OsO4 Complex

A new chiral polymer-metal complex, wool-osmium tetroxide(wool-OsO4) complex was prepared by a very simple method. This complex was found to be able to catalyze the asymmetric dihydroxylation of allylamine to get (R)-( )-3-amino-1, 2-propanediol. The experimental results showed that OsO4 content in the complex, reaction time, allylamine/OsO4 molar ratio all have great effects on the chemical and optical yields of product. Additionally, wool-OsO4 complex catalyst could be reused without remarkable change in optical catalytic activity.     

Esterification and Chemoselective Synthesis of R-Tetrahydrothiazo-2-thione-4-carboxylic Esters Catalyzed by TiCl4

A series of esters of R-tetrahydrothiazo-2-thione-4-carboxylic acid[R-TTCA] was synthesized by direct esterification of R-TTCA with alcohols(CH3OH,C2H5OH,n-C3H7OH,i-C3H7OH,n-C4H9OH,sec-C4H9OH)in the presence of TiCl4 as the catalyst at room temperature without using any other solvent or dehydrant in high yields,91.6%-99.1% for primary alcohols and 55%- 80% for secondary alcohols.The catalyst has a strong chemoselective activity for the esterification of primary alcohols with R-TTCA in the presence of secondary alcohols.Owing to high yield,high chemoselectivity,and mild conditions used,this is an efficient method for the esterification of primary alcohols with R-TTCA.     

X-ray scattering by the phases of 4-methoxybenzylidene-4′-n-butylaniline quenched under a magnetic field

Normally 4-methoxybenzylidene-4′-n-butylaniline exhibits only one liquid-crystalline phase; it is nematic at room temperature. However, after quenching it at liquid nitrogen temperature it is possible to reach four new phases by successive annealing. We report here an experiment aimed at providing a better understanding of these phases by studying their texture after quenching in a magnetic field large enough to orient the sample in the nematic phase.     

Catalytic Enantioselective Methanolysis of 4 -substituted-2-phenyl-5(4H)-oxazolones by Cinchonine

Theopeningoftheringof5(4H)-oxazolonesisoneofthemethodsforthesynthesisof-..-non-racemica-aminoacids.Thediastereoselectivering-openingof5(4H)-oxazolonesbychiralnucleophilesandenantioselectivehydrolysisandalcoholysisof5(4H)-oxazolonesbyenzymeshavebeenextensivelyinvestigated'.However,toourknow1edgenon-enzymecatalyzedenantioselectivealcoholysisof5(4H)-oxazoloneshasnotbeenreported.Inthispaper,wereportonthefirstnon-enzymecatalyzedenantioselectivealcoholysisof5(4H)-oxazolonesbycinchonine.As4-substit…     

Asymmetric Induction by β-Cyclodextrins in NaBH4 Reduction of Ketones

Asymmetric reduction of various prochiral ketones was achieved with sodium borohydride utilizing -CD or its derivative, mono-6-deoxy-6-[N-(2-aminoethyl)]amino--CD (-CD-en) as a chiral template. It was found that pre-equilibrium between ketone and -CD derivative and low reaction temperature increase asymmetric induction. The extent of asymmetric induction and the absolute configuration of the resulting secondary alcohols are highly dependent upon the nature of the ketones and also -CD derivatives. A mechanistic scheme is suggested to explain the dependency.     

Specific hydrolysis of DNA by Ce~(4+) -ODN hybrid

The cerium complex bound to the derivative of oligoDNA has been synthesized successfully that can hydrolyze DNA with sequence-specificity. The synthesized derivative of oligoDNA, 5'-EDTA-P-10 mers ODN, was demonstrated by HPLC. The fluorescence spectrum of Tb3+ was detected after its interaction with the hybrid of 10-mers ODN and 26-mers ODN and the results show that the artificial endo-enzyme can recognize and combine firmly with the substrate DNA. The electrophorogram shows that the cerium-oligoDNA hybrid can specifically hydrolyze its substrate DNA and the cleavage site of this hydrolysis reaction is also discussed. This artificial nuclease can be widely used in molecular biology and genetic engineering as one kind of endo-enzyme.     

Sustainable Polyamides Enabled by Controlled Ring-opening Polymerization of 4-Hydroxyproline-derived Lactams

Aliphatic polyamides have been considered as eco-friendly materials, useful for a wide range of applications. However, it still presents obstacle to produce sustainable aliphatic polyamides from abundant renewable sources. Herein, we describe that 4-hydroxyproline(4-HYP), a renewable resource, was readily converted to its corresponding bicyclic bridged lactam monomers bearing pendant Boc-protected secondary amino group, and oligo-ethylene glycol group. Lithium hexamethyldisilazide(LiHMDS)-mediat...     

2-Chloromercuri-4-nitrophenol-modified Sites of Creatine Kinase Confirmed by FPLC

MNP-modified tryptic peptides of creatine kinase have been separated with two-dimensional electrophoresis, but the location of the SH groups of creatine kinase modified by MNP still seemed to be vague until recently (Laue, M. C. & Quiocho, F. A. , 1977). Two peptides have now been found to be the MNP-modified peptides with reversed-phase FPLC methods, and the amino acid compositions of these two peptides are in agreement with those of the two peptides around Cys-145 and Cys-253, respectively. These findings indicate that the two buried SH groups of creatine kinase have been modified by MNP.     

Photocatalytic Activity of Nanosized ZnWO4 Prepared by the Sol-gel Method

Nanosized ZnWO4 photocatalysts were successfully synthesized via the sol-gel process in a temperature range of 450-800 ℃.The grain size,crystal size,and crystallinity of ZnWO4 particles increased with the increase of calcination temperature and prolonging calcination time.The photocatalytic activity was measured for the degradation of an aqueous Rhodamine-B(RhB)solution and gaseous formaldehyde(FAD).With the increase of calcination temperature and time,the activities increased to a maximum and then decreased.ZnWO4 photocatalyst prepared at 550 ℃ for 10 h showed the highest activity,which is similar to the photocatalytic activity of P25TiO2 for the degradation of gaseous FAD.High crystallinity,large surface area,and good dispersion are responsible for the high photocatalytic performance of the prepared ZnWO4.     

Electrocatalytic Oxidation of Vitamin B6 by 4-Hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl

Introduction Nitroxides such as 2,2,6,6-tetramethylpiperidine-N- oxyl (TEMPO) are well-known stable free radicals which have been extensively used in spin labeling,1 spin trapping2 and as antioxidants.3 Nitroxides are also easy to undergo reversible one-electron oxidation to form the corresponding oxoammonium ions.4 Oxoammonium ions are mild one-electron oxidants which have been used in organic synthesis5-8 and to generate radical cations.9 We10 found recently that electrochemically generat…     

Synthesis of 4-aryl-substituted β-lactam enantiomers by enzyme-catalyzed kinetic resolution

Enantiopure 4-phenyl- and 4-(p-tolyl)-2-azetidinones 3a, 3b, 4a and 4b (with e.e.s of ≥96%) were prepared through lipase-catalyzed asymmetric butyrylation of the primary OH group of N-hydroxymethylated β-lactams (±)-5 and (±)-6 at the (R)-stereogenic centre or by lipase-catalyzed asymmetric debutyrylation of O-butyryloxymethyl-2-azetidinones (±)-7 and (±)-8 at the (R)-stereogenic centre. The ring-opening of lactams 5a, 5b, 6b and 8a with HCl/EtOH afforded the corresponding β-amino ester enantiomers 9a, 9b, 10a and 10b with e.e.s of ≥92%.     

Ab Initio Potential Surface in CH_4 Activation by PTCL_2

IntroductionC-HachvationofmethanebytransihonmetalcomplexeshasbeenthesubjectofconsiderablestUdr'asaresultofitshoportanceincatalylicmethane....ersi..I'l.Inmostcasesoftransihonmetalcomplexes,C-HbondareachvatedbyandaddoxidahvelytocoordinativelyunsatUratedintermwhates.ThefirstSystemofC-HachvahonisaccomplishedbyShil.vl'],asshownineq.lftCl2+CH4-(CH3)ftHCl2(I)Therealmechamsmofreachon(1)isapparentlyclosetotheokidahveaddihonofC-Hbondtoelectron-richspeciesl'].Thedrivingforceofthereachonistheform…     

Ion—molecule reactions in GeH4/SiH4 systems studied by ion trap mass spectrometry

Gas phase ion—molecule reactions occurring in GeH₄/SiH₄ systems under different partial pressures and their mechanisms have been investigated by ion trap mass spectrometry (ITMS). SiH⁺_n (n=0–3) and GeH⁺_n (n = 0–3) are the main ionic species at zero reaction time when the GeH₄: SiH₄ ratio is in the range 1:1 to 1:12. Self-condensation sequences are observed at increasing reaction times. Moreover, formation of ions containing GeSi bonds, such as GeSiH⁺_n (in = 2–5) and GeSi₂H⁺_n (n = 4, 5), occurs by reactions of Si₂H⁺_n (n = 2–5) and Si₃H⁺_n (n = 4, 5) with GeH₄. At longer reaction times, further substitution of silicon with germanium in GeSiH⁺_n (n = 2–5) ions has been observed, to give Ge₂H⁺_n (n = 2–5).     

Regioselective tetrahydropyranylation of alcohols catalyzed by Fe（HSO4）3

Alcohols are selectively and efficiently protected as their tetrahydropranyl ethers in the presence of a catalytic amount of Fe(HSO4)3 in good to high yields. All reactions are performed under mild and completely heterogeneous reaction conditions.     

Distortion of the Cucurbituril Molecule by an Included 4‐Methylpyridinum Cation

The crystal and molecular structures of a guest–host complex of cucurbituril with 4methylpyridinium, {(4MePyH) (C₃₆H₃₆N₂₄O₁₂)}(NO₃) · 4H₂O, were determined by Xray structural analysis. The crystals are monoclinic with a = 26.276(3) , b = 25.861(2) , c = 17.375(2) , = 124.17(1)°, V_cell =9768.6(18) ³, space group Cc, and Z = 8. The structure contains two crystallographically independent supramolecular complexes. They are arranged in pillars oriented along the a axis. In each pillar, the complexes are parallel to each other. The pillars are shifted with respect to each other by onehalf of the crystallographic translation. The centers of the supermolecules are arranged according to a pseudobodycentered motif. Distortions of the cucurbituril molecule depending on the guest type have been analyzed with the use of results obtained in the present and previous studies.     

Hydrogenolysis of β-O-4 lignin model dimers by a ruthenium-xantphos catalyst

Hydrogenolysis reactions of so-called lignin model dimers using a Ru-xantphos catalyst are presented (xantphos = 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene). For example, of some nine models studied, the alcohol, 2-(2-methoxyphenoxy)-1-phenylethanol (), with 5 mol% Ru(H)(2)(CO)(PPh(3))(xantphos) () in toluene-d(8) at 135 °C for 20 h under N(2), gives in ～95% yield the C-O cleavage hydrogenolysis products, acetophenone () and guaiacol (), and a small amount (<5%) of the ketone, 2-(2-methoxyphenoxy)-1-phenylethanone (), as observed by (1)H NMR spectroscopy. The in situ Ru(H)(2)(CO)(PPh(3))(3)/xantphos system gives similar findings, confirming a recent report (J. M. Nichols et al., J. Am. Chem. Soc., 2010, 132, 12554). The active catalyst is formulated 'for convenience' as 'Ru(CO)(xantphos)'. The hydrogenolysis mechanism proceeds by initial dehydrogenation to give the ketone , which then undergoes hydrogenolysis of the C-O bond to give and . Hydrogenolysis of to and also occurs using the Ru catalyst under 1 atm H(2); in contrast, use of 3-hydroxy-2-(2-methoxyphenoxy)-1-phenyl-1-propanone (), for example, where the CH(2) of has been changed to CHCH(2)OH, gives a low yield (≤15%) of hydrogenolysis products. Similarly, the diol substrate, 2-(2-methoxyphenoxy)-1-phenyl-1,3-propanediol (), gives low yields of hydrogenolysis products. These low yields are due to formation of the catalytically inactive complexes Ru(CO)(xantphos)[C(O)C(OC(6)H(4)OMe)[double bond, length as m-dash]C(Ph)O] () and/or Ru(CO)(xantphos)[C(O)CH[double bond, length as m-dash]C(Ph)O] (), where the organic fragments result from dehydrogenation of CH(2)OH moieties in and . Trace amounts of Ru(CO)(xantphos)(OC(6)H(4)O), a catecholate complex, are isolated from the reaction of with . Improved syntheses of and lignin models are also presented.     

Reductive Deoxygenation of Carbonyl to Methylene by LiAlH4／InBr3

The reductive deoxygenation of aldehydes and ketones into the corresponding alkanes is accomplished by LiAlH4 in the presence of Lewis acid InBr3. It provides a convenient method to complete the transformation from carbonyl compounds to alkanes.