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101.
Tea polyphenols are well known for their beneficial health effects that involve their anti-carcinogenic, anti-mutagenic, anti-pathogenic and anti-oxidative properties. The main polyphenols of green tea are favan-3-ols (catechins) and their corresponding gallate compounds, which constitute about one-third of the dry weight of tea leaves. Their main ingredients are (+)-catechin (C), (−)-epicatechin (EC), (−)-gallocatechin (GC), (−)-epigallocatechin (EGC), (−)-catechin gallate (CG), (−)-epicatechin gallate (ECG), (−)-gallocatechin gallate (GCG) and (−)-epigallocatechin gallate (EGCG). Each has slightly different biological properties. We have developed a method to simultaneously analyze all these compounds in plasma and urine. The samples were first incubated with β-d-glucuronidase and sulfatase to release the catechin residues from their corresponding conjugates for subsequent extraction by selective solid phase column, Waters Oasis HLB extraction cartridges. The extracted molecules were resolved by reversed phase HPLC and monitored by coulometric chemical detection on a CoulArray detector. All eight catechin compounds were analyzed in a single chromatogram within 25 min. For plasma and urine analyses, good linearity (>0.9950) was validated in the range 10-2000 and 10-5000 ng/ml, respectively. The coefficients of variance (CV) were less than 5%. Absolute recovery was greater than 85% and detection limit was 5 ng/ml. The chromatogram exhibited minimal interference as a result of the highly selective solid phase extraction and CoulArray detection. 相似文献
102.
Qiu L Kwong FY Wu J Lam WH Chan S Yu WY Li YM Guo R Zhou Z Chan AS 《Journal of the American Chemical Society》2006,128(17):5955-5965
A series of chiral diphosphine ligands denoted as PQ-Phos was prepared by atropdiastereoselective Ullmann coupling and ring-closure reactions. The Ullmann coupling reaction of the biaryl diphosphine dioxides is featured by highly efficient central-to-axial chirality transfer with diastereomeric excess >99%. This substrate-directed diastereomeric biaryl coupling reaction is unprecedented for the preparation of chiral diphosphine dioxides, and our method precludes the tedious resolution procedures usually required for preparing enantiomerically pure diphosphine ligands. The effect of chiral recognition was also revealed in a relevant asymmetric ring-closure reaction. The chiral tether bridging the two aryl units creates a conformationally rigid scaffold essential for enantiofacial differentiation; fine-tuning of the ligand scaffold (e.g., dihedral angles) can be achieved by varying the chain length of the chiral tether. The enantiomerically pure Ru- and Ir-PQ-Phos complexes have been prepared and applied to the catalytic enantioselective hydrogenations of alpha- and beta-ketoesters (C=O bond reduction), 2-(6'-methoxy-2'-naphthyl)propenoic acid, alkyl-substituted beta-dehydroamino acids (C=C bond reduction), and N-heteroaromatic compounds (C=N bond reduction). An excellent level of enantioselection (up to 99.9% ee) has been attained for the catalytic reactions. In addition, the significant ligand dihedral angle effects on the Ir-catalyzed asymmetric hydrogenation of N-heteroaromatic compounds were also revealed. 相似文献
103.
P. P. Povinec M. K. Pham J. A. Sanchez-Cabeza G. Barci-Funel R. Bojanowski T. Boshkova W. C. Burnett F. Carvalho B. Chapeyron I. L. Cunha H. Dahlgaard N. Galabov L. K. Fifield J. Gastaud J. -J. Geering I. F. Gomez N. Green T. Hamilton F. L. Ibanez M. Ibn Majah M. John G. Kanisch T. C. Kenna M. Kloster M. Korun L. Liong Wee Kwong J. La Rosa S. -H. Lee I. Levy-Palomo M. Malatova Y. Maruo P. Mitchell I. V. Murciano R. Nelson A. Nouredine J. -S. Oh B. Oregioni G. Le Petit H. B. L. Pettersson A. Reineking P. A. Smedley A. Suckow T. D. B. van der Struijs P. I. Voors K. Yoshimizu E. Wyse 《Journal of Radioanalytical and Nuclear Chemistry》2007,273(2):383-393
A reference material designed for the determination of anthropogenic and natural radionuclides in sediment, IAEA-384 (Fangataufa
Lagoon sediment), is described and the results of certification are presented. The material has been certified for 8 radionuclides
(40K, 60Co, 155Eu, 230Th, 238U, 238Pu, 239+240Pu and 241Am). Information values are given for 12 radionuclides (90Sr, 137Cs, 210Pb (210Po), 226Ra, 228Ra, 232Th, 234U, 235U, 239Pu, 240Pu and 241Pu). Less reported radionuclides include 228Th, 236U, 239Np and 242Pu. The reference material may be used for quality management of radioanalytical laboratories engaged in the analysis of radionuclides
in the environment, as well as for the development and validation of analytical methods and for training purposes. The material
is available from IAEA in 100 g units.
Retired from IAEA in 2003. 相似文献
104.
The catalytic, user-friendly phosphination and arsination of aryl halides and triflates by triphenylphosphine and triphenylarsine using palladium catalysts have provided a facile synthesis of functionalized aryl phosphines and arsines in neutral media. Modification of the cynaoarisne yielded optically active N, As ligands which will be screened in various asymmetric catalysis. 相似文献
105.
Millward SW Henning RK Kwong GA Pitram S Agnew HD Deyle KM Nag A Hein J Lee SS Lim J Pfeilsticker JA Sharpless KB Heath JR 《Journal of the American Chemical Society》2011,133(45):18280-18288
We describe the use of iterative in situ click chemistry to design an Akt-specific branched peptide triligand that is a drop-in replacement for monoclonal antibodies in multiple biochemical assays. Each peptide module in the branched structure makes unique contributions to affinity and/or specificity resulting in a 200 nM affinity ligand that efficiently immunoprecipitates Akt from cancer cell lysates and labels Akt in fixed cells. Our use of a small molecule to preinhibit Akt prior to screening resulted in low micromolar inhibitory potency and an allosteric mode of inhibition, which is evidenced through a series of competitive enzyme kinetic assays. To demonstrate the efficiency and selectivity of the protein-templated in situ click reaction, we developed a novel QPCR-based methodology that enabled a quantitative assessment of its yield. These results point to the potential for iterative in situ click chemistry to generate potent, synthetically accessible antibody replacements with novel inhibitory properties. 相似文献
106.
Semilinear elliptic problems in annular domains 总被引:9,自引:0,他引:9
The method of shooting is used to establish existence of positive radially symmetric solutions to nonlinear elliptic equations of the form u+f(r, u)=0 on annular regionsa<r=|x|<b inR
N
, satisfying Dirichlet or Neumann conditions on the boundary. This extends recent work done by Bandle, Coffman and Marcus. A result concerning uniqueness of such solutions is also extended.
This work was supported by the Applied Mathematical Sciences subprogram of the Office of Energy Research, U.S. Department of Energy, under contract W-31-109-Eng-38. The author also wants to thank the Mathematics Institute, University of Basel, for supporting a visit in Oct., 1987 during which the project was initiated. 相似文献
Zusammenfassung Mit Hilfe eines Schiessverfahrens wird die Existenz von Lösungen nichtlinearer Probleme der Form u+f(r, u)=0 in ringförmigen Gebieten nachgewiesen, die verschiedenen Randbedingungen genügen. Es wird auch ihre Eindeutigkeit untersucht. Diese Arbeit verallgemeinert gewisse Ergebnisse von Bandle, Coffman und Marcus.
Résumé On utilise une méthode de tir pour établir l'existence de solutions de problèmes non linéaires du type u+f(r, u)=0 dans des anneaux, vérifiant différentes conditions aux limites. Ensuite on discute l'unicité de ces solutions. Ce travail généralise certains résultats de Bandle, Coffman et Marcus.
This work was supported by the Applied Mathematical Sciences subprogram of the Office of Energy Research, U.S. Department of Energy, under contract W-31-109-Eng-38. The author also wants to thank the Mathematics Institute, University of Basel, for supporting a visit in Oct., 1987 during which the project was initiated. 相似文献
107.
Cheng C Shi Y Zhu C Li W Wang L Fung KK Wang N 《Physical chemistry chemical physics : PCCP》2011,13(22):10631-10634
We report a direct precipitation method for mass production of ZnO microflowers (MFs) containing hierarchical structures. The ZnO MFs are constructed by interlaced single crystalline and porous nanosheets which are ideal photoanode material for dye-sensitized solar cells (DSCs) because the MFs can largely improve the energy harvesting performance and the efficiency of DSCs. Compared with other forms of nano-sized structures, the novel hierarchical structures show obvious advantages in DSC application because of their large surface area for dye-loading, good light scattering efficiency and excellent electrical transport property. The quasi-solid state DSCs fabricated with the MF hierarchical structures exhibited an efficiency of 4.12%, much higher than that of ZnO nanoparticle-based DSCs, indicating a great potential for the development of highly-efficient quasi-solid DSCs. 相似文献
108.
Lam WW Yiu SM Lee JM Yau SK Kwong HK Lau TC Liu D Lin Z 《Journal of the American Chemical Society》2006,128(9):2851-2858
The oxidation of alkanes and arylalkanes by KMnO(4) in CH(3)CN is greatly accelerated by the presence of just a few equivalents of BF(3), the reaction occurring readily at room temperature. Carbonyl compounds are the predominant products in the oxidation of secondary C-H bonds. Spectrophotometric and kinetics studies show that BF(3) forms an adduct with KMnO(4) in CH(3)CN, [BF(3).MnO(4)](-), which is the active species responsible for the oxidation of C-H bonds. The rate constant for the oxidation of toluene by [BF(3).MnO(4)](-) is over 7 orders of magnitude faster than by MnO(4)(-) alone. The kinetic isotope effects for the oxidation of cyclohexane, toluene, and ethylbenzene at 25.0 degrees C are as follows: k(C6H12)/k(C6D12) = 5.3 +/- 0.6, k(C7H8)/k(C7D8) = 6.8 +/- 0.5, k(C8H10)/k(C8D10) = 7.1 +/- 0.5. The rate-limiting step for all of these reactions is most likely hydrogen-atom transfer from the substrate to an oxo group of the adduct. A good linear correlation between log(rate constant) and C-H bond energies of the hydrocarbons is found. The accelerating effect of BF(3) on the oxidation of methane by MnO(4)(-) has been studied computationally by the Density Functional Theory (DFT) method. A significant decrease in the reaction barrier results from BF(3) coordination to MnO(4)(-). The BF(3) coordination increases the ability of the Mn metal center to achieve a d(1) Mn(VI) electron configuration in the transition state. Calculations also indicate that the species [2BF(3).MnO(4)](-) is more reactive than [BF(3).MnO(4)](-). 相似文献
109.
L. Liong Wee Kwong J. J. La Rosa S. H. Lee P. P. Povinec 《Journal of Radioanalytical and Nuclear Chemistry》2001,248(3):751-755
Liquid scintillation spectrometry has become the most widespread method for quantitative analysis of low level -emitters in environmental samples. This technique has been applied in the measurements of 241Pu, 3H and 90Sr in seawater and sediment samples. 241Pu can be measured by direct analysis of an electrodeposited source using - discrimination or by extraction of electrodeposited plutonium into a liquid form compatible with scintillation cocktail. Sediment from Mururoa and Fangataufa atolls showed activities ranging from 18 to 44 Bq/kg. A sediment profile sampled around Bikini Atoll in 1997 showed 241Pu activities ranging from 0.3 to 30 Bq/kg. 3H activities in pore water sediment from Mururoa and Fangataufa atolls were of the order of 103 Bq/m3 which demonstrated its underground origin. 90Sr was measured in the presence of 90Y. The counting efficiency was 92.41.5% and the background 0.027±0.001 s-1. The average chemical recovery for 90Sr was 673%. 相似文献
110.
Tze-Lock Chan Si-San Kwong Thomas C. W. Mak Russell Kwok Xiao-Ming Chen Kai-Liang Shi 《Journal of inclusion phenomena and macrocyclic chemistry》1988,6(5):507-513
C19H19NO3·x CH3CN (x=0.3),M
r=643.35, hexagonal, space groupP61 (No. 169),a=23.027(5),c=5.775(1) Å,V=2652(1) Å3,Z=6. The structure was solved by direct methods and refined toR=0.077 for 1562 observed MoK
reflections. The title heterocyclic carboxylic acid was established as thetrans isomer, with the phenyl and carboxyl substituents occupying pseudo-equatorial and equatorial positions, respectively, of the piperidin-2-one ring in a half-chair conformation. Acid host molecules related by the 61 screw operation are linked by intermolecular O–H...O (cyclic amide) hydrogen bonds to generate an open channel bounded by coaxial intertwined helices each having a pitch of 5c. Within each channel of free diameterca. 6.0 Å the acetonitrile molecules partially occupy highly disordered sites which do not lie on thec axis.
Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82067 (13 pages). 相似文献