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11.
A previous publication1 utilizing the INDO2 and CND0/23 semi-empirical SCF-MO techniques has shown that these methods predict anomalous minima in the potential surfaces of small molecules and molecular ions, particularly those of type 0-X-0. Two studies have bcmen published concerning the removal of such anomalous pre-dictiors. The first approach4 involved reparameterization of the INDO method – specifically involving the Slater exponents α, and the bonding parameters B° of carbon and oxygen – to remove the anomalous iinimum from the potential surface of C02. It was de-monstrated that reparameterization could be used to remove the Salse minimum in this case; but only at the expense of the other predictive qualities of INDO, or with the prediction of an unreal-istically broad energy minimum – neither of which could b e con-sidered an acceptable solution. 相似文献
12.
Donald W. Combs Jeffery B. Press Dennis Mulvey Yolanda Gray-Nunez Stanley C. Bell 《Journal of heterocyclic chemistry》1986,23(4):1263-1264
A ring contraction of 1,4-benzodiazepin-2-one to 2-chloromethylquinazoline in phosphoryl chloride is described. The intermediacy of an aziridinoquinazoline is proposed. 相似文献
13.
14.
Raphaël Trouillon Zachary Combs Bhavik Anil Patel Danny O’Hare 《Electrochemistry communications》2009,11(7):1409-1413
Stability of sensors in biosamples is a critical issue and can be mitigated by membranes. The effect of different membranes (Nafion, cellulose acetate, chitosan, fibronectin, PSS/PL) on the electrochemistry of an outer-sphere redox couple (ruthenium II/III hexaammine) and on the electrocatalytic reduction of dissolved oxygen are described. Biofouling has been induced by albumin solutions. Results demonstrate good performances of fibronectin in all situations investigated. Other membranes do not provide a satisfactory protection from biofouling and some of them, PSS/PL in particular, seriously disturb electrochemical mechanisms. 相似文献
15.
Stephen MT Hoke Gaoyang Liang A Irina Mutiu Julie Genereaux Christopher J Brandl 《BMC biochemistry》2007,8(1):16
Background
Spt7 is an integral component of the multi-subunit SAGA complex that is required for the expression of ~10% of yeast genes. Two forms of Spt7 have been identified, the second of which is truncated at its C-terminus and found in the SAGA-like (SLIK) complex. 相似文献16.
Fluorides are determined by the back-titration of excess of samarium with EDTA to the canary yellow end-point of Methylthymol Blue. The fluoride is precipitated and digested in a solution buffered at pH 2.5-3.0 with monochloroacetate buffer. After digestion, the pH is adjusted to 5.6-5.8 with pyridine and the excess of samarium is back-titrated in the presence of the precipitate, for samples with small quantities of fluoride. The procedure was used to analyse simple fluorides, fluoroborates and some other fluoro-complexes. 相似文献
17.
Monte L. Helm Kristi D. Loveday Charles M. Combs Elizabeth L. Bentzen Donald G. VanDerveer Robin D. Rogers Gregory J. Grant 《Journal of chemical crystallography》2003,33(5-6):447-455
We report here two crystal structures of heavy metal complexes containing macrocyclic trithioethers. The trithioether, 10S3 (1,4,7-trithiacyclodecane) complexes Pb(II) to form a compound of the formula [Pb(10S3)](ClO4)2(H2O) (Compound 1). This behavior contrasts the related trithioether 9S3 (1,4,7-trithianonane), which readily forms a bis Pb(II) complex. Crystals of Compound 1 consist of [Pb(10S3)(H2O)]2+ units and perchlorate anions which are weakly bound to the Pb2+ center. The two perchlorate anions serve as bidentate ligands to a single lead(II) center. However, a third oxygen in one of the perchlorates also serves as a bridging group between two lead(II) centers, linking the [Pb(10S3)(H2O)]2+ units into zigzag chains. Thus, a highly irregular nine-coordinate (S3O6) environment around the Pb2+ion is formed by the three sulfur donors from the 10S3 ligand, one coordinated water, and five oxygens from three different perchlorate anions. Also, the lone pair electrons on the Pb center are stereochemically active. Compound 2, [Cd(9S3)2](ClO4)2 2 CH3NO2, forms a distorted octahedral structure with unusual hexakis(thioether) coordination to the Cd(II) center. Bond distances and angles are very comparable to those found in the structure of the tetrafluoroborate salt of the complex cation. (1): P21/c, a = 9.1720(6) Å, b = 15.7687(11) Å, c = 11.8427(8) Å, = 93.0180(10) , V = 1710.4 (2) Å3, Z = 4; (2): P21/c , a = 10.4305(10) Å, b = 15.2059(6) Å, c = 9.4919(7) Å, = 99.324(9), V = 1485.6(2) Å3, Z = 2. 相似文献
18.
[structure: see text]. The first asymmetric synthesis of the (S)-1,1-dioxido-isothiazolidin-3-one ((S)-IZD) pTyr mimetic, which has been incorporated into the recently reported potent protein tyrosine phosphatase 1B (PTP1B) inhibitors, is presented herein. The key reaction is the reduction of the (R)-oxido-isothiazolidin-3-one heterocycle with excellent regiochemical and stereochemical control (>98% ee; 82% yield). 相似文献
19.
Grotjahn DB Van S Combs D Lev DA Schneider C Rideout M Meyer C Hernandez G Mejorado L 《The Journal of organic chemistry》2002,67(26):9200-9209
Syntheses of pyrazoles featuring a functionalized side chain attached to carbon 3 and varying alkyl and aryl substituents attached to carbon 5 are presented. Installation of R = methyl, isopropyl, tert-butyl, adamantyl, or phenyl groups at C5 is reported here, starting by coupling protected alkynols with acid chlorides RCOCl, forming alkynyl ketones, which are reacted with hydrazine to form the pyrazole nucleus. Alcohol deprotection and conversion to a chloride gave 5-substituted 3-(chloromethyl)- or 3-(2-chloroethyl)pyrazoles. This sequence can be done within 2 d on a 30 g scale in excellent overall yield. Through nucleophilic substitution reactions, the chlorides are useful precursors to other polyfunctional pyrazoles. In the work here, derivatives with side chains LCH(2)- and LCH(2)CH(2)- at C3 (L = thioether or phosphine) were made as ligands. The significance of the ligands made here is that by placing a ligating side chain on a ring carbon (C3), rather than on a ring nitrogen, the ring nitrogen not bound to the metal and its attached proton will be available for hydrogen bonding, depending on the steric environment created by R at C5. 相似文献
20.
A platinum-lined, flowing autoclave facility was used to investigate the solubility behavior of titanium dioxide (TiO2) in aqueous sodium phosphate, sodium hydroxide and ammonium hydroxide solutions between 17 and 288°. Baseline Ti(IV) solubilities were found to be on the order of one nanomolal, which were enhanced by the formation of anionic hydroxo- and phosphato-complexes. The measured solubility behavior was examined via a titanium(IV) ion hydrolysis/complexing reaction equilibria were obtained from a least squares analysis of the data. The existence of three new Ti(IV) ion complexes is reported for the first time: Ti(OH)4(HPO4)2–, Ti(OH)5(H2PO4)2– and Ti(OH)5(HPO4)3–. The triply-charged anionic complex was the dominant Ti(IV) species in concentrated, alkaline phosphate solutions at elevated temperatures. This complex is expected to exhibit C.N.=4 (i.e., Ti(OH)2OPO
4
3–
). A summary of thermochemical properties for species in the systems TiO2-H2O and TiO2-P2O5-H2O is also provided. 相似文献