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21.
In-situ gelation of aqueous sulfomethylated resorcinol formaldehyde (SMRF) system inBerea core has been investigated. Two sets of displacement experiments were conducted with thissystem (containing 5% NaCl, 0. 036% CaCl_2. 2H_2O). The brine permeabilities of the coreswere reduced significantly from about 600 to 0.1 md. The in-situ gelation in Berea core occurreda little bit earlier than gelation anticipated from bulk test in the experiments. The gel time waseasier to control at initial pH between 6 and 8. During injection of SMRF system, the apparentviscosity was less than 1 mPa·s at 41℃. 相似文献
22.
Richard P. Stanley 《Graphs and Combinatorics》1987,3(1):55-66
I. Bárány and L. Lovász [Acta Math. Acad. Sci. Hung.40, 323–329 (1982)] showed that ad-dimensional centrally-symmetric simplicial polytopeP has at least 2
d
facets, and conjectured a lower bound for the numberf
i
ofi-dimensional faces ofP in terms ofd and the numberf
0 =2n of vertices. Define integers
A. Björner conjectured (unpublished) that
(which generalizes the result of Bárány-Lovász sincef
d–1
= h
i
), and more strongly that
, which is easily seen to imply the conjecture of Bárány-Lovász. In this paper the conjectures of Björner are proved.Partially supported by NSF grant MCS-8104855. The research was performed when the author was a Sherman Fairchild Distinguished Scholar at Caltech. 相似文献
23.
Stanley Bruckenstein Alex Fensore Zhufen Li A.Robert Hillman 《Journal of Electroanalytical Chemistry》1994,370(1-2)
Absolute resonant frequency measurements were made on gold-coated AT-cut quartz crystals with one face in contact with a series of liquids. The effect of surface roughness and liquid properties (viscosity and density) was analyzed in terms of a “trapped liquid” model. In this model, liquid present in surface imperfections is viewed as rigidly coupled mass. In some of the literature this density-dependent, but not viscosity-dependent, term is viewed as being additive to the hydrodynamic shift seen for a smooth surface. Data obtained using 1 μm and 5 μm surface finish crystals are inconsistent with the predictions of the trapped liquid model. This suggests hydrodynamic coupling between liquid internal and external to the crevices. Despite the lack of a theoretical model for the liquid motion, it is possible to compensate for frequency variations resulting from changing liquid properties and for roughness effects by making direct measurements of the resonant frequency difference between two crystals exposed to the same solution. This novel procedure works to the extent that the two crystals have similar surface topographies. Compensation is excellent for 1 μm finish crystals and good for 5 μm finish crystals. 相似文献
24.
Ermann M Simkovsky NM Roberts SM Parry DM Baxter AD 《Journal of combinatorial chemistry》2002,4(4):352-358
A solid-phase synthesis of substituted cyclic urea derivatives as potential heterocyclic library scaffolds is described. 2-Amino-3-nitropyridine is attached to Wang resin via a carbamate linkage. Reduction of the nitro group was achieved with SnCl(2).2H(2)O. Reductive alkylation with a range of substituted benzaldehydes followed by cyclative cleavage afforded a small library of 3-substituted imidazo[4,5-b]pyridine-2-ones in 33-45% yield and 59-88% purity. Subsequently, this methodology was applied to the synthesis of 3-substituted imidazo[4,5-f]quinolin-2-ones. 相似文献
25.
De novo structural prediction of transition metal complexes is investigated. Technetium complexes are chosen given their importance in medical imaging and nuclear waste remediation and for the chemical diversity they display. A new conformational searching algorithm (LIGB) for transition metals is described that allows one to search for different conformational and geometric isomers within a single simulation. In the preponderance of cases, both conformational searching techniques (LIGB and high-temperature molecular dynamics/simulated annealing) provide comparable results, while LIGB is superior for macrocyclic complexes. A genetic algorithm-optimized PM3(tm) parametrization for Tc is compared with the standard implementation and found to yield a significant improvement in predictive ability for the most prevalent Tc structural motifs. The utility of a coupled molecular mechanics-semiempirical quantum mechanics protocol is demonstrated for very rapid, efficient, and effective de novo prediction of transition metal complex geometries. 相似文献
26.
Nicholas D. Adams Stanley J. Schmidt Steven D. Knight Dashyant Dhanak 《Tetrahedron letters》2007,48(23):3983-3986
A novel synthesis of 4H-pyrazolo-[3,4-d]pyrimidin-4-ones is described. This approach utilizes an in situ generated iminochloride as a key precursor for amidine formation, with subsequent base-catalyzed ring closure. This method represents a mild and efficient entry into this ring system which is amenable to diversification of the core template. 相似文献
27.
A systematic optimization strategy for reverse-phase h.p.l.c. is used to produce complete separation of all components of a mixture containing two coumarins, umbelliferone and scopoletin, and the cis-trans isomers of two cinnamic acids, p-coumaric and ferulic. A series of experiments gives retention time data for each of these substances in four citric acid-buffered mobile phases. A mathematical model fitted to this data gives model parameters that provide the basis for a window diagram of relative retentions vs. mobile phase pH. The window diagram gives an estimate of the mobile phase pH required for optimum separation. 相似文献
28.
Burford N Cameron TS Clyburne JA Eichele K Robertson KN Sereda S Wasylishen RE Whitla WA 《Inorganic chemistry》1996,35(19):5460-5467
The phosphadiazonium cation [MesNP](+) reacts quantitatively with the fluorenylide anion, MesNH(2), and MesOH (Mes = 2,4,6-tri-tert-butylphenyl), resulting in formal insertion of the N-P moiety into the H-Y (Y = C, N, O) bonds. Specifically, reaction of MesNPCl with fluorenyllithium gives the aminofluorenylidenephosphine [crystal data: C(31)H(38)NP, monoclinic, P2(1)/c, a = 9.568(8) ?, b = 24.25(2) ?, c = 11.77(1) ?, beta = 101.38(8) degrees, Z = 4]. Similarly, reaction of [MesNP][GaCl(4)] with MesNH(2) gives the diaminophosphenium salt [MesN(H)PN(H)Mes][GaCl(4)] [crystal data: C(36)H(60)Cl(4)GaN(2)P, monoclinic, C2/c, a = 24.921(2) ?, b = 10.198(4) ?, c = 16.445(2) ?, beta = 93.32(1) degrees, Z = 4], and reaction with MesOH gives the first example of an aminooxyphosphenium salt [MesN(H)POMes][GaCl(4)]. It is proposed that the reactions involve nucleophilic attack at phosphorus followed by a 1,3-hydrogen migration from Y to N. Experimental evidence for the formation of sigma-complex intermediates is provided by the isolation of [MesNP-PPh(3)][SO(3)CF(3)] [crystal data: C(37)H(44)F(3)NO(3)P(2)S, triclinic, P&onemacr;, a = 10.663(1) ?, b = 19.439(1) ?, c = 10.502(1) ?, alpha = 103.100(7) degrees, beta = 113.311(7) degrees, gamma = 93.401(7) degrees, Z = 2]. As part of the unequivocal characterization of the aminooxyphosphenium salt, detailed solid-state (31)P NMR studies and GIAO calculations on the phosphenium cations have been performed. Contrary to popular belief, the phosphorus shielding in dicoordinate cations is not caused by the positive charge but results from efficient mixing between the phosphorus lone pair and pi orbitals. 相似文献
29.
Wang J Firestone MA Auciello O Carlisle JA 《Langmuir : the ACS journal of surfaces and colloids》2004,20(26):11450-11456
The surface functionalization of ultrananocrystalline diamond (UNCD) thin films via the electrochemical reduction of aryl diazonium cations is described. The one-electron-transfer reaction leads to the formation of solution-based aryl radicals, which in turn react with the UNCD surface forming stable covalent C-C bonds. Cyclic voltammetry (CV), X-ray photoelectron spectroscopy (XPS), ac impedance spectroscopy, and contact angle measurements have been employed to characterize the organic overlayer and estimate the surface coverage. The grafting of 3,5-dichlorophenyl groups renders the UNCD surface hydrophobic, whereas the attachment of 4-aminophenyl groups makes the surface relatively hydrophilic. The surface coverage, estimated from the electrochemical and XPS measurements, is as high as 70% of a compact monolayer. The aminophenyl terminated surface was obtained by electrochemical reduction of the tethered nitrophenyl groups. This two-step approach yields a UNCD surface with functional moieties available for the potential covalent coupling of a wide variety of biomolecules (e.g., DNA and proteins). 相似文献
30.
Bailey NJ Stanley PD Hadfield ST Lindon JC Nicholson JK 《Rapid communications in mass spectrometry : RCM》2000,14(8):679-684
Reconstructed ion chromatograms have been used to identify relevant high performance liquid chromatography (HPLC) peaks in a directly coupled high performance liquid chromatography/nuclear magnetic resonance spectroscopy/mass spectrometry (HPLC/NMR/MS) experiment. This has been applied to a study of the metabolism of a model compound, 5-nitropyridone (2-hydroxy-5-nitropyridine), in maize plants grown hydroponically. By monitoring the on-flow reconstructed ion chromatogram corresponding to the 5-nitropyridone fragment at m/z 143, and additional molecular ions corresponding to metabolites identified as products from similar compounds, relevant peaks were identified rapidly for subsequent stopped-flow 1H NMR spectroscopic analysis. The combination of coupled HPLC/NMR/MS enabled the direct identification of three metabolites, namely the N-glucoside, N-malonylglucoside, and O-malonylglucoside. This work demonstrates the power of HPLC/NMR/MS for the structural elucidation of xenobiotic metabolites in complex biological matrices (such as plant material) with minimal sample preparation. In particular, using mass spectrometry for the initial identification of relevant HPLC peaks allows the analysis of complex samples without the necessity for other spectroscopic markers, such as 19F NMR signal for fluorinated compounds or UV spectroscopy for molecules with strong UV chromophores. 相似文献