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81.
Chan J Burke BJ Baucom K Hansen K Bio MM DiVirgilio E Faul M Murry J 《The Journal of organic chemistry》2011,76(6):1767-1774
Two new, reliable syntheses of a pyrido[2,3-d]-pyrimidine inhibitor of the CXCR3 receptor are described. A nine-step synthesis of the CXCR3 inhibitor (1) from 2-aminonicotinic acid was demonstrated on a multikilogram scale and incorporates a classic resolution to deliver the enantioenriched active pharmaceutical ingredient (API). A second synthesis of the CXCR3 inhibitor starts from (+)-(D)-Boc alanine and 2-chloronicotinic acid and utilizes a Goldberg coupling. This second synthesis, performed on a gram scale, intersects the former route at a common intermediate thereby completing a formal synthesis of the enantioenriched API in higher overall yield without the need for a resolution. 相似文献
82.
Lebedeva NV Schmidt RD Concepcion JJ Brennaman MK Stanton IN Therien MJ Meyer TJ Forbes MD 《The journal of physical chemistry. A》2011,115(15):3346-3356
The proton-coupled electron transfer (PCET) reaction between the bpz-based photoexcited (3)MLCT state of [Ru(II)(bpy)(2)(bpz)](2+) (bpy = 2,2'-bipyridine, bpz = 2,2'-bipyrazine) and a series of substituted hydroquinones (H(2)Q) has been studied by transient absorption (TA) and time-resolved electron paramagnetic resonance (TREPR) spectroscopy at X-band. When the reaction is carried out in a CH(3)CN/H(2)O mixed solvent system with unsubstituted hydroquinone, the neutral semiquinone radical (4a) and its conjugate base, the semiquinone radical anion (4b), are both observed. Variation of the acid strength in the solvent mixture allows the acid/base dependence of the PCET reaction to be investigated. In solutions with very low acid concentrations, TREPR spectra exclusively derived from radical anion 4b are observed, while at very high acid concentrations, the spectrum is assigned to the protonated structure 4a. At intermediate acid concentrations, either a superposition of spectra is observed (slow exchange between 4a and 4b) or substantial broadening in the TREPR spectrum is observed (fast exchange between 4a and 4b). Variation of substituents on the H(2)Q ring substantially alter this acid/base dependence and provide a means to investigate electronic effects on both the ET and PT components of the PCET process. The TA results suggest a change in mechanism from PCET to direct ET quenching in strongly basic solutions and with electron withdrawing groups on the H(2)Q ring system. Changing the ligand on the Ru complex also alters the acid/base dependence of the TREPR spectra through a series of complex equilibria between protonated and deprotonated hydroquinone radicals and anions. The relative intensities of the signals from radical 4a versus 4b can be rationalized quantitatively in terms of these equilibria and the relevant pK(a) values. An observed equilibrium deuterium isotope effect supports the conclusion that the post-PCET HQ(?)/Q(?-) equilibrium is the most important in determining the 4a/4b ratio at early delay times. 相似文献
83.
Broaders KE Pastine SJ Grandhe S Fréchet JM 《Chemical communications (Cambridge, England)》2011,47(2):665-667
Acid-degradable microcapsules were prepared via an interfacial polymerization. Degradation of the thin wall of the capsules leads to all-or-nothing cargo release. The only byproducts of degradation are acetone, and a non-toxic triamide. Proof-of-concept experiments showed that cargo can be delivered to and released in cells. 相似文献
84.
Bantz KC Meyer AF Wittenberg NJ Im H Kurtuluş O Lee SH Lindquist NC Oh SH Haynes CL 《Physical chemistry chemical physics : PCCP》2011,13(24):11551-11567
This perspective gives an overview of recent developments in surface-enhanced Raman scattering (SERS) for biosensing. We focus this review on SERS papers published in the last 10 years and to specific applications of detecting biological analytes. Both intrinsic and extrinsic SERS biosensing schemes have been employed to detect and identify small molecules, nucleic acids, lipids, peptides, and proteins, as well as for in vivo and cellular sensing. Current SERS substrate technologies along with a series of advancements in surface chemistry, sample preparation, intrinsic/extrinsic signal transduction schemes, and tip-enhanced Raman spectroscopy are discussed. The progress covered herein shows great promise for widespread adoption of SERS biosensing. 相似文献
85.
Kyle Pula 《Discrete Mathematics》2011,311(8-9):577-581
86.
Thin films of SnSb2S4 have been prepared on glass substrate by using thermal evaporation techniques. The films were annealed in argon gas at low pressure in sealed glass ampoules at 85 °C, 150 °C, 275 °C and 325 °C. XRD of the films reveal that the low temperature annealed films are poly crystalline while the as deposited films and high annealed films are in amorphous states. There is no adequate variation in the photoconductivity response of the amorphous and crystalline phases. The transmittance of the films is low and having no transmittance below 740 nm. The band gap calculated by ellipsometry technique is in the range of 1.82–3.1 eV. The films have n-type conductivity but the film annealed at 325 °C show p-type conductivity. 相似文献
87.
Campbell CJ Smoukov SK Bishop KJ Grzybowski BA 《Langmuir : the ACS journal of surfaces and colloids》2005,21(7):2637-2640
Hydrogel stamps are used to reactively micropattern various types of substrates. The method, called reactive wet stamping (r-WETS), is general in nature and overcomes several limitations of conventional soft-lithographic techniques. Illustrative applications of r-WETS in surface wettability modification, deposition of metallic microstructures, preparation of supports for electrostatic self-assembly, and multistep reactive patterning are discussed. 相似文献
88.
J. Arvieux G. Audit P. Catillon J. Domingo J.L. Faure K. Gabathuler Q. Ingram G. Kyle J.M. Laget J. Martin G. Tamas E. Vincent 《Nuclear Physics A》1985,444(4):579-588
We have studied the excitation function of the reaction 2H(π±, p)X at a fixed proton angle of 90° for several fixed proton momenta of the detected proton as a function of the incident pion energy. No signal was found for a previous candidate for a dibaryon resonance around a mass of 2.23 GeV. The general trend of the data is reproduced by a multiple scattering theory 相似文献
89.
The filling behavior of a room temperature solvent, perfluoromethylcyclohexane, in approximately 20 nm nanoporous alumina membranes was investigated in situ with small angle x-ray scattering. Adsorption in the pores was controlled reversibly by varying the chemical potential between the sample and a liquid reservoir via a thermal offset, DeltaT. The system exhibited a pronounced hysteretic capillary filling transition as liquid was condensed into the nanopores. These results are compared with Kelvin-Cohan theory, with a modified Derjaguin approximation, as well as with predictions by Cole and Saam. 相似文献
90.