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101.
Sinoj Abraham Larry D. Unsworth 《Journal of polymer science. Part A, Polymer chemistry》2011,49(5):1051-1060
Biomaterials generally suffer from rapid nonspecific protein adsorption, which initiates many deleterious host responses, and complex chemistries that are employed to facilitate cellular interactions. A chemical approach that, based upon current literature, combines a nonfouling architecture with a biomemtic cell‐adhesive end‐group, is presented. Namely, surface‐initiated polymerization of zwitterionic [poly (carboxybetaine methacrylamide)] brushes, with controlled charge densities and phosphonate head groups. Nitroxide mediated free radical polymerization (NMFRP) was employed for various reasons: reduces presence of potentially cytotoxic organometallic catalysts common in atom transfer radical polymerization (ATRP); and it allows a phosphonate end‐group instead of the common brominated end‐group. Thermally oxidized silicon wafers were covalently functionalized with diethyl‐(1‐(N‐(1‐(3‐(trimethoxysilyl)propylcarbamoyl)ethoxy)‐N‐tert‐butylamino)ethyl)phosphonate. NMFRP was used to graft zwitterionic carboxybetaine methacrylamide monomers of varying inter‐charge separation. The resulting thin films were characterized using Attenuated Total Reflectance‐Fourier Transform Infrared (ATR‐FTIR) and X‐ray photoelectron (XPS) spectroscopy, ellipsometry, water contact angle analysis, and thermo gravimetric analysis (TGA). The effect of spacer group on the surface charge density was determined using zeta potential techniques. It is thought that this stratagem will facilitate the ability to tailor systematically both the interior and terminal polymer properties, providing a platform for further understanding how these conditions affect protein adsorption as well as cell‐surface interactions. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献
102.
Larry Guth 《Inventiones Mathematicae》2008,172(3):477-489
If P and P
′ are symplectic polydisks of radii R
1≤...≤R
n
and R
1
′≤...≤R
n
′, respectively, then we prove that P symplectically embeds in P
′ provided that C(n)R
1≤R
1
′ and C(n)R
1...R
n
≤R
1
′...R
n
′. Up to a constant factor, these conditions are optimal. 相似文献
103.
Liquid-liquid extraction employing supercritical carbon dioxide has been developed for removal of polar materials from water. 相似文献
104.
Larry Bates 《manuscripta mathematica》1990,66(1):109-111
Abstract A proof of the rigidity of closed symplectic polydiscs is given. 相似文献
105.
The acute toxicity for tri-n-butyltin taurocholate (TBT-TA), a newly synthesized organotin steroid, was determined using Long Evans rats. The organotin compound was suspended in corn oil and administered by gavage using standard techniques. The TBT-TA exhibited a taurocholic acid toxicity at 24 h and a tributyltin toxicity at three days. The LD50 values were 611 and 384 mg kg?1 respectively. The dead rats exhibited distended stomachs, enlarged cecums, and lesions in the gastrointestinal tract. The toxicity is similar to that observed with other trialkyltin compounds. 相似文献
106.
107.
Juraj Černák Juraj Kuchár Monika Stolárová Marcela Kajňaková Martin Vavra Ivan Potočňák Larry R. Falvello Milagros Tomás 《Transition Metal Chemistry》2010,35(6):737-744
From the systems Cu(II)–cyclam–[M(CN)4]2? (cyclam = 1,4,8,11-tetraazacyclotetradecane; M = Ni, Pd, Pt), three cyanidocomplexes Cu(cyclam)M(CN)4 [M = Ni (1), Pd (2), Pt (3)] were isolated and characterized by chemical analysis, IR and UV–VIS spectroscopy. The three compounds are isostructural, and their crystal structures are formed by quasi-linear chains exhibiting [–Cu(cyclam)–μ–NC–M(CN)2–μ–CN–]n composition. The Cu(II) atoms reside on centres of symmetry and are coordinated in the form of an elongated octahedron with mean equatorial Cu–N bonds of 2.015(12), 2.017(13) and 2.011(11) Å in (1), (2) and (3), respectively, and weakly N-bonded bridging cyanido ligands in the axial positions [2.5321(9) Å in (1), 2.518(2) Å in (2) and 2.549(3) Å in (3)]. Hydrogen bonds of the N–H···Ncyanido···H–N type link neighbouring chains, and a topologically square network of paramagnetic Cu(II) atoms is formed. The magnetic susceptibilities of all three complexes follow the Curie-Weiss law with a weak antiferromagnetic exchange coupling below 5 K. 相似文献
108.
Cannon JS Kirsch SF Overman LE Sneddon HF 《Journal of the American Chemical Society》2010,132(43):15192-15203
The catalytic enantioselective S(N)2' displacement of (Z)-allylic trichloroacetimidates catalyzed by the palladium(II) complex [COP-OAc](2) is a broadly useful method for the asymmetric synthesis of chiral branched allylic esters. A variety of experiments aimed at elucidating the nature of the catalytic mechanism and its rate- and enantiodetermining steps are reported. Key findings include the following: (a) the demonstration that a variety of bridged-dipalladium complexes are present and constitute resting states of the COP catalyst (however, monomeric palladium(II) complexes are likely involved in the catalytic cycle); (b) labeling experiments establishing that the reaction proceeds in an overall antarafacial fashion; (c) secondary deuterium kinetic isotope effects that suggest substantial rehybridization at both C1 and C3 in the rate-limiting step; and (d) DFT computational studies (B3-LYP/def2-TZVP) that provide evidence for bidentate substrate-bound intermediates and an anti-oxypalladation/syn-deoxypalladation pathway. These results are consistent with a novel mechanism in which chelation of the imidate nitrogen to form a cationic palladium(II) intermediate activates the alkene for attack by external carboxylate in the enantiodetermining step. Computational modeling of the transition-state structure for the acyloxy palladation step provides a model for enantioinduction. 相似文献
109.
Berwyck L. J. Poad Huong T. Pham Michael C. Thomas Jessica R. Nealon J. Larry Campbell Todd W. Mitchell Stephen J. Blanksby 《Journal of the American Society for Mass Spectrometry》2010,21(12):1989-1999
Ozone-induced dissociation (OzID) exploits the gas-phase reaction between mass-selected lipid ions and ozone vapor to determine
the position(s) of unsaturation. In this contribution, we describe the modification of a tandem linear ion-trap mass spectrometer
specifically for OzID analyses wherein ozone vapor is supplied to the collision cell. This instrumental configuration provides
spatial separation between mass-selection, the ozonolysis reaction, and mass-analysis steps in the OzID process and thus delivers
significant enhancements in speed and sensitivity (ca. 30-fold). These improvements allow spectra revealing the double-bond
position(s) within unsaturated lipids to be acquired within 1 s: significantly enhancing the utility of OzID in high-throughput
lipidomic protocols. The stable ozone concentration afforded by this modified instrument also allows direct comparison of
relative reactivity of isomeric lipids and reveals reactivity trends related to (1) double-bond position, (2) substitution
position on the glycerol backbone, and (3) stereochemistry. For cis- and trans-isomers, differences were also observed in the branching ratio of product ions arising from the gas-phase ozonolysis reaction,
suggesting that relative ion abundances could be exploited as markers for double-bond geometry. Additional activation energy
applied to mass-selected lipid ions during injection into the collision cell (with ozone present) was found to yield spectra
containing both OzID and classical-CID fragment ions. This combination CID-OzID acquisition on an ostensibly simple monounsaturated
phosphatidylcholine within a cow brain lipid extract provided evidence for up to four structurally distinct phospholipids
differing in both double-bond position and sn-substitution. 相似文献
110.
Travis J. Moore Darron P. Cundick Dale R. Tree Larry L. Baxter 《Journal of Quantitative Spectroscopy & Radiative Transfer》2011,112(12):1978-1986
The spectral emittance of deposits left by bituminous and sub-bituminous coals under oxidizing conditions have been measured in situ. Pulverized coal is injected into a down-fired entrained-flow reactor. Ash accumulates on a probe in the reactor effluent and radiation emitted by the ash layer is recorded using a Fourier transform infrared (FTIR) spectrometer. Values for the spectral emissive power emitted by the ash and the surface temperature of the ash are extracted from these data. These results are then used to calculate the spectral emittance of the deposit. The spectral emittances of ash deposits formed by burning Illinois #6 (bituminous) coal and Powder River Basin (sub-bituminous) coal were measured between 3000 and 500 wavenumbers. The spectral emittance of the deposit left by the bituminous coal has a constant value of approximately 0.46 between 3000 and 2400 wavenumbers. Between 2200 and 1200 wavenumbers, the spectral emittance of the deposit increases from approximately 0.47 to approximately 0.61. Between 1200 and 500 wavenumbers, the spectral emittance is relatively constant at 0.61. The spectral emittance of the deposit left by the sub-bituminous coal is also relatively constant between 3000 and 2400 wavenumbers at a value of 0.29. Between 2200 and 500 wavenumbers, the spectral emittance of deposits from the sub-bituminous coal increases from approximately 0.29 to 0.55. Differences between these spectral emittance measurements and those measured ex situ illustrate the importance of making in situ measurements. Band emittances were calculated using the measured spectral emittances, and band emittances of the deposits are reported as functions of temperature. 相似文献