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991.
Sun Y Akhremitchev B Walker GC 《Langmuir : the ACS journal of surfaces and colloids》2004,20(14):5837-5845
An atomic force microscope (AFM) method for measuring surface elasticity based on the adhesive interactions between an AFM tip and sample surfaces is introduced. The method is particularly useful when there is a large adhesion between the tip and soft samples, when the indentation method would be less accurate. For thin and soft samples, this method will have much less interference from the substrate than is found using the indentation method because there is only passive indentation induced by tip-sample adhesion; in contrast, a large indentation with a sharp tip in the sample may break its stress-strain linearity, or even make it fracture. For the case where it is difficult to accurately locate the tip-sample contact point, which is problematic for the indentation method, the method based on adhesive interactions is helpful because it does not require locating the tip-sample contact point when fitting the whole retraction force curve. The model is tested on PDMS polymers with different degrees of cross-linking. 相似文献
992.
Schultz T Clarke JS Gilbert T Deyerl HJ Fischer I 《Faraday discussions》2000,(115):17-31; discussion 79-102
We report picosecond time-resolved pump-probe photoelectron spectra of the allyl radical, C3H5, and the fully deuterated allyl, C3D5, carried out in order to elucidate the primary photophysical processes upon UV excitation. It is shown that the UV bands of allyl decay in a two-step process: the first step is an internal conversion to the lower-lying A-state within 20 ps or less, while the second step is a very fast decay from the A-state to the electronic ground state through a conical intersection. In addition we report the first zero kinetic energy (ZEKE) photoelectron spectrum of allyl, yielding an ionisation energy of 65762 cm-1. 相似文献
993.
The effect of digestion conditions (amount of effective alkali, digestion time) on the surface compositions of unbleached softwood (Pinus sylvestris) kraft pulp has been investigated by electron spectroscopy for chemical analysis (ESCA). The quantities monitored were the angular dependence of the total O/C ratio, the relative amounts of carbons in different states of oxidation and the adsorption of Al and Ca ions to the carboxyl groups in the surface. Examination of the angular dependence of ESCA intensities shows that the concentration of alkyl carbon is high in a very thin surface layer and that it decreases linearly with decreasing kappa number. The concentration of alkyl carbon is decreased by extraction of the fibres with dichloromethane, but the amount remaining in the surface after extraction still decreases linearly with decreasing kappa number (i.e. it decreases with increasing digestion time). It is suggested that the observed enrichment of alkyl carbon in the outermost surface layers most probably is due to reprecipitation of lignin. In pulp that has not been extracted, there is also strong enrichment of extractives in the surface. This amount increases with increasing effective alkali but is relatively independent of digestion time. ESCA analysis of the Al and Ca bound to the carboxyl groups shows that the amount depends on digestion time; the results are consistent with the notion that the reprecipitated lignin contains carboxyl groups. 相似文献
994.
Gilbert L. GradyJohn R. Saucier William J. Foley IIIDaniel J. O'hern William J. Weidmann 《Journal of organometallic chemistry》1972
The relative rates for tri-n-butyltin hydride additions to substituted benzaldehydes under free radical and polar conditions have been determined from competitive reactions. The relative rates have been correlated by the Hammett σ or σ+ constants. The polar addition is correlated best by σ and the free radical addition by σ+. Interpretations of the results are presented. 相似文献
995.
996.
Gilbert J. Mains Philip George Charles W. Bock Mendel Trachtman Alistair M. Brett 《Journal of Molecular Structure》1977,41(1):87-98
The results of ab initio STO-3G and STO-4G calculations are reported on tTt- and tCt-1,3,5-hexatriene, including a STO-3G partial geometry optimization of all C/C bond lengths in both isomers. Results are also reported from a partial INDO geometry optimization on.the tTt-isomer, and complete optimizations on both isomers using empirical consistent force Meld programs. Significant discrepancies are found to exist between these calculated structures and those based on the electron diffraction analysis of Traetteberg. In addition, further results of a CNDO/S spectral analysis are presented and compared with experiment. 相似文献
997.
Molecular delivery via electroporation is typically done via molecular diffusion and tissue perfusion. The inherent variability in those distribution methods limits the efficacy of this medical and laboratory technique. Electrophoresis has been shown to improve the distribution and placement of the molecule [Gene Therapy 9 (2002) 1286]. This paper presents a fluid flow model for electrophoresis in tissues. Parallel plate and four-needle needle array electrodes are the electrodes modeled as the delivery devices. The parallel plate electrode produces a homogeneous distribution of the analyte but the needle array electrode creates a peak where the electric field effects diminish. 相似文献
998.
Robert G. Gilbert 《Chemical physics letters》1983,96(2):259-262
It is shown that the optimal means of tabulating collisional energy transfer parameters in gas-phase uni- and ter-molecular reactions is as the average downward energy transfer, rather than the total energy transferred or the collision efficiency. 相似文献
999.
含间位取代苯基聚醚酮酮的结晶与晶体结构研究 总被引:1,自引:0,他引:1
通过差示扫描法(DSC)及广角X 射线衍射(WAXD)技术研究了含间位取代苯基聚醚酮酮(PEKmK)的结晶行为与晶体结构.X 射线结果表明,从熔融态及玻璃态结晶时,PEKmK只有一种晶型,其晶胞参数为:a=07672nm,b=06149nm,c=1599nm.DSC结果表明,PEKmK热分析曲线都出现了熔融双峰,低熔融峰(DOWn)热焓占总热焓4~7%,它源于初始结晶形成的同一晶型不同厚度片晶.低熔融峰在250℃以上结晶转化成高熔融峰(I),PEKmK平衡熔点为295℃ 相似文献
1000.
Bradley R. Morrison Ian A. Maxwell Donald H. Napper Robert G. Gilbert Joop L. Ammerdorffer Anton L. German 《Journal of polymer science. Part A, Polymer chemistry》1993,31(2):467-483
The concentrations and probable nature of charged oligomers formed by aqueous-phase termination in the persulfate-initiated emulsion polymerization of styrene were measured by isotachophoresis. Isotachophoresis has some advantages over other techniques (e.g., GPC, UV spectroscopy) in that it separates species according to their molecular weight, geometry, and charge. The charged water-soluble oligomeric species were detected in experiments in which particles were nucleated in a surfactant-free environment. Identification of the moieties present was made by comparison with model compounds. Evidence was found for bimolecular combination as a major mechanism of termination in the aqueous phase, although the possibility of disproportionation could not be ruled out. The species formed in the aqueous phase under saturated monomer conditions were found to be subject to further reaction towards the end of polymerization. The surface adsorption characteristics of the compounds formed were compared with those of known surfactants and showed good agreement with the assumptions in the model of Maxwell et. al. [Macromolecules, 24 , 1629 (1991)] for initiator efficiencies in emulsion polymerization. The relatively large concentrations of nonradical aqueous–soluble oligomeric compounds demonstrate conclusively that initiator efficiencies are not 100%, as is often assumed in such systems. © 1993 John Wiley & Sons, Inc. 相似文献