全文获取类型
收费全文 | 135篇 |
免费 | 0篇 |
专业分类
化学 | 58篇 |
晶体学 | 1篇 |
力学 | 1篇 |
数学 | 5篇 |
物理学 | 70篇 |
出版年
2022年 | 2篇 |
2021年 | 1篇 |
2020年 | 4篇 |
2019年 | 1篇 |
2018年 | 1篇 |
2014年 | 1篇 |
2013年 | 2篇 |
2012年 | 6篇 |
2011年 | 4篇 |
2010年 | 6篇 |
2009年 | 3篇 |
2008年 | 7篇 |
2007年 | 11篇 |
2006年 | 3篇 |
2005年 | 7篇 |
2004年 | 3篇 |
2003年 | 2篇 |
2002年 | 2篇 |
2001年 | 4篇 |
2000年 | 5篇 |
1999年 | 7篇 |
1998年 | 1篇 |
1996年 | 2篇 |
1995年 | 5篇 |
1994年 | 10篇 |
1993年 | 5篇 |
1992年 | 3篇 |
1991年 | 5篇 |
1990年 | 3篇 |
1989年 | 1篇 |
1987年 | 1篇 |
1986年 | 3篇 |
1985年 | 5篇 |
1983年 | 3篇 |
1978年 | 1篇 |
1973年 | 1篇 |
1970年 | 1篇 |
1968年 | 1篇 |
1922年 | 2篇 |
排序方式: 共有135条查询结果,搜索用时 31 毫秒
81.
Leitch JJ Collins J Friedrich AK Stimming U Dutcher JR Lipkowski J 《Langmuir : the ACS journal of surfaces and colloids》2012,28(5):2455-2464
Quantitative subtractively normalized interfacial Fourier transform infrared reflection spectroscopy (SNIFTIRS) was used to determine the conformation and orientation of sodium dodecyl sulfate (SDS) molecules adsorbed at the single crystal Au(111) surface. The SDS molecules form a hemimicellar/hemicylindrical (phase I) structure for the range of potentials between -200 ≤ E < 450 mV and condensed (phase II) film for electrode potentials ≥500 mV vs Ag/AgCl. The SNIFTIRS measurements indicate that the alkyl chains within the two adsorbed states of SDS film are in the liquid-crystalline state rather than the gel state. However, the sulfate headgroup is in an oriented state in phase I and is disordered in phase II. The newly acquired SNIFTIR spectroscopy measurements were coupled with previous electrochemical, atomic force microscopy, and neutron reflectivity data to improve the current existing models of the SDS film adsorbed on the Au(111) surface. The IR data support the existence of a hemicylindrical film for SDS molecules adsorbed at the Au(111) surface in phase I and suggest that the structure of the condensed film in phase II can be more accurately modeled by a disordered bilayer. 相似文献
82.
Megan E. Leitch Elizabeth Casman Gregory V. Lowry 《Journal of nanoparticle research》2012,14(12):1-23
Many international groups study environmental health and safety (EHS) concerns surrounding the use of engineered nanomaterials (ENMs). These researchers frequently use the ??Project on Emerging Nanotechnologies?? (PEN) inventory of nano-enabled consumer products to prioritize types of ENMs to study because estimates of life-cycle ENM releases to the environment can be extrapolated from the database. An alternative ??snapshot?? of nanomaterials likely to enter commerce can be determined from the patent literature. The goal of this research was to provide an overview of nanotechnology intellectual property trends, complementary to the PEN consumer product database, to help identify potentially ??risky?? nanomaterials for study by the nano-EHS community. Ten?years of nanotechnology patents were examined to determine the types of nano-functional materials being patented, the chemical compositions of the ENMs, and the products in which they are likely to appear. Patenting trends indicated different distributions of nano-enabled products and materials compared to the PEN database. Recent nanotechnology patenting is dominated by electrical and information technology applications rather than the hygienic and anti-fouling applications shown by PEN. There is an increasing emphasis on patenting of nano-scale layers, coatings, and other surface modifications rather than traditional nanoparticles, and there is widespread use of nano-functional semiconductor, ceramic, magnetic, and biological materials that are currently less studied by EHS professionals. These commonly patented products and the nano-functional materials they contain may warrant life-cycle evaluations to determine the potential for environmental exposure and toxicity. The patent and consumer product lists contribute different and complementary insights into the emerging nanotechnology industry and its potential for introducing nanomaterials into the environment. 相似文献
83.
84.
MJ Lazaro AA Herod M Domin Y Zhuo CA Islas R Kandiyoti 《Rapid communications in mass spectrometry : RCM》1999,13(14):1401-1412
Three methods for determining a 'safe' estimate for high-mass limits of MALDI spectra of coal derived liquids were explored, using a sample of coal-tar pitch and its pyridine-insoluble fraction. Co-addition of increasing numbers of single-shot spectra (10, 30, 50 and 100 pulses) showed visually observable reductions in noise levels, consistent with robust and statistically meaningful signals. Three separate types of post-acquisition calculation were used to identify high-mass limits of the spectra. (i) A literature method indicated high-mass limits similar to those observed visually-as a shift from baseline at the highest masses, nearly 350 000 u for the coal tar pitch and about 390 000 u for its pyridine insoluble fraction. (ii) Comparing instrument signal with pre-selected multiples of the standard deviation, upper mass estimates of between 40-60 000 u for the coal-tar pitch and about 95 000 u for its pyridine-insoluble fraction were found. (iii) Calculation of the slope was used to identify 'lift-off' of the spectrum from baseline. The angle between the smoothed spectrum and the baseline was matched to a pre-selected value (e.g. 0.5 degrees and 1 degrees ). However, the arbitrary specification of the key parameter did not establish this last method on a firm basis. The choice of a criterion for estimating high-mass limits of MALDI spectra remains a semi-quantitative procedure; a reasonably conservative high-mass limit may be estimated by comparison of signal with five times the standard deviation. However, evaluation of size exclusion chromatograms of the present samples using polystyrene standards suggests that molecular mass distributions of pitch samples arrived at by MALDI mass spectrometry are, at least partly, determined by the limitations of available instruments. Copyright 1999 John Wiley & Sons, Ltd. 相似文献
85.
Zhu LY Peng JC Reimer PE Awes TC Brooks ML Brown CN Bush JD Carey TA Chang TH Cooper WE Gagliardi CA Garvey GT Geesaman DF Hawker EA He XC Isenhower LD Kaplan DM Kaufman SB Klinksiek SA Koetke DD Lee DM Lee WM Leitch MJ Makins N McGaughey PL Moss JM Mueller BA Nord PM Papavassiliou V Park BK Petitt G Sadler ME Sondheim WE Stankus PW Thompson TN Towell RS Tribble RE Vasiliev MA Webb JC Willis JL Wise DK Young GR;FNAL E/NuSea Collaboration 《Physical review letters》2007,99(8):082301
We report a measurement of the angular distributions of Drell-Yan dimuons produced using an 800 GeV/c proton beam on a deuterium target. The muon angular distributions in the dilepton rest frame have been measured over the kinematic range 4.5相似文献
86.
Zhang Z Leitch DC Lu M Patrick BO Schafer LL 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(7):2012-2022
Amidate-supported titanium amido complexes are efficient and regioselective precatalysts for intermolecular hydroamination of terminal alkynes with primary amines. The synthesis and characterization of the first bis(amidate)-supported titanium-imido complex is reported. Its role as the active catalytic species is suggested in the course of product distribution studies using deuterated substrates. The bis(amidate)-supported precatalysts exhibit good functional-group tolerance, even performing hydroaminations in the presence of ester and amide groups. This functional-group tolerance was exploited in the synthesis of a variety of 1-substituted tetrahydroisoquinoline alkaloids and a one-pot hydroaminative procedure for the high yielding preparation of the benzo[a]quinolizine skeleton. 相似文献
87.
We report on a study of the hydrogenation of melt-grown Zn-doped GaAs, using a remote DC plasma system. Depth profiles of the free carrier concentration revealed the extent of passivation of the hydrogenated GaAs. Annealing at temperatures between 90 and 160° C for various times, with a reverse bias applied to the Schottky diode, allowed us to observe the reactivation of the Zn-acceptors in the high-field space-charge region of the diode. The thermal dissociation of the electrically neutral ZnH complex is found to obey first-order kinetics, with a dissociation energy EZnH = 1.33 ± 0.03 eV. 相似文献
88.
A broad mechanistic investigation regarding hydroamination reactions catalyzed by a tethered bis(ureate) zirconium species, [ureate(2-)]Zr(NMe(2))(2)(HNMe(2)), is described. The cyclization of both primary and secondary aminoalkene substrates gives similar kinetic profiles, with zero-order dependence on substrate concentration up to ~60-75% conversion, followed by first-order dependence for the remainder of the reaction. The addition of 2-methylpiperidine changes the observed substrate dependence to first order throughout the reaction, but does not act as a competitive inhibitor. The reactions are first order in precatalyst up to loadings of ~0.15 M, indicating that a well-defined, mononuclear catalytic species is operative. Several model complexes have been structurally characterized, including dimeric imido and amido species, and evaluated for catalytic performance. These results indicate that imido species need not be invoked as catalytically relevant intermediates, and that the mono(amido) complex [ureate(2-)]Zr(NMe(2))(Cl)(HNMe(2)) is much less active than its bis(amido) counterpart. Structural evidence suggests that this is due to differences in coordination geometry between the mono- and bis(amido) complexes, and that an equatorial amido ligand is required for efficient catalytic turnover. On the basis of the determination of kinetic isotope effects and stoichiometric reactivity, the catalytic turnover-limiting step is proposed to be a concerted C-H, C-N bond-forming process with a highly ordered, unimolecular transition state (ΔS(?) = -21 ± 1 eu). In addition to this key bond-forming step, the catalytic cycle involves an on-cycle pre-equilibrium between six- and seven-coordinate intermediates, leading to the observed switch from zero- to first-order kinetics. 相似文献
89.
Leitch AA Lekin K Winter SM Downie LE Tsuruda H Tse JS Mito M Desgreniers S Dube PA Zhang S Liu Q Jin C Ohishi Y Oakley RT 《Journal of the American Chemical Society》2011,133(15):6051-6060
The bromo-substituted bisdiselenazolyl radical 4b (R(1) = Et, R(2) = Br) is isostructural with the corresponding chloro-derivative 4a (R(1) = Et, R(2) = Cl), both belonging to the tetragonal space group P(4)2(1)m and consisting of slipped π-stack arrays of undimerized radicals. Variable temperature, ambient pressure conductivity measurements indicate a similar room temperature conductivity near 10(-4) S cm(-1) for the two compounds, but 4b displays a slightly higher thermal activation energy E(act) (0.23 eV) than 4a (0.19 eV). Like 4a, radical 4b behaves as a bulk ferromagnet with an ordering temperature of T(C) = 17.5 K. The coercive field H(c) (at 2 K) of 1600 Oe for 4b is, however, significantly greater than that observed for 4a (1370 Oe). High pressure (0-15 GPa) structural studies on both compounds have shown that compression reduces the degree of slippage of the π-stacks, which gives rise to changes in the magnetic and conductive properties of the radicals. Relatively mild loadings (<2 GPa) cause an increase in T(C) for both compounds, that of 4b reaching a maximum value of 24 K; further compression to 5 GPa leads to a decrease in T(C) and loss of magnetization. Variable temperature and pressure conductivity measurements indicate a decrease in E(act) with increasing pressure, with eventual conversion of both compounds from a Mott insulating state to one displaying weakly metallic behavior in the region of 7 GPa (for 4a) and 9 GPa (for 4b). 相似文献
90.
Mark Cecchini Joseph Ecker Michael Kupferschmid Robert Leitch 《European Journal of Operational Research》2013
While significant progress has been made, analytic research on principal-agent problems that seek closed-form solutions faces limitations due to tractability issues that arise because of the mathematical complexity of the problem. The principal must maximize expected utility subject to the agent’s participation and incentive compatibility constraints. Linearity of performance measures is often assumed and the Linear, Exponential, Normal (LEN) model is often used to deal with this complexity. These assumptions may be too restrictive for researchers to explore the variety of relationships between compensation contracts offered by the principal and the effort of the agent. In this paper we show how to numerically solve principal-agent problems with nonlinear contracts. In our procedure, we deal directly with the agent’s incentive compatibility constraint. We illustrate our solution procedure with numerical examples and use optimization methods to make the problem tractable without using the simplifying assumptions of a LEN model. We also show that using linear contracts to approximate nonlinear contracts leads to solutions that are far from the optimal solutions obtained using nonlinear contracts. A principal-agent problem is a special instance of a bilevel nonlinear programming problem. We show how to solve principal-agent problems by solving bilevel programming problems using the ellipsoid algorithm. The approach we present can give researchers new insights into the relationships between nonlinear compensation schemes and employee effort. 相似文献