全文获取类型
收费全文 | 821篇 |
免费 | 13篇 |
国内免费 | 7篇 |
专业分类
化学 | 521篇 |
晶体学 | 6篇 |
力学 | 19篇 |
数学 | 155篇 |
物理学 | 140篇 |
出版年
2021年 | 6篇 |
2020年 | 5篇 |
2019年 | 4篇 |
2018年 | 13篇 |
2017年 | 5篇 |
2016年 | 14篇 |
2015年 | 8篇 |
2014年 | 10篇 |
2013年 | 47篇 |
2012年 | 36篇 |
2011年 | 64篇 |
2010年 | 23篇 |
2009年 | 26篇 |
2008年 | 59篇 |
2007年 | 60篇 |
2006年 | 53篇 |
2005年 | 36篇 |
2004年 | 36篇 |
2003年 | 38篇 |
2002年 | 23篇 |
2001年 | 10篇 |
2000年 | 17篇 |
1999年 | 8篇 |
1998年 | 14篇 |
1997年 | 10篇 |
1996年 | 10篇 |
1995年 | 20篇 |
1994年 | 11篇 |
1993年 | 9篇 |
1992年 | 16篇 |
1991年 | 9篇 |
1990年 | 4篇 |
1989年 | 10篇 |
1988年 | 7篇 |
1986年 | 8篇 |
1985年 | 9篇 |
1984年 | 11篇 |
1983年 | 5篇 |
1982年 | 13篇 |
1981年 | 16篇 |
1980年 | 7篇 |
1979年 | 5篇 |
1978年 | 6篇 |
1977年 | 4篇 |
1976年 | 5篇 |
1975年 | 4篇 |
1974年 | 7篇 |
1970年 | 3篇 |
1966年 | 2篇 |
1942年 | 2篇 |
排序方式: 共有841条查询结果,搜索用时 15 毫秒
141.
Besides microbiological methods, fecal pollution of surface waters is estimated by gas chromatographic (GC) determination of sterols present in human and animal sewage effluents. The most frequently used biomarkers for the evaluation of contamination levels include coprostanol, cholesterol, dihydrocholesterol, stigmasterol, beta-sitosterol, and stigmastanol. Although several GC techniques are used to measure these compounds in aquatic systems, the analytical performance of GC-mass spectrometric (MS) determination of these sterols has not been systematically characterized. Therefore, the aim of this work is to validate a simple and rapid GC-MS method for the simultaneous analysis of six sterols, considering all parameters and requirements defined by Good Laboratory Practice. Following liquid-liquid extraction of spiked surface water samples, the extracts are silylated and analyzed by GC-MS. The method is evaluated for linearity and limits of detection and quantitation, as well as for precision, extraction efficiency, and stability. The assay is linear up to 160 ng; the limits of detection and quantitation are 5-10 ng and 20 ng, respectively. The within- and between-day precision ranged from 1% to 9% and 1% to 16%, respectively. The extraction efficiency was 65-80%. The stability studies indicate that the sterols in surface water samples begin to degrade after 24 h of refrigerated storage. However, three freeze/thaw cycles could be performed without their decomposition. The method is applied to the analysis of surface water and wastewater samples. The technical advantages make this GC-MS analysis suitable for routine environmental monitoring of fecal pollution in aquatic systems. 相似文献
142.
We have recorded five high resolution (200 MHz), rotationally resolved, vibrational bands of the B-X electronic transition of 2-butoxy. Two bands of the 2-butoxy spectrum have been rotationally analyzed and assigned to two different geometrical conformers of the molecule. The analyses allow the determination of the six experimental rotational constants defined by the geometry of the species in the ground (X) and excited (B) electronic states and also four spin-rotation constants for the X electronic state of the conformers. Comparison of the experimental rotational constants with the results of ab initio computations provides unambiguous conformational assignment of these bands. This approach can be extended to assign two other spectral bands to the third 2-butoxy conformer. 相似文献
143.
Navaza AP Montes-Bayón M LeDuc DL Terry N Sanz-Medel A 《Journal of mass spectrometry : JMS》2006,41(3):323-331
The accumulation of As and Cd in Brassica juncea plants and the formation of complexes of these elements with bioligands such as glutathione and/or phytochelatins (PCs) is studied. The genetic manipulation of these plants to induce higher As and Cd accumulation has been achieved by overexpressing the genes encoding for gamma-glutamyl cysteine synthetase (gamma-ECS) and glutathione synthetase (GS). These two enzymes are responsible for glutathione (GSH) formation in plants, which is the first step in the production of PCs. The biomass produced in both the wild type and the genetically modified plants, has been evaluated. Additionally, the total Cd and As concentration accumulated in the plant tissues was measured by inductively coupled plasma mass spectrometry (ICP-MS) after extraction. Speciation studies on the extracts were conducted using size exclusion liquid chromatography (SEC) coupled online with ICP-MS to monitor As, Cd and S. For further purification of the As fractions, reversed phase high performance liquid chromatography (RP-HPLC) was used. Structural elucidation of the PCs and other thiols, as well as their complexes with As and Cd, was performed by electrospray-quadrupole-time-of-flight (ESI-Q-TOF). In both the Cd and As exposed plants it was possible to observe the presence of oxidized PC2 ([M + H]+, m/z 538), GS-PC2(-Glu) ([M + H]+, m/z 716) as well as reduced GSH ([M + H]+, m/z 308) and oxidized glutathione (GSSG) ([M + H]+, m/z 613). However, only the GS plants exhibited the presence of As(GS)3 complex ([M + H]+, m/z 994) that was further confirmed by MS/MS. This species is reported for the first time in B. juncea plant tissues. 相似文献
144.
p-Biphenylyldiazomethane was excited by femtosecond pulses of UV light in acetonitrile, in cyclohexane, and in methanol. Ultrafast photolysis produces a singlet excited state of p-biphenylyldiazomethane with lambdamax = 490 nm, and lifetimes of less than 300 fs in acetonitrile, in cyclohexane, and in methanol. The decay of the excited state is accompanied by the growth of transient absorption with lambdamax = 360 nm. The carrier of this transient absorption is attributed to singlet p-biphenylylcarbene, a result that is consistent with the predictions of TD-DFT calculations. The singlet carbene lifetimes are 200 and 77 ps in acetonitrile and cyclohexane, respectively, and are controlled by intersystem crossing to the lower energy triplet state. The transient absorption does not decay to baseline in acetonitrile, because of the formation of nitrile ylide. The equilibrium mixture of singlet and triplet p-biphenylylcarbene reacts with acetonitrile to form a nitrile ylide (lambdamax = 370 nm), and with cyclohexane by C-H insertion 1-20 ns after the laser pulse. The singlet carbene lifetime is only 7.9 ps in methanol, owing to a rapid reaction with the solvent. Reaction with the solvent gives rise, in part, to a p-biphenylylbenzyl cation (lambdamax = 450 nm, tau = 6.3 ps) in methanol. 相似文献
145.
Xia C Kumar M Kulkarni OP Islam MN Terry FL Freeman MJ Poulain M Mazé G 《Optics letters》2006,31(17):2553-2555
A mid-infrared supercontinuum (SC) is generated in ZBLAN (ZrF4-BaF2-LaF3-AlF3-NaF...) fluoride fibers from amplified nanosecond laser diode pulses with a continuous spectrum from approximately 0.8 microm to beyond 4.5 microm. The SC has an average power of approximately 23 mW, a pump-to-SC power conversion efficiency exceeding 50%, and a spectral power density of approximately -20 dBm/nm over a large fraction of the spectrum. The SC generation is initiated by the breakup of nanosecond laser diode pulses into femtosecond pulses through modulation instability, and the spectrum is then broadened primarily through fiber nonlinearities in approximately 2-7 m lengths of ZBLAN fiber. The SC long-wavelength edge is consistent with the intrinsic ZBLAN material absorption. 相似文献
146.
Weston M. Eldredge Pál Tóth Laurie Centauri Eric G. Eddings Kerry E. Kelly Terry A. Ring Axel Schönbucher Jeremy N. Thornock Philip J. Smith 《Flow, Turbulence and Combustion》2016,97(2):427-449
An effective approach to the model VUQ process by means of direct collaboration between computationalist and experimental data analyst is proposed. An analysis of data from a laminar helium plume experiment provides a demonstration of the proposed collaboration process. Consistency analysis serves a central role in the collaboration. It takes the data and uncertainties from both analyst and computationalist and provides an objective and quantifiable measure of agreement between the two. Despite the simplicity of the laminar helium system and the computational model, certain phenomena brought to light in the collaboration process make it difficult to find quantitative agreement in the data. These phenomena include the unsteady behavior of air flow in an open room, and the presence of helium permeation to the region near the plume. Important sources of error in the simulation include uncertainty in the room temperature (295.15 to 305.15 K), uncertainty in the helium inlet velocity (0.1215 \(\frac {m}{s}\) to 0.1415 \(\frac {m}{s}\)), and uncertainty in local helium permeation (0 % to 3 % by mass.) The collaboration process allows for a better understanding of the phenomena affecting the plume and the relative sensitivies of the system to these phenomena. 相似文献
147.
Vidjayacoumar B Ilango S Ray MJ Chu T Kolpin KB Andreychuk NR Cruz CA Emslie DJ Jenkins HA Britten JF 《Dalton transactions (Cambridge, England : 2003)》2012,41(26):8175-8189
A rigid NSN-donor proligand, 4,5-bis(2,6-diisopropylanilino)-2,7-di-tert-butyl-9,9-dimethylthioxanthene (H(2)[TXA(2)], 1) was prepared by palladium-catalyzed coupling of 2,6-diisopropylaniline with 4,5-dibromo-2,7-di-tert-butyl-9,9-dimethylthioxanthene. Deprotonation of 1 using (n)BuLi provided Li(2)(DME)(2)[TXA(2)] (2), and subsequent reaction with UCl(4) afforded [Li(DME)(3)][(TXA(2))UCl(3)] (4). The analogous NON-donor ligated complex [(XA(2))UCl(3)K(DME)(3)] [3; XA(2) = 4,5-bis(2,6-diisopropylanilino)-2,7-di-tert-butyl-9,9-dimethylxanthene] was prepared by the reaction of K(2)(DME)(x)[XA(2)] with UCl(4). A cyclic voltammogram (CV) of 3 in THF/[NBu(4)][B(C(6)F(5))(4)] at 200 mV s(-1) showed an irreversible reduction to uranium(III) at E(pc) = -2.46 V versus FeCp(2)(0/+1), followed by a product wave at E(1/2) = -1.83 V. Complex 4 also underwent irreversible reduction to uranium(iii) [E(pc) = -2.56 V], resulting in an irreversible product peak at E(pa) = -1.83 V. One-electron reduction of complexes 3 and 4 using K(naphthalenide) under an argon atmosphere in DME yielded 6-coordinate [(XA(2))UCl(DME)] (5) and the thermally unstable 7-coordinate [(TXA(2))U(DME)Cl(2)Li(DME)(2)] (6), respectively. The U-S distances in 4 and 6 are uncommonly short, the C-S-U angles are unusually acute, and the thioxanthene backbone of the TXA(2) ligand is significantly bent. By contrast, the xanthene backbone in XA(2) complexes 3 and 5 is planar. However, κ(3)-coordination and an approximately meridional arrangement of the ancillary ligand donor atoms is maintained in all complexes. DFT and Atoms in Molecules (AIM) calculations were carried out on 3, 4, 5, 6, [(XA(2))UCl(3)](-) (3B), [(TXA(2))UCl(2)(DME)](-) (6B) and [(TXA(2))UCl(DME)] (6C) to probe the extent of covalency in U-SAr(2) bonding relative to U-OAr(2) bonding. 相似文献
148.
Zachary Nuño Brandon Hessler Bryan Heiberg Ralph Damato Terry Dunlap Young-Seok Shon Yohannes Abate 《Journal of nanoparticle research》2012,14(3):766
Spectroscopic near-field imaging of single silica-shell/Au-core and pure silica nanoparticles deposited on a silicon substrate
is performed in the infrared wavelength range (λ = 9–11 μm) using scattering-type scanning near-field optical microscopy (s-SNOM).
By tuning the wavelength of the incident light, we have acquired information on the spectral phonon–polariton resonant near-field
interactions of the silica-shell/Au-core and pure silica nanoparticles with the probing tip. We made use of the enhanced near-field
coupling between the high index Au-core and the probing tip to achieve spectral near-field contrast of the thin silica coating
(thickness < 10 nm). Our results show that spectroscopic imaging of thin coating layers and complex core–shell nanoparticles
can be directly performed by s-SNOM. 相似文献
149.
The amount of correlation attainable between the components of a quantum system is constrained if the system is closed. We provide some examples, largely from the field of quantum thermodynamics, where knowing the maximal possible variation in correlations is useful. The optimization problem it raises requires us to search for the maximally and minimally correlated states on a unitary orbit, with and without energy conservation. This is fully solvable for the smallest system of two qubits. For larger systems, the problem is reduced to a manageable, classical optimization. 相似文献
150.
The adiabatic capture centrifugal sudden approximation (ACCSA) has been applied to the C + NO and O + CN reactions, along with quasiclassical trajectory simulations. Existing global analytic fits to the potential energy surfaces of the CNO system in the (2)A', (2)A", and (4)A" electronic states have been used. Thermal rate constants for reaction in each of the electronic states have been calculated. In all cases a strong temperature dependence is evident in the calculated rate constants. The agreement between the calculated adiabatic capture and quasiclassical trajectory rate constants is excellent in some cases, but these rate constants differ considerably in other cases. This behavior is analyzed in terms of the anisotropy of the potential energy surfaces. On the basis of this analysis, we propose a new diagnostic for the reliability of ACCSA capture calculations. 相似文献