全文获取类型
收费全文 | 4843篇 |
免费 | 128篇 |
国内免费 | 29篇 |
专业分类
化学 | 3482篇 |
晶体学 | 49篇 |
力学 | 128篇 |
数学 | 594篇 |
物理学 | 747篇 |
出版年
2023年 | 26篇 |
2022年 | 32篇 |
2021年 | 50篇 |
2020年 | 66篇 |
2019年 | 68篇 |
2018年 | 42篇 |
2017年 | 47篇 |
2016年 | 115篇 |
2015年 | 95篇 |
2014年 | 111篇 |
2013年 | 208篇 |
2012年 | 273篇 |
2011年 | 331篇 |
2010年 | 183篇 |
2009年 | 138篇 |
2008年 | 268篇 |
2007年 | 292篇 |
2006年 | 304篇 |
2005年 | 264篇 |
2004年 | 224篇 |
2003年 | 220篇 |
2002年 | 199篇 |
2001年 | 59篇 |
2000年 | 62篇 |
1999年 | 37篇 |
1998年 | 47篇 |
1997年 | 50篇 |
1996年 | 79篇 |
1995年 | 40篇 |
1994年 | 42篇 |
1993年 | 39篇 |
1991年 | 39篇 |
1990年 | 40篇 |
1989年 | 33篇 |
1988年 | 39篇 |
1987年 | 23篇 |
1986年 | 28篇 |
1985年 | 57篇 |
1984年 | 59篇 |
1983年 | 33篇 |
1982年 | 62篇 |
1981年 | 60篇 |
1980年 | 55篇 |
1979年 | 43篇 |
1978年 | 52篇 |
1977年 | 46篇 |
1976年 | 36篇 |
1975年 | 39篇 |
1974年 | 34篇 |
1973年 | 35篇 |
排序方式: 共有5000条查询结果,搜索用时 0 毫秒
71.
A fluorimetric method for the determination of citrate is described. Through a series of reactions, citrate is converted into citrazinic acid. The ammonium salt of this compound exhibits a fluorescence maximum at 430 nm when an excitation source of 340 nm is used. The method does not suffer from the normal interferences. The limit of detection is 0.01 μg ml-, and the best working range is 0.1–10 μg ml-1. 相似文献
72.
73.
Kirmaier C Bautista JA Laible PD Hanson DK Holten D 《The journal of physical chemistry. B》2005,109(50):24160-24172
Subpicosecond transient absorption studies are reported for a set of Rhodobacter (R.) capsulatus bacterial photosynthetic reaction centers (RCs) designed to probe the origins of the unidirectionality of charge separation via one of two electron transport chains in the native pigment-protein complex. All of the RCs have been engineered to contain a heterodimeric primary electron donor (D) consisting of a bacteriochlorophyll (BChl) and a bacteriopheophytin (BPh). The BPh component of the M heterodimer (Mhd) or L heterodimer (Lhd) is introduced by substituting a Leu for His M200 or His L173, respectively. Previous work on primary charge separation in heterodimer mutants has not included the Lhd RC from R. capsulatus, which we report for the first time. The Lhd and Mhd RCs are used as controls against which we assess RCs that combine the heterodimer mutations with a second mutation (His substituted for Leu at M212) that results in replacement of the native L-side BPh acceptor with a BChl (beta). The transient absorption spectra reveal clear evidence for charge separation to the normally inactive M-side BPh acceptor (H(M)) in Lhd-beta RCs to form D+H(M)- with a yield of approximately 6%. This state also forms in Mhd-beta RCs but with about one-quarter the yield. In both RCs, deactivation to the ground state is the predominant pathway of D decay, as it is in the Mhd and Lhd single mutants. Analysis of the results indicates an upper limit ofV2L/V2m < or = 4 for the contribution of the electronic coupling elements to the relative rates of electron transfer to the L versus M sides of the wild-type RC. In comparison to the L/M rate ratio (kL/kM) approximately 30 for wild-type RCs, our findings indicate that electronic factors contribute approximately 35% at most to directionality with the other 65% deriving from energetic considerations, which includes differences in free energies, reorganization energies, and contributions of one- and two-step mechanisms on the two sides of the RC. 相似文献
74.
Huang F Switek KA Zakharov LN Fronczek FR Slebodnick C Lam M Golen JA Bryant WS Mason PE Rheingold AL Ashraf-Khorassani M Gibson HW 《The Journal of organic chemistry》2005,70(8):3231-3241
Four new bis(m-phenylene)-32-crown-10-based cryptands with different third bridges were prepared. Their complexes with paraquat derivatives were studied by proton NMR spectroscopy, mass spectrometry, and X-ray analysis. It was found that these cryptands bind paraquat derivatives very strongly. Specifically, a diester cryptand with a pyridyl nitrogen atom located at a site occupied by either water or a PF(6) anion in analogous complexes exhibited the highest association constant K(a) = 5.0 x 10(6) M(-1) in acetone with paraquat, 9000 times greater than the crown ether system. X-ray structures of this and analogous complexes demonstrate that improved complexation with this host is a consequence of preorganization, adequate ring size for occupation by the guest, and the proper location of the pyridyl N-atom for binding to the beta-pyridinium hydrogens of the paraquat guests. This readily accessible cryptand is one of the most powerful hosts reported for paraquats. 相似文献
75.
Reppert PM Morgan FD Lesmes DP Jouniaux L 《Journal of colloid and interface science》2001,234(1):194-203
An experimental apparatus and data acquisition system was constructed to measure the streaming potential coupling coefficients as a function of frequency. The purpose of the experiments was to measure, for the first time, the real and imaginary portion of streaming potentials. In addition, the measured frequency range was extended beyond any previous measurements. Frequency-dependent streaming potential experiments were conducted on one glass capillary and two porous glass filters. The sample pore diameters ranged from 1 mm to 34 μm. Two frequency-dependent models (Packard and Pride) were compared to the data. Both Pride's and Packard's models have a good fit to the experimental data in the low- and intermediate-frequency regime. In the high-frequency regime, the data fit the theory after being corrected for capacitance effects of the experimental setup. Pride's generalized model appears to have the ability to more accurately estimate pore sizes in the porous medium samples. Packard's model has one unknown model parameter while Pride's model has four unknown model parameters, two of which can be independently determined experimentally. Pride's additional parameters may allow for a determination of permeability. Copyright 2001 Academic Press. 相似文献
76.
Alkyl, aromatic, benzylic and benzoyl halides have been successfully coupled in good yields using lithium wire suspended in tetrahydrofuran and ultrasound. 相似文献
77.
The title compounds may be made from bis(phenylthio) acetals and aldehydes by routes involving PhS migration. 相似文献
78.
We find all torsion-free, spherically symmetric, vacuum solutions to the theory of gravity recently proposed by Hehl, Ne'eman, Nitsch, and von der Heyde. There are three classes of solutions: (A) the Schwarzschild metrics with arbitrary mass,M, and arbitrary cosmological constant, ; (B) the Nariai-Bertotti metrics with arbitrary positive cosmological constant, ; and (C) the conformally flat metrics whose conformai factor is 2/
2 where is a function of only the time coordinate , and the radial coordinate, and satisfies the wave equation in these variables. Hence there is no Birkhoff theorem for this theory. In fact, solutions (C) include some asymptotically flat but nonstationary solutions. On the other hand, solutions (A) include a gravitational confinement potential, as was sought by Hehl et al., since when <0, the weak field limit of the Schwarzschild metric becomes a harmonic oscillator potential. We also discuss the relationship of this theory to the Eddington theory, the Lichnerowicz-Kilmister-Newman-Yang theory, the Nordström theory and the Einstein theory with a cosmological constant. 相似文献
79.
The cofactor (M-center) of the MoFe protein of nitrogenase, a MoFe(7)S(9):homocitrate cluster, contains six Fe sites with a (distorted) trigonal sulfido coordination. These sites exhibit unusually small quadrupole splittings, Delta E(Q) approximately 0.7 mm/s, and isomer shifts, delta approximately 0.41 mm/s. M?ssbauer and ENDOR studies have provided the magnetic hyperfine tensors of all iron sites in the S = 3/2 state M(N). To assess the intrinsic zero-field splittings and hyperfine parameters of the cofactor sites, we have studied with M?ssbauer spectroscopy two salts of the three-coordinated Fe(II) thiolate complex [Fe(SR)(3)](-) (R = C(6)H(2)-2,4,6-tBu(3)). One of the salts, [Ph(4)P][Fe(SR)(3)] x 2MeCN x C(7)H(8), 1, has a planar geometry with idealized C(3h) symmetry. This S = 2 complex has an axial zero-field splitting with D = +10.2 cm(-1). The magnetic hyperfine tensor components A(x) = A(y) = -7.5 MHz and A(z) = -29.5 MHz reflect an orbital ground state with d(z(2)) symmetry. A(iso) = (A(x) +A(y) +A(z))/3 = -14.9 MHz, which includes the contact interaction (kappa P = -21.9 MHz) and an orbital contribution (+7 MHz), which is substantially smaller than A(iso) approximately -22 MHz of the tetrahedral Fe(II)(S-R)(4) sites of both rubredoxin and [PPh(4)](2)[Fe(II)(SPh)(4)]. The largest component of the electric field gradient (EFG) tensor is negative, as expected for a d(z(2)) orbital. However, Delta E(Q) = -0.83 mm/s, which is smaller than expected for a high-spin ferrous site. This reduction can be attributed to a ligand contribution, which in planar complexes provides a large positive EFG component perpendicular to the ligand plane. The isomer shift of 1, delta = 0.56 mm/s, approaches the delta-values reported for the six trigonal cofactor sites. The parameters of 1 and their importance for the cofactor cluster of nitrogenase are discussed. 相似文献
80.
Digrazia Philip M. Blackburn James W. Bienkowski Paul R. Hilton Barry Reed Gregory D. King J. M. Henry Sayler Gary S. 《Applied biochemistry and biotechnology》1990,(1):237-252
An experimental and mathematical method is developed for the microbial systems analysis of polyaromatic hydrocarbon (PAH)-degrading
mixed cultures in PAH-contaminated “town gas” soil systems. Frequency response is the primary experimental and data analysis
tool used to probe the structure of these complicated systems. The objective is to provide a fundamental protocol for evaluating
the performance of specific mixed microbial cultures on specific soil systems by elucidating the salient system variables
and their interactions. Two well-described reactor systems, a constant volume stirred tank reactor (CSTR) and a plug flow
differential volume reactor, are used in order to remove performance effects that are related to reactor type as opposed to
system structure. These two reactor systems are well-defined systems that can be described mathematically and represent the
two extremes of one potentially important system variable, macroscopic mass transfer. The experimental and mathematical structure
of the protocol is described, experimental data is presented, and data analysis is demonstrated for the stripping, sorption,
and biodegradation of napththalene. 相似文献