全文获取类型
收费全文 | 4130篇 |
免费 | 76篇 |
国内免费 | 35篇 |
专业分类
化学 | 2742篇 |
晶体学 | 32篇 |
力学 | 210篇 |
数学 | 667篇 |
物理学 | 590篇 |
出版年
2021年 | 32篇 |
2020年 | 35篇 |
2019年 | 25篇 |
2018年 | 43篇 |
2017年 | 24篇 |
2016年 | 74篇 |
2015年 | 58篇 |
2014年 | 68篇 |
2013年 | 231篇 |
2012年 | 130篇 |
2011年 | 194篇 |
2010年 | 110篇 |
2009年 | 109篇 |
2008年 | 160篇 |
2007年 | 173篇 |
2006年 | 176篇 |
2005年 | 190篇 |
2004年 | 208篇 |
2003年 | 190篇 |
2002年 | 175篇 |
2001年 | 80篇 |
2000年 | 89篇 |
1999年 | 52篇 |
1998年 | 42篇 |
1997年 | 50篇 |
1996年 | 63篇 |
1995年 | 59篇 |
1994年 | 61篇 |
1993年 | 57篇 |
1992年 | 46篇 |
1991年 | 48篇 |
1990年 | 50篇 |
1989年 | 46篇 |
1988年 | 45篇 |
1987年 | 39篇 |
1986年 | 39篇 |
1985年 | 65篇 |
1984年 | 75篇 |
1983年 | 57篇 |
1982年 | 71篇 |
1981年 | 61篇 |
1980年 | 75篇 |
1979年 | 68篇 |
1978年 | 63篇 |
1977年 | 55篇 |
1976年 | 51篇 |
1975年 | 51篇 |
1974年 | 61篇 |
1973年 | 39篇 |
1972年 | 35篇 |
排序方式: 共有4241条查询结果,搜索用时 781 毫秒
81.
The 4,6-bis(10-mesityl-5,15-di-p-tolylporpyrinyl)dibenzothiophene (H4DPSN) free base was obtained in five steps from commercially available materials. The metalation of DPSN2- with zinc(II), copper(II), and palladium(II) led to three new homobimetallic systems, (Zn)2DPSN, (Cu)2DPSN, and (Pd)2DPSN, respectively. The cofacial structures of these molecules offer the possibility of having dioxygen molecules inside the cavity for a period of time, allowing dynamic (collisional) phosphorescence quenching to be more efficient. The bimolecular excited-state deactivation rate constant for deactivation by dioxygen (kQ: (Pd)2DPB, 2.98x10(9); (Pd)2DPSN, 3.99x10(9); (Pd)2DPX, 6.94x10(9); (Pd)TPP, 8.95x10(9); (Pd)2DPS, 8.95x10(9) M-1 s-1) of (Pd)2DPSN, which exhibits an intense phosphorescence at 699 nm, was compared to those observed for (Pd)TPP, (Pd)2DPS, (Pd)2DPX, and (Pd)2DPB (TPP2-=tetraphenylporphyrin dianion, DPS4-=4,6-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]dibenzothiophene tetraanion, DPX4-=4,5-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]-9,9-dimethylxanthene tetraanion, and DPB4-=1,8-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]biphenylene tetraanion). These collision-induced deactivation data were interpreted by estimating a series of physical parameters such as the surface area and bisporphyrin radii, the diffusion coefficient of the bismacrocycles, and the theoretical deactivation efficiency for the five compounds addressing the role of steric hindrance of the macrocycles on each other and the aryl groups at the meso positions. For sensing purposes, (Pd)2DPX is characterized by a Stern-Volmer constant kSV of 2.91x10(6) M-1, placing the lower detection limit for [O2] in solution at 0.58 ppm, which is better than that for (Pd)TPP (kSV=2.31x10(6) M-1; lower detection limit of 0.73 ppm), the classically used monoporphyrin complex. 相似文献
82.
Photodegradation of Polychlorinated Dibenzo-p-dioxins in Liquid Samples by Near UV Light Irradiation
Photodegradation of 1,2,3,4-tetrachlorodibenzo-p-dioxin (1,2,3,4-TCDD) in hexane solution was studied under controlled near-UV light exposure in the spectral region from 325 to 269 nm. GC-MS was used to detect the amount of unreacted dioxin and to characterize the relevant degradation products. Irradiation experiments carried out at a constant light energy (700 mJ) showed that the percentage of 1,2,3,4-TCDD left in the solution after irradiation changed from about 55 to 75%, with a minimum of 55% at 310 nm. Further irradiation experiments carried out at two wavelengths, namely 310 and 269 nm, and light energy ranging from 0 to 4000 mJ, showed that the photodegradation reaction of the TCDD always followed a pseudo-first-order kinetic, with a rate constant of 8 × 10−4and 5 × 10−4mJ−1, respectively. These experiments also showed that trichloro- and dichloro-dibenzo-p-dioxins were produced with less than 15% of the initial quantity of TCDD, leading to the conclusion that the dechlorination process is a minor photolysis pathway. 相似文献
83.
Queiroz MJ Abreu AS Ferreira PM Oliveira MM Dubest R Aubard J Samat A 《Organic letters》2005,7(22):4811-4814
[structure: see text] A new photochromic thieno-2H-chromene alpha-amino acid derivative was prepared by C-N palladium-catalyzed cross-coupling of a bromothieno-2H-chromene with the aminated aromatic side chain of the methyl ester of a N,N-diprotected amino acid. Its good photochromic properties demonstrated by flash photolysis and continuous irradiation indicate a possible application in ophthalmic lenses. It may also be inserted into peptides to give photoinduced reversible structural changes. 相似文献
84.
Alan M. Bond Roger J. OHalloran Ivica Ruzic Donald E. Smith 《Journal of Electroanalytical Chemistry》1978,90(3):381-388
Rate laws presented to date for analysis of a.c. cyclic voltammetric data have invoked the so-called “slow scan limit approximation” which requires that ΔEω ? v, where Δ E and ω are the applied a.c. potential amplitude and angular frequency, respectively, and v is the d.c. potential scan rate. To provide a more useful guideline for the experimentalist than this qualitative condition, a pure digital simulation approach has been used to compute the a.c. cyclic time domain waveform for a reversible process under small amplitude conditions. The a.c. content of this waveform is extracted by the digital FFT alogirthm. Results of this study are presented here. Among the conclusions reached are more quantitative limitations for the slow scan limit rate laws describing the fundamental and second harmonic responses (approximately 128 a.c. cycles/d.c. cyclic sweep and 512 a.c. cycles/d.c. cyclic sweep, respectively) and an interesting prediction that the latter limitations can be relaxed further by a current waveform subtraction strategy, to as low as about 16 a.c. cycles/d.c. cyclic sweep for the fundamental and second harmonics. The cycles/sweep values assume one triangular wave potential scan of ±200 mV is encompassed. 相似文献
85.
Excess enthalpies and excess volumes were determined at 298.15 K for: dimethoxymethane+heptane, diethoxymethane+heptane, 1,1-dimethoxyethane+heptane, 1,1-diethoxyethane+heptane, 2,2-dimethoxypropane+heptane and 1,1-diethoxypropane+heptane. 相似文献
86.
87.
88.
Work which has recently appeared on the structures of Celastraceae alkaloids in addition to physical and chemical evidence adduced with respect to cathidine D permits formulation of structure 7a or 7b for this component of Catha edulis. 相似文献
89.
Tomás Moya-Pizarro Roger Salmon Léopold Fournes Gilles Le Flem Barbara Wanklyn Paul Hagenmuller 《Journal of solid state chemistry》1984,53(3):387-397
Single crystals of the high-temperature form of NaFeP2O7 have been grown by a flux technique. II-NaFeP2O7 crystallizes in the monoclinic space group with lattice parameters: a = 7.298(2) Å, b = 7.874(2) Å, c = 9.536(3) Å, β = 111.85(2)°. The structure refined from 1481 independent reflections leads to R = 0.044 and confirms the work previously published by M. Gabelica-Robert, M. Goreaud, P. Labbe, and B. Raveau (J. Solid State Chem.45, 389, 1982). Magnetic Mössbauer resonance studies have shown the existence of antiferromagnetic ordering with a weak ferromagnetic component below 30 K. The FeO bond is markedly ionic in character due to the highly polarizing power of phosphorus in tetrahedral site. 相似文献
90.
The products of hydrolysis of C60F48 (which contains six isolated double bonds) by either aq. acetone or aq. THF show that no more than twelve fluorines are replaced through nucleophilic substitution, as predicted by the recently identified S(N)2' mechanism. Subsequent HF elimination gives fragments containing a maximum of six epoxide oxygens. Calculated heats of formation of models for the possible initial hydroxy derivatives indicate that there is little energetic discrimination between them, so that a complex mixture is likely to be formed. Overall the data show that hydrolytic degradation of fluorofullerenes is less severe than believed previously, requires a specific motif, and explains the low susceptibility of C60F18 towards hydrolysis and the high stability of trannulenes. 相似文献