全文获取类型
收费全文 | 5057篇 |
免费 | 187篇 |
国内免费 | 16篇 |
专业分类
化学 | 3322篇 |
晶体学 | 54篇 |
力学 | 109篇 |
数学 | 555篇 |
物理学 | 1220篇 |
出版年
2023年 | 47篇 |
2022年 | 103篇 |
2021年 | 154篇 |
2020年 | 123篇 |
2019年 | 147篇 |
2018年 | 123篇 |
2017年 | 116篇 |
2016年 | 195篇 |
2015年 | 162篇 |
2014年 | 158篇 |
2013年 | 329篇 |
2012年 | 353篇 |
2011年 | 413篇 |
2010年 | 261篇 |
2009年 | 260篇 |
2008年 | 349篇 |
2007年 | 313篇 |
2006年 | 251篇 |
2005年 | 223篇 |
2004年 | 212篇 |
2003年 | 143篇 |
2002年 | 115篇 |
2001年 | 88篇 |
2000年 | 83篇 |
1999年 | 61篇 |
1998年 | 34篇 |
1997年 | 39篇 |
1996年 | 44篇 |
1995年 | 42篇 |
1994年 | 34篇 |
1993年 | 37篇 |
1992年 | 46篇 |
1991年 | 25篇 |
1990年 | 16篇 |
1989年 | 16篇 |
1988年 | 10篇 |
1987年 | 9篇 |
1986年 | 11篇 |
1985年 | 10篇 |
1984年 | 13篇 |
1983年 | 6篇 |
1982年 | 10篇 |
1981年 | 7篇 |
1980年 | 9篇 |
1978年 | 8篇 |
1977年 | 10篇 |
1976年 | 5篇 |
1975年 | 6篇 |
1974年 | 7篇 |
1968年 | 4篇 |
排序方式: 共有5260条查询结果,搜索用时 31 毫秒
981.
3-Phosphinyl 1-aza-1,3-butadienes 2 are obtained by aldol condensation between hydrazonoalkyl phosphine oxides and N,N-dimethylformamide dimethyl acetal. Transamination reaction of these azadienes with amines yields functionalized 1-aza-1,3-butadienes 3. Cycloaddition processes of these azadienes 2a with electron-poor dienophiles to give phosphorylated pyridine derivatives 9 and 15 are also reported, while intramolecular cyclization reaction of heterodiene 2b affords phosphorylated pyrazole 17. 相似文献
982.
Clementina M. M. Santos Artur M. S. Silva Jos A. S. Cavaleiro Tams Patonay Albert Lvai 《Journal of heterocyclic chemistry》2006,43(5):1319-1326
983.
Aparicio D Attanasi OA Filippone P Ignacio R Lillini S Mantellini F Palacios F de Los Santos JM 《The Journal of organic chemistry》2006,71(16):5897-5905
The preparation of tetrahydropyrazines, dihydropyrazines, pyrazines, piperazinones, and quinoxalines by 1,4-addition of 1,2-diamines to 1,2-diaza-1,3-butadienes bearing carboxylate, carboxamide, or phosphorylated groups at the terminal carbon and subsequent internal heterocyclization is described. The solvent-free reaction of carboxylated 1,2-diaza-1,3-butadienes with the same reagents affords piperazinones, while phosphorylated 1,2-diaza-1,3-butadienes yield phosphorylated pyrazines. The solid-phase reaction of polymer-bound 1,2-diaza-1,3-butadienes with 1,2-diamines produces pyrazines. 相似文献
984.
Noronha LA Judson TJ Dias JF Santos LS Eberlin MN Mota CJ 《The Journal of organic chemistry》2006,71(7):2625-2629
The intrinsic acidity of dimethylhalonium ions has been determined, both by theoretical methods and by gas-phase reactions of the isolated ions with pyridine bases. The calculated geometry of the dimethylhalonium ions shows a bent structure with the C-X-C angle decreasing in the order Cl > Br > I. Thermochemical calculations for the reaction of the dimethylhalonium ions with pyridine, 2,6-dimethylpyridine, and 2,6-di-tert-butylpyridine indicate that proton transfer, with the formation of the dimethylhalonium ylide is endothermic, whereas methyl transfer, with formation of methylhalide, is exothermic. The endothermicities for proton transfer are, nevertheless, dependent on the steric hindrance of the base. The bulkier the bases, the less endothermic the proton-transfer reaction is. Experimental gas-phase reactions support the calculations, showing that methyl transfer is the major reaction of dimethylchloronium and dimethyliodonium with pyridine, whereas proton transfer, as well as single electron transfer, is observed for the bulkier bases. The calculations also indicate that acidity increases in the order chloronium > bromonium > iodonium. NBO calculations predict that hyperconjugation with the sigma carbon-halogen orbital plays a role in stabilizing the halonium ylide species in the gas phase. 相似文献
985.
Zanatta N Schneider JM Schneider PH Wouters AD Bonacorso HG Martins MA Wessjohann LA 《The Journal of organic chemistry》2006,71(18):6996-6998
A simple and regiospecific synthesis of 4-alkoxy(amino)-2-trifluoromethyl pyrroles from 5-azido-4-alkoxy(amino)-1,1,1-trifluoro-pent-3-en-2-ones by an aza-Wittig cyclization of aminophosphoranes is described. The structures of the pyrroles and their synthetic intermediates were supported by NMR and HRMS analysis. 相似文献
986.
Ito VM Martins PF Batistella CB Filho RM Wolf Maciel MR 《Applied biochemistry and biotechnology》2006,131(1-3):716-726
Soybean oil deodorized distillate (SODD) is a byproduct from refining edible soybean oil; however, the deodorization process removes unsaponifiable materials, such as sterols and tocopherols. Tocopherols are highly added value materials. Molecular distillation has large potential to be used in order to concentrate tocopherols, because it uses very low levels of temperatures because of the high vacuum and short operating time for separation and, also, it does not use solvents. However, nowadays, the conventional way to recover tocopherols is carrying out chemical reactions prior to molecular distillation, making the process not so suitable to deal with natural products. The purpose of this work is to use only molecular distillation in order to recover tocopherols from SODD. Experiments were performed in the range of 140-220 degrees C. The feed flow rate varied from 5 to 15 g/min. The objective of this study was to remove the maximum amount of free fatty acids (FFA) and, so, to increase the tocopherol concentration without add any extra component to the system. The percentage of FFA in the distillate stream of the molecular still is large at low feed flow rates and low evaporator temperatures, avoiding thermal decomposition effects. 相似文献
987.
N.M.P. Pinto O. Frazo J.M. Baptista J.L. Santos 《Optics and Lasers in Engineering》2006,44(8):771-778
A quasi-distributed displacement sensor for structural monitoring using an optical time domain reflectometer is demonstrated. Four displacement sensing heads are placed along a standard single mode optical fibre in several locations with different intervals. Their configurations introduce power loss through the decrease of their fibre loop radius when displacement is applied. The decrease of the light intensity with displacement variation is reported. Losses of 9 dB for a 120 mm displacement with a sensitivity of 0.027 dB/mm are reported. The quasi-distributed configuration is able to address sensors with 1 m distance resolution between them. 相似文献
988.
The midgut epithelium of bees is formed by the digestive cells, responsible for enzyme secretion and nutrient absorption and for small regenerative cells that are placed in nests scattered among the digestive cells. During metamorphosis, the larval midgut epithelium degenerates and a new adult midgut epithelium is built during larval differentiation of regenerative cells. The present work focuses on the midgut epithelial modifications during the post-embryonic development of the stingless bee Melipona quadrifasciata anthidioides worker and the occurrence of regenerative cell proliferation during midgut metamorphosis in order to test the hypothesis that adult midgut epithelium of worker bees results from regenerative cell proliferation during the pupal stage. Regenerative cell proliferation was detected during larval lifespan. Larval aging is followed by an increase in the number and the size of the nests of regenerative cells. Larval epithelium degeneration begins 2 days after the start of defecation process and in this period the nests of regenerative cells are in contact by means of cytoplasmic extension which have many septate desmosomes and gap junctions. The BrdU immunoreactive regenerative cells were found in the prepupae 12 h after BrdU injection, suggesting that regenerative cell population increase during this larval period. Regenerative cell proliferation results in the increase of the regenerative cell population and not in the formation of new digestive cells because the proliferation of regenerative cells would not be enough to reestablish the nests of regenerative cells and at the same time form new adult digestive cells. In this sense the hypothesis that digestive adult cells originate from regenerative cell proliferation during midgut metamorphosis in M. quadrifasciata anthidioides was rejected. 相似文献
989.
Discrepancies between classical model (CM) predictions and experimental data for deep bed filtration (DBF) have been reported by various authors. In order to understand these discrepancies, an analytic continuum model for DBF is proposed. In this model, a filter coefficient is attributed to each distinct retention mechanism (straining, diffusion, gravity interception, etc.). It was shown that these coefficients generally cannot be merged into an effective filter coefficient, as considered in the CM. Furthermore, the derived analytic solutions for the proposed model (PM) were applied for fitting experimental data, and a very good agreement between experimental data and PM predictions were obtained. Comparison of the obtained results with empirical correlations allowed identifying the dominant retention mechanisms. In addition, it was shown that the larger the ratio of particle to pore sizes, the more intensive the straining mechanism and the larger the discrepancies between experimental data and CM predictions. Finally, the CM and PM were compared via statistical analysis. The obtained $p$ values allow concluding that the PM should be preferred especially when straining plays an important role. 相似文献
990.
A. C. Marta C. A. Mader J. R. R. A. Martins E. Van der Weide J. J. Alonso 《International Journal of Computational Fluid Dynamics》2013,27(9-10):307-327
A methodology for the rapid development of adjoint solvers for computational fluid dynamics (CFD) models is presented. The approach relies on the use of automatic differentiation (AD) tools to almost completely automate the process of development of discrete adjoint solvers. This methodology is used to produce the adjoint code for two distinct 3D CFD solvers: a cell-centred Euler solver running in single-block, single-processor mode and a multi-block, multi-processor, vertex-centred, magneto-hydrodynamics (MHD) solver. Instead of differentiating the entire source code of the CFD solvers using AD, we have applied it selectively to produce code that computes the transpose of the flux Jacobian matrix and the other partial derivatives that are necessary to compute sensitivities using an adjoint method. The discrete adjoint equations are then solved using the Portable, Extensible Toolkit for Scientific Computation (PETSc) library. The selective application of AD is the principal idea of this new methodology, which we call the AD adjoint (ADjoint). The ADjoint approach has the advantages that it is applicable to any set of governing equations and objective functions and that it is completely consistent with the gradients that would be computed by exact numerical differentiation of the original discrete solver. Furthermore, the approach does not require hand differentiation, thus avoiding the long development times typically required to develop discrete adjoint solvers for partial differential equations, as well as the errors that result from the necessary approximations used during the differentiation of complex systems of conservation laws. These advantages come at the cost of increased memory requirements for the discrete adjoint solver. However, given the amount of memory that is typically available in parallel computers and the trends toward larger numbers of multi-core processors, this disadvantage is rather small when compared with the very significant advantages that are demonstrated. The sensitivities of drag and lift coefficients with respect to different parameters obtained using the discrete adjoint solvers show excellent agreement with the benchmark results produced by the complex-step and finite-difference methods. Furthermore, the overall performance of the method is shown to be better than most conventional adjoint approaches for both CFD solvers used. 相似文献