全文获取类型
收费全文 | 624篇 |
免费 | 90篇 |
国内免费 | 99篇 |
专业分类
化学 | 96篇 |
晶体学 | 1篇 |
力学 | 48篇 |
综合类 | 24篇 |
数学 | 525篇 |
物理学 | 119篇 |
出版年
2024年 | 1篇 |
2023年 | 6篇 |
2022年 | 13篇 |
2021年 | 13篇 |
2020年 | 18篇 |
2019年 | 14篇 |
2018年 | 16篇 |
2017年 | 15篇 |
2016年 | 22篇 |
2015年 | 23篇 |
2014年 | 26篇 |
2013年 | 37篇 |
2012年 | 21篇 |
2011年 | 34篇 |
2010年 | 33篇 |
2009年 | 45篇 |
2008年 | 42篇 |
2007年 | 48篇 |
2006年 | 36篇 |
2005年 | 37篇 |
2004年 | 36篇 |
2003年 | 45篇 |
2002年 | 30篇 |
2001年 | 24篇 |
2000年 | 30篇 |
1999年 | 32篇 |
1998年 | 12篇 |
1997年 | 17篇 |
1996年 | 17篇 |
1995年 | 7篇 |
1994年 | 20篇 |
1993年 | 2篇 |
1992年 | 6篇 |
1991年 | 6篇 |
1990年 | 4篇 |
1988年 | 2篇 |
1987年 | 1篇 |
1986年 | 1篇 |
1985年 | 2篇 |
1984年 | 3篇 |
1983年 | 1篇 |
1982年 | 4篇 |
1981年 | 2篇 |
1980年 | 1篇 |
1979年 | 3篇 |
1978年 | 2篇 |
1975年 | 1篇 |
1972年 | 2篇 |
排序方式: 共有813条查询结果,搜索用时 15 毫秒
11.
M. Zeeman C. M. Auer R. G. Clements J. V. Nabholz R. S. Boethling 《SAR and QSAR in environmental research》2013,24(3):179-201
Abstract As testing is not required, ecotoxicity or fate data are available for ≈ 5% of the approximately 2,300 new chemicals/year (26,000 + total) submitted to the US-EPA. The EPA's Office of Pollution Prevention and Toxics (OPPT) regulatory program was forced to develop and rely upon QSARs to estimate the ecotoxicity and fate of most of the new chemicals evaluated for hazard and risk assessment. QSAR methods routinely result in ecotoxicity estimations of acute and chronic toxicity to fish, aquatic invertebrates, and algae, and in fate estimations of physical/chemical properties, degradation, and bioconcentration. The EPA's Toxic Substances Control Act (TSCA) Inventory of existing chemicals currently lists over 72,000 chemicals. Most existing chemicals also appear to have little or no ecotoxicity or fate data available and the OPPT new chemical QSAR methods now provide predictions and cross-checks of test data for the regulation of existing chemicals. Examples include the Toxics Release Inventory (TRI), the Design for the Environment (DfE), and the OECD/SIDS/HPV Programs. QSAR screening of the TSCA Inventory has prioritized thousands of existing chemicals for possible regulatory testing of: 1) persistent bioaccumulative chemicals, and 2) the high ecotoxicity of specific discrete organic chemicals. 相似文献
12.
Jan Rosenboom Dr. Lukas Chojetzki Dr. Tim Suhrbier Dr. Jabor Rabeah Dr. Alexander Villinger Dr. Ronald Wustrack Dr. Jonas Bresien Prof. Dr. Axel Schulz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(36):e202200624
The activation of C−Br bonds in various bromoalkanes by the biradical [⋅P(μ-NTer)2P⋅] ( 1 ) (Ter=2,6-bis-(2,4,6-trimethylphenyl)-phenyl) is reported, yielding trans-addition products of the type [Br−P(μ-NTer)2P−R] ( 2 ), so-called 1,3-substituted cyclo-1,3-diphospha-2,4-diazanes. This addition reaction, which represents a new easy approach to asymmetrically substituted cyclo-1,3-diphospha-2,4-diazanes, was investigated mechanistically by different spectroscopic methods (NMR, EPR, IR, Raman); the results suggested a stepwise radical reaction mechanism, as evidenced by the in-situ detection of the phosphorus-centered monoradical [⋅P(μ-NTer)2P-R].< To provide further evidence for the radical mechanism, [⋅P(μ-NTer)2P-Et] ( 3Et ⋅) was synthesized directly by reduction of the bromoethane addition product [Br-P(μ-NTer)2P-Et] ( 2 a ) with magnesium, resulting in the formation of the persistent phosphorus-centered monoradical [⋅P(μ-NTer)2P-Et], which could be isolated and fully characterized, including single-crystal X-ray diffraction. Comparison of the EPR spectrum of the radical intermediate in the addition reaction with that of the synthesized new [⋅P(μ-NTer)2P-Et] radical clearly proves the existence of radicals over the course of the reaction of biradical [⋅P(μ-NTer)2P⋅] ( 1 ) with bromoethane. Extensive DFT and coupled cluster calculations corroborate the experimental data for a radical mechanism in the reaction of biradical [⋅P(μ-NTer)2P⋅] with EtBr. In the field of hetero-cyclobutane-1,3-diyls, the demonstration of a stepwise radical reaction represents a new aspect and closes the gap between P-centered biradicals and P-centered monoradicals in terms of radical reactivity. 相似文献
13.
Jessica Lin 《偏微分方程通讯》2015,40(9):1688-1704
This note establishes an interior quantitative lower bound for nonnegative supersolutions of fully nonlinear uniformly parabolic equations. The result may be interpreted as a quantitative version of a growth lemma established by Krylov and Safonov for nonnegative supersolutions of linear uniformly parabolic equations in nondivergence form. Our approach is different, and follows from an application of a reverse Holder inequality. The result is the parabolic analogue of an elliptic regularity estimate established by Caffarelli, Souganidis, and Wang in the stochastic homogenization of fully nonlinear uniformly elliptic equations. 相似文献
14.
采用改进的反相高效液相色谱法(RP-HPLC)测定了持久性有机污染物(POPs)包括多环芳烃(PAHs)、多氯二苯并二恶英(PCDDs)、多氯二苯并呋喃(PCDFs)和十溴二苯乙烷(DBDPE)等的正辛醇-水分配系数(logKow)。采用保留时间双点校正法(DP-RTC)校正因色谱柱老化等引起的保留时间漂移。以37种有可靠logKow实验值的苯系物、PAHs、PCDD/Fs类似物为模型化合物,建立了logKow和外推至纯水相的保留因子logkw的定量结构-色谱保留关系(QSRR)模型,回归方程为logKow=(1.18±0.02)logkw+(0.36±0.11),其相关系数(R2)为0.985,交叉验证相关系数(R2cv)为0.983,标准偏差(SD)为0.16。进而,用4个已有可靠logKow实验值的验证化合物(联苯、芴、PCDD 1和PCDF 114)对模型进行了外部验证,表明RP-HPLC测得的logKow值与摇瓶法/慢搅法结果有很好的一致性,尤其是对疏水性强的化合物。采用该模型测定了29种特别受关注的POPs的logKow值,这些化合物的logKow实验值均未见报道。所建立的DP-RTC-HPLC是测定强疏水性POPs的logKow值的一种值得推荐的方法。 相似文献
15.
16.
电子垃圾拆解所引起的环境问题已经受到广泛关注,根据联合国环境规划署统计,全球约70%的电子垃圾通过各种途径进入我国,而我国自身也产生大量的电子垃圾。我国电子垃圾拆解活动采用的工艺较为原始,位于广东的贵屿和浙江的台州是我国最大的两个电子垃圾拆解地,拆解过程中电子垃圾本身含有和不当处置所产生的大量持久性有毒化学污染物(如重金属、二 NFDA1 英类、溴代阻燃剂等)释放到环境中,对拆解地生态系统及居民健康造成严重的威胁。本文重点针对我国电子垃圾拆解所造成的持久性有毒污染物(PTS)污染现状、管理措施和法规、拆解区居民所面临的持久性有毒污染物暴露健康风险及其相关研究最新进展进行了分析和概括,并对电子垃圾拆解区域持久性有毒污染物及新型环境污染物研究和发展方向作了展望。 相似文献
17.
本文利用专著(1) ̄(3)中的有关方法,讨论了一类具有滞后的中立型时变非线性控制系统的镇定与次优控制问题,得出了滞后量与非线性项的估计公式,并推广了文(4),(5)的结果。 相似文献
18.
Towards a unified recurrent neural network theory: The uniformly pseudo-projection-anti-monotone net
In the past decades, various neural network models have been developed for modeling the behavior of human brain or performing
problem-solving through simulating the behavior of human brain. The recurrent neural networks are the type of neural networks
to model or simulate associative memory behavior of human being. A recurrent neural network (RNN) can be generally formalized
as a dynamic system associated with two fundamental operators: one is the nonlinear activation operator deduced from the input-output
properties of the involved neurons, and the other is the synaptic connections (a matrix) among the neurons. Through carefully
examining properties of various activation functions used, we introduce a novel type of monotone operators, the uniformly
pseudo-projectionanti-monotone (UPPAM) operators, to unify the various RNN models appeared in the literature. We develop a
unified encoding and stability theory for the UPPAM network model when the time is discrete. The established model and theory
not only unify but also jointly generalize the most known results of RNNs. The approach has lunched a visible step towards
establishment of a unified mathematical theory of recurrent neural networks. 相似文献
19.
也谈均匀带电细圆环的电场分布 总被引:1,自引:0,他引:1
用Mathematica研究均匀带电细圆环的电场的空间分布,准确地绘制出电场强度量值的分布图和电场方向的分布图,并纠正了最近文献中一幅场强量值分布图的失误. 相似文献
20.
Factors affecting the dimerization of persistent nitrogen‐centered 1‐phenyl urazole radicals to tetrazanes 下载免费PDF全文
1‐Phenyl urazole radicals are persistent air‐stable nitrogen‐centered radicals that engage in an equilibrium with the corresponding N―N tetrazane dimers in solution. While the equilibrium typically weakly favors the dimer form, for some 1‐phenyl urazole radicals bearing substituents at the ortho position of the benzene ring, the equilibrium instead strongly favors the dimer form. With the recent surge of interest in the properties and potential applications of heterocyclic radicals, the factors that affect this equilibrium are important to determine. We examined the effect of the extent of ortho substitution (none, 1, or 2 substituents) on the equilibrium by experimentally using variable temperature 1H nuclear magnetic resonance and UV‐visible spectroscopy in addition to supporting computational investigations at the (U)B3LYP/6‐311G(d,p) level of theory. We confirmed that the equilibrium generally favored the dimer in all cases. However, the equilibrium was more favorable towards dimer formation for urazole radicals substituted with 1 and 2 ortho substituents on the aromatic ring. The activation enthalpies for dissociation of singly substituted dimers were greater than that for dimers without ortho substituents, but lower than that for doubly substituted dimers. The greater preference for dimer formation for the ortho‐substituted urazole radicals is attributed to a greater enthalpic advantage for N―N bond formation. This advantage may be traced to a higher concentration of spin density on the urazole unit of the radicals and a lesser deformation energy required for N―N bond formation. 相似文献