全文获取类型
收费全文 | 103139篇 |
免费 | 6581篇 |
国内免费 | 12902篇 |
专业分类
化学 | 81995篇 |
晶体学 | 1134篇 |
力学 | 2939篇 |
综合类 | 913篇 |
数学 | 13001篇 |
物理学 | 22640篇 |
出版年
2023年 | 866篇 |
2022年 | 1460篇 |
2021年 | 1979篇 |
2020年 | 2742篇 |
2019年 | 2585篇 |
2018年 | 2273篇 |
2017年 | 3285篇 |
2016年 | 3599篇 |
2015年 | 3104篇 |
2014年 | 3997篇 |
2013年 | 7777篇 |
2012年 | 7389篇 |
2011年 | 6073篇 |
2010年 | 5082篇 |
2009年 | 6959篇 |
2008年 | 7016篇 |
2007年 | 7400篇 |
2006年 | 6645篇 |
2005年 | 5715篇 |
2004年 | 5285篇 |
2003年 | 4277篇 |
2002年 | 3623篇 |
2001年 | 2932篇 |
2000年 | 2575篇 |
1999年 | 2426篇 |
1998年 | 2070篇 |
1997年 | 1714篇 |
1996年 | 1429篇 |
1995年 | 1580篇 |
1994年 | 1418篇 |
1993年 | 1164篇 |
1992年 | 1091篇 |
1991年 | 818篇 |
1990年 | 637篇 |
1989年 | 580篇 |
1988年 | 422篇 |
1987年 | 336篇 |
1986年 | 305篇 |
1985年 | 251篇 |
1984年 | 258篇 |
1983年 | 141篇 |
1982年 | 226篇 |
1981年 | 185篇 |
1980年 | 192篇 |
1979年 | 176篇 |
1978年 | 157篇 |
1977年 | 93篇 |
1976年 | 84篇 |
1974年 | 43篇 |
1973年 | 45篇 |
排序方式: 共有10000条查询结果,搜索用时 343 毫秒
11.
Large amounts of flowback and produced water (FPW) have been generated from hydraulic fracturing process for the production of unconventional gas such as shale gas. Complex organic pollutants are abundantly present in FPW with revealed toxicity to aquatic organisms and these contaminants may transfer into surrounding aquatic environment. Characterization and determination of complicated organic pollutants in FPW remains a challenge due to its complex composition and high salinity matrix. This review article covers the progress of recent 5 years regarding the sample preparation and instrumental analysis methods and thus summarizes the advantages and disadvantages of these methods for critical analysis of organic contaminants in FPW samples. Furthermore, the natural distribution of detected organic compounds and their transformation were reviewed and discussed to enhance the understanding of spatial and temporal behaviors of these organic pollutants in natural environment, paving the way for future development of pollution control policies and strategies. Enlightened by the studies of FPW contamination in the US, the investigations of FPW contamination in China continued to grow due to rapidly growing production of shale gas in China and resulted pollution. 相似文献
12.
本文以咪唑衍生物为配体,通过水热合成法与钴离子制备出两个配位聚合物:{[Co(DTA)(1,4-DIB)(H2O)]·H2O}n(1)和[Co(DTA)(1,3-BMIB)]n(2)(1,4-DIB=1,4-二(1H-咪唑-1-基)苯; 1,3-BMIB=1,3-二(4-甲基-1H-咪唑-1-基)苯;H2DTA=2,5-二甲氧基对苯二甲酸)。利用X射线单晶衍射、粉末衍射、热失重、元素分析、红外光谱以及固体紫外-可见光谱等对两个配合物进行了表征。结构分析证实配合物1和2是通过二维结构堆积成的三维超分子化合物。粉末衍射测试则显示两个配合物在水中有很好的稳定性。固体紫外-可见光谱显示两个配合物属半导体材料,对紫外-可见光有很强的吸收作用。在光催化实验中,配合物1和2可加快亚甲基蓝的降解速度。 相似文献
13.
Chemical bonding in representative astrophysically relevant neutral,cation, and anion HCnH chains 下载免费PDF全文
Ioan Baldea 《中国物理 B》2022,31(12):123101-123101
Most existing studies assign a polyynic and cumulenic character of chemical bonding in carbon-based chains relying on values of the bond lengths. Building on our recent work, in this paper we add further evidence on the limitations of such an analysis and demonstrate the significant insight gained via natural bond analysis. Presently reported results include atomic charges, natural bond order and valence indices obtained from ab initio computations for representative members of the astrophysically relevant neutral and charged HC2k/2k+1H chain family. They unravel a series of counter-intuitive aspects and/or help naive intuition in properly understanding microscopic processes, e.g., electron removal from or electron attachment to a neutral chain. Demonstrating that the Wiberg indices adequately quantify the chemical bonding structure of the HC2k/2k+1H chains—while the often heavily advertised Mayer indices do not—represents an important message conveyed by the present study. 相似文献
14.
Dr. Zaifa Shi Dr. Yihuang Jiang Dr. Jingxiong Yu Prof. Shanjun Chen Prof. Jun Chen Prof. Zichao Tang Prof. Lansun Zheng 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(8):e202103546
At present, the reactivity of cyclic alkanes is estimated by comparison with acyclic hydrocarbons. Due to the difference in the structure of cycloalkanes and acycloalkanes, the thermodynamic data obtained by analogy are not applicable. In this study, a molecular beam sampling vacuum ultraviolet photoionization time-of-flight mass spectrometer (MB-VUV-PI-TOFMS) was applied to study the low-temperature oxidation of cyclopentane (CPT) at a total pressure range from 1–3 atm and low-temperature range between 500 and 800 K. Low-temperature reaction products including cyclic olefins, cyclic ethers, and highly oxygenated intermediates (e. g., ketohydroperoxide KHP, keto-dihydroperoxide KDHP, olefinic hydroperoxides OHP and ketone structure products) were observed. Further investigation of the oxidation of CPT – electronic structure calculations – were carried out at the UCCSD(T)-F12a/aug-cc-pVDZ//B3LYP/6-31+ G(d,p) level to explore the reactivity of O2 molecules adding sequentially to cyclopentyl radicals. Experimental and theoretical observations showed that the dominant product channel in the reaction of CPT radicals with O2 is HO2 elimination yielding cyclopentene. The pathways of second and third O2 addition – the dissociation of hydroperoxide – were further confirmed. The results of this study will develop the low-temperature oxidation mechanism of CPT, which can be used for future research on accurately simulating the combustion process of CPT. 相似文献
15.
《Mendeleev Communications》2022,32(1):123-125
The synthesis, structure and properties of copper(II) perchlorate complexes with antipyrine (AP), [Cu(AP)4(H2O)](ClO4)2 and [Cu(AP)5](ClO4)2, are described and compared with those of alternative compounds containing different AP ligands. 相似文献
16.
通过3,3′-((乙烷-1,2-二基双(2-甲基吡啶杂氮二基)双(亚甲基))双(2-羟基-5-甲基苯甲醛)与2-羟基-1,3-丙二胺的缩合反应得到一种具有双吡啶悬臂的双核锰配合物。通过X射线单晶衍射确定了该配合物结构,结果显示其分子式为[Mn2(C37H43N6O6)]·(ClO4)2。该配合物属于单斜晶系,P21/c空间群,晶胞参数为:a=1.096 50(19) nm, b=1.419 5(3) nm, c=3.109 4(5) nm, β=108.153(5)°。进一步分析表明两个二价锰离子分别与(Namine)2(Nimine)2O3和(Nimine)2O4体系配位,它们与配位原子形成的几何构型分别是十面体和扭曲的八面体。两个中心锰离子距离为0.331 6 nm,由酚氧原子和醋酸根共同桥联。另外,本文也利用伏安法和黏度法对该配合物与小牛胸腺DNA的结合能力进行研究,实验结果表明它们之间的结合方式为弱的插入作用。 相似文献
17.
《Mendeleev Communications》2022,32(6):777-779
The reactions of aryllithium reagents o-LiC6H4CH2NR2 with (MeO)2CO afford two new tris(aryl)carbinols bearing pendant-NR2 donor groups in the side chain [o-R NCH C H ] COH [R = Me, R + R = (CH) ]. These alcohols feature helical chirality due to differently inclined aromatic fragments and are presented in a crystalline cell as two M and P enantiomers. Carbinol (R = Me) readily reacts with (Me3SiCH2)3Sc(THF)2 to give a scandium bis(alkyl) complex [(o-C6H4CH2NMe2)3CO]Sc(CH2SiMe3)2 featuring rigid binding of the alkoxy anion through a κ1-O, κ2-N chelating coordination mode 相似文献
18.
基于低温等离子体设计并实现了一套热解吸反压低温等离子体电离(TD-iLTPI)装置。TD-iLTPI装置由热解吸模块和电离源模块集成在一个π型四通管上组成,进样探针取得样品后插入热解吸模块使其气化,之后随载气进入电离区域被电离。iLTPI内部的针电极接交流电,外部的环形电极接地,电极连接方式与LTP相反。该文对热解吸反压低温等离子体电离源进行了参数的优化,并与三重四极杆质谱联用检测了12种代表性的邻苯二甲酸酯,同时考察了TD-iLTPI-MS的分析性能,并对含有邻苯二甲酸酯的实际样品进行了检测。结果表明,邻苯二甲酸丁苄酯(BBP)的标准曲线具有良好的线性相关系数(R;=0.9958),加标回收率为89.7%~116.8%,相对标准偏差为4.5%~8.2%,对邻苯二甲酸酯的检出限也远低于其他敞开式离子源。对白酒、果汁、面包、奶酪和黄油中的邻苯二甲酸酯进行了快速筛查,并定量检测了果汁中的邻苯二甲酸丁苄酯。 相似文献
19.
Comprehensive performance of a ball-milled La0.5Pr0.5Fe11.4Si1.6B0.2Hy/Al magnetocaloric composite 下载免费PDF全文
Jiao-Hong Huang 《中国物理 B》2022,31(4):47503-047503
Due to the hydrogen embrittlement effect, La(Fe,Si)13-based hydrides can only exist in powder form, which limits their practical application. In this work, ductile and thermally conductive Al metal was homogeneously mixed with La0.5Pr0.5Fe11.4Si1.6B0.2 using the ball milling method. Then hydrogenation and compactness shaping of the magnetocaloric composites were performed in one step via a sintering process under high hydrogen pressure. As the Al content reached 9 wt.%, the La0.5Pr0.5Fe11.4Si1.6B0.2Hy/Al composite showed the mechanical behavior of a ductile material with a yield strength of ~44 MPa and an ultimate strength of 269 MPa accompanied by a pronounced improvement in thermal conductivity. Due to the ease of formation of Fe-Al-Si phases and the several micron and submicron sizes of the composite particles caused by ball milling process, the magnetic entropy change of the composites was substantially reduced to ~1.2 J/kg· K-1.5 J/kg· K at 0 T-1.5 T. 相似文献
20.
为解决深度学习在图像水印算法中计算量大且模型冗余的问题,提高图像水印算法在抵抗噪声、旋转和剪裁等攻击时的鲁棒性,提出基于快速神经网络架构搜索(neural architecture search,NAS)的鲁棒图像水印网络算法。通过多项式分布学习快速神经网络架构搜索算法,在预设的搜索空间中搜索最优网络结构,进行图像水印的高效嵌入与鲁棒提取。首先,将子网络中线性连接的全卷积层设置为独立的神经单元结构,并参数化表示结构单元内节点的连接,预先设定结构单元内每个神经元操作的搜索空间;其次,在完成一个批次的数据集训练后,依据神经元操作中的被采样次数和平均损失函数值动态更新概率;最后,重新训练搜索完成的网络。水印网络模型的参数量较原始网络模型缩减了92%以上,大大缩短了模型训练时间。由于搜索得到的网络结构更为紧凑,本文算法具有较高的时间性能和较好的实验效果,在隐藏图像时,对空域信息的依赖比原始网络更少。对改进前后的2个网络进行了大量鲁棒性实验,对比发现,本文算法在CIFAR-10数据集上对抵抗椒盐噪声和旋转、移除像素行(列)等攻击优势显著;在ImageNet数据集上对抵抗椒盐高斯噪声、旋转、中值滤波、高斯滤波、JPEG压缩、裁剪等攻击优势显著,特别是对随机移除行(列)和椒盐噪声有较强的鲁棒性。 相似文献