全文获取类型
收费全文 | 8385篇 |
免费 | 1064篇 |
国内免费 | 443篇 |
专业分类
化学 | 5081篇 |
晶体学 | 356篇 |
力学 | 282篇 |
综合类 | 74篇 |
数学 | 1205篇 |
物理学 | 2894篇 |
出版年
2023年 | 42篇 |
2022年 | 117篇 |
2021年 | 187篇 |
2020年 | 187篇 |
2019年 | 201篇 |
2018年 | 192篇 |
2017年 | 240篇 |
2016年 | 319篇 |
2015年 | 268篇 |
2014年 | 317篇 |
2013年 | 546篇 |
2012年 | 344篇 |
2011年 | 340篇 |
2010年 | 287篇 |
2009年 | 312篇 |
2008年 | 311篇 |
2007年 | 349篇 |
2006年 | 306篇 |
2005年 | 432篇 |
2004年 | 633篇 |
2003年 | 526篇 |
2002年 | 409篇 |
2001年 | 309篇 |
2000年 | 265篇 |
1999年 | 215篇 |
1998年 | 200篇 |
1997年 | 201篇 |
1996年 | 232篇 |
1995年 | 204篇 |
1994年 | 223篇 |
1993年 | 161篇 |
1992年 | 139篇 |
1991年 | 78篇 |
1990年 | 71篇 |
1989年 | 62篇 |
1988年 | 58篇 |
1987年 | 74篇 |
1986年 | 54篇 |
1985年 | 42篇 |
1984年 | 45篇 |
1983年 | 15篇 |
1982年 | 47篇 |
1981年 | 39篇 |
1980年 | 45篇 |
1979年 | 60篇 |
1978年 | 48篇 |
1977年 | 50篇 |
1976年 | 37篇 |
1974年 | 15篇 |
1973年 | 17篇 |
排序方式: 共有9892条查询结果,搜索用时 15 毫秒
71.
Dr. Abdulghani Ismail Dr. Silvia Voci Lucie Descamps Dr. Arnaud Buhot Prof. Dr. Neso Sojic Dr. Loïc Leroy Dr. Aurélie Bouchet-Spinelli 《Chemphyschem》2021,22(11):1094-1100
This work depicts the original combination of electrochemiluminescence (ECL) and bipolar electrochemistry (BPE) to map in real-time the oxidation of silicon in microchannels. We fabricated model silicon-PDMS microfluidic chips, optionally containing a restriction, and monitored the evolution of the surface reactivity using ECL. BPE was used to remotely promote ECL at the silicon surface inside microfluidic channels. The effects of the fluidic design, the applied potential and the resistance of the channel (controlled by the fluidic configuration) on the silicon polarization and oxide formation were investigated. A potential difference down to 6 V was sufficient to induce ECL, which is two orders of magnitude less than in classical BPE configurations. Increasing the resistance of the channel led to an increase in the current passing through the silicon and boosted the intensity of ECL signals. Finally, the possibility of achieving electrochemical reactions at predetermined locations on the microfluidic chip was investigated using a patterning of the silicon oxide surface by etched micrometric squares. This ECL imaging approach opens exciting perspectives for the precise understanding and implementation of electrochemical functionalization on passivating materials. In addition, it may help the development and the design of fully integrated microfluidic biochips paving the way for development of original bioanalytical applications. 相似文献
72.
李杰阳 《中国无机分析化学》2021,(2)
近年来,随着全自动红外测硫仪的快速发展,仪器性能的升级优化,加之对固体矿物质种类和高硫含量检测技术有了新的技术突破。因此将全自动红外测硫仪应用于硫化矿矿石中全硫量的测定,采用国家硫矿石标准样品中不同段的硫含量(标准值),建立标准工作曲线,再结合实际样品校正该曲线,建立了一种用全自动红外吸收光谱法测定硫化矿矿石中全硫量的检测方法。方法的主要特点是包括样品称量在内的整个测试过程由计算机控制自动完成,自动化程度极高,分析时间短,结果准确、可靠。选取当地不同矿物特性的8个样品,测定的相对标准偏差RSD(n=11)均小于2.5%,样品加标回收率为86.2%~117%,与化学法(空气或氧气燃烧-碘量法)测定结果对照,测定结果都在允许误差范围内,完全能够满足日常硫化矿矿石中全硫含量的检测要求。 相似文献
73.
Graphene is scientifically and commercially important because of its unique molecular structure which is monoatomic in thickness, rigorously two-dimensional and highly conjugated. Consequently, graphene exhibits exceptional electrical, optical, thermal and mechanical properties. Herein, we critically discuss the surface modification of graphene, the specific advantages that graphene-based materials can provide over other materials in sensor research and their related chemical and electrochemical properties. Furthermore, we describe the latest developments in the use of these materials for sensing technology, including chemical sensors and biosensors and their applications in security, environmental safety and diseases detection and diagnosis. 相似文献
74.
Dr. Natalie Spomer Dr. Sven Holl Dr. Larissa Zherlitsyna Dr. Fariba Maysamy Andreas Frost Prof. Dr. Norbert Auner 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(14):5600-5616
Amorphous silicon is synthesized by treating the tetrahalosilanes SiX4 (X=Cl, F) with molten sodium in high boiling polar and non‐polar solvents such as diglyme or nonane to give a brown or a black solid showing different reactivities towards suitable reagents. With regards to their technical relevance, their stability towards oxygen, air, moisture, chlorine‐containing reaction partners RCl (R=H, Cl, Me) and alcohols is investigated. In particular, reactions with methanol are a versatile tool to deliver important products. Besides tetramethoxysilane formation, methanolysis of silicon releases hydrogen gas under ambient conditions and is thus suitable for a decentralized hydrogen production; competitive insertion into the MeO?H versus the Me?OH bond either yields H‐ and/or methyl‐substituted methoxy functional silanes. Moreover, compounds, such as MenSi(OMe)4?n (n=0–3) are simply accessible in more than 75 % yield from thermolysis of, for example, tetramethoxysilane over molten sodium. Based on our systematic investigations we identified reaction conditions to produce the methoxysilanes MenSi(OMe)4?n in excellent (n=0:100 %) to acceptable yields (n=1:51 %; n=2:27 %); the yield of HSi(OMe)3 is about 85 %. Thus, the methoxysilanes formed might possibly open the door for future routes to silicon‐based products. 相似文献
75.
Asymmetric Catalysis with Silicon‐Based Cuprates: Enantio‐ and Regioselective Allylic Substitution of Linear Precursors 下载免费PDF全文
Alexander Hensel Prof. Dr. Martin Oestreich 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(25):9062-9065
An enantio‐ and regioselective allylic silylation of linear allylic phosphates that makes use of catalytically generated cuprate‐type silicon nucleophiles is reported. The method relies on soft bis(triorganosilyl) zincs as silicon pronucleophiles that are prepared in situ from the corresponding hard lithium reagents by transmetalation with ZnCl2. With a preformed chiral N‐heterocyclic carbene–copper(I) complex as catalyst, exceedingly high enantiomeric excesses are achieved. The new method is superior to existing ones using a silicon–boron reagent as the source of the silicon nucleophile. 相似文献
76.
崔莹 《分析测试技术与仪器》2015,(3):176-179
使用元素分析仪进行土壤、沉积物样品碳、氮含量检测时,样品前处理过程(烘干和酸化)、包样质量以及参考标准品等因素均会对检测结果造成影响.试验结果表明:酸化导致氮百分质量的测定结果降低2.6%~40.0%,碳百分质量的测定受包样质量的影响较大,使用的校正标准与被测样品越相似,校正结果越准确. 相似文献
77.
Rhodium‐Catalyzed Enantioselective Intramolecular CH Silylation for the Syntheses of Planar‐Chiral Metallocene Siloles 下载免费PDF全文
Dr. Qing‐Wei Zhang Kun An Li‐Chuan Liu Yuan Yue Prof. Dr. Wei He 《Angewandte Chemie (International ed. in English)》2015,54(23):6918-6921
Reported herein is the rhodium‐catalyzed enantioselective C? H bond silylation of the cyclopentadiene rings in Fe and Ru metallocenes. Thus, in the presence of (S)‐TMS‐Segphos, the reactions took place under very mild conditions to afford metallocene‐fused siloles in good to excellent yields and with ee values of up to 97 %. During this study it was observed that the steric hindrance of chiral ligands had a profound influence on the reactivity and enantioselectivity of the reaction, and might hold the key to accomplishing conventionally challenging asymmetric C? H silylations. 相似文献
78.
Synthesis of an [(NHC)2Pd(SiMe3)2] Complex and Catalytic cis‐Bis(silyl)ations of Alkynes with Unactivated Disilanes 下载免费PDF全文
Melvyn B. Ansell Dr. Debbie E. Roberts Prof. F. Geoffrey N. Cloke Dr. Oscar Navarro Dr. John Spencer 《Angewandte Chemie (International ed. in English)》2015,54(19):5578-5582
The novel complex cis‐[(ITMe)2Pd(SiMe3)2 (ITMe=1,3,4,5‐tetramethylimidazol‐2‐ylidene) has been synthesized by mild oxidative cleavage of Me3SiSiMe3 using [(ITMe)2Pd0]. The use of this complex as precatalyst for the cis‐bis(silyl)ation of alkynes using unactivated disilanes is reported. 相似文献
79.
A. K. Khe 《Journal of Applied Mechanics and Technical Physics》2004,45(2):181-186
The steadystate threedimensional motion of an ideal gas in a thin layer of variable height is considered. In the longwave approximation, the equations of gas dynamics reduce to a system of integrodifferential equations. The generalized characteristics and hyperbolicity conditions of the obtained system are found. 相似文献
80.