全文获取类型
收费全文 | 509篇 |
免费 | 50篇 |
国内免费 | 4篇 |
专业分类
化学 | 331篇 |
晶体学 | 1篇 |
力学 | 8篇 |
数学 | 115篇 |
物理学 | 108篇 |
出版年
2023年 | 10篇 |
2022年 | 6篇 |
2021年 | 11篇 |
2020年 | 19篇 |
2019年 | 28篇 |
2018年 | 11篇 |
2017年 | 10篇 |
2016年 | 36篇 |
2015年 | 29篇 |
2014年 | 20篇 |
2013年 | 81篇 |
2012年 | 39篇 |
2011年 | 34篇 |
2010年 | 18篇 |
2009年 | 10篇 |
2008年 | 21篇 |
2007年 | 12篇 |
2006年 | 9篇 |
2005年 | 11篇 |
2004年 | 9篇 |
2003年 | 7篇 |
2002年 | 6篇 |
2001年 | 6篇 |
2000年 | 7篇 |
1999年 | 6篇 |
1998年 | 2篇 |
1997年 | 6篇 |
1996年 | 2篇 |
1994年 | 3篇 |
1993年 | 2篇 |
1989年 | 2篇 |
1988年 | 2篇 |
1984年 | 6篇 |
1983年 | 3篇 |
1977年 | 3篇 |
1939年 | 2篇 |
1937年 | 3篇 |
1909年 | 2篇 |
1900年 | 3篇 |
1893年 | 3篇 |
1892年 | 4篇 |
1891年 | 4篇 |
1890年 | 4篇 |
1889年 | 3篇 |
1888年 | 6篇 |
1887年 | 2篇 |
1884年 | 8篇 |
1883年 | 2篇 |
1881年 | 4篇 |
1880年 | 3篇 |
排序方式: 共有563条查询结果,搜索用时 31 毫秒
1.
Timm Bergholz Dr. Benjamin Oelkers Dr. Benedikt Huber Prof. Bernhard Roling Prof. Dr. Jörg Sundermeyer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2613-2620
New salts based on imidazolium, pyrrolidinium, phosphonium, guanidinium, and ammonium cations together with the 5‐cyanotetrazolide anion [C2N5]? are reported. Depending on the nature of cation–anion interactions, characterized by XRD, the ionic liquids (ILs) have a low viscosity and are liquid at room temperature or have higher melting temperatures. Thermogravimetric analysis, cyclic voltammetry, viscosimetry, and impedance spectroscopy display a thermal stability up to 230 °C, an electrochemical window of 4.5 V, a viscosity of 25 mPa s at 20 °C, and an ionic conductivity of 5.4 mS cm?1 at 20 °C for the IL 1‐butyl‐1‐methylpyrrolidinium 5‐cyanotetrazolide [BMPyr][C2N5]. On the basis of these results, the synthesized compounds are promising electrolytes for lithium‐ion batteries. 相似文献
2.
A. Paesano Jr. S. C. Zanatta S. N. De Medeiros L. F. CÓtica J. B. M. Da Cunha 《Hyperfine Interactions》2005,161(1-4):211-220
We have investigated the mechanosynthesis of gadolinium and yttrium iron garnets by high-energy ball-milling of α-Fe2O3 and Gd2O3 or α-Fe2O3 and Y2O3, respectively, followed by short thermal annealings conducted at moderate temperatures. The samples were characterized by X-ray diffraction and Mössbauer spectroscopy, in order to determine the influence of the milling time and annealing conditions on the final products. For as-milled samples of each rare-earth system, the results revealed the formation of perovskite phases, in relative amounts that depend on the milling time. The formation of garnet phases was observed in as-annealed samples treated at 1000°C for 2 h or 1100°C for 3 h, i.e., at very modest annealing requirements when compared with ordinary solid-state-reaction processes performed without previous high-energy milling. Also, the occurrence was verified of a milling time for which the relative amount of garnet phases formed by annealing was maximized. This time depends on the rare-earth composing the garnet phase and on the annealing temperature. 相似文献
3.
Tuo Jiang Samuele Bordi Angus E. McMillan Kuang-Yen Chen Fumito Saito Paula L. Nichols Benedikt M. Wanner Jeffrey W. Bode 《Chemical science》2021,12(20):6977
The current laboratory practices of organic synthesis are labor intensive, impose safety and environmental hazards, and hamper the implementation of artificial intelligence guided drug discovery. Using a combination of reagent design, hardware engineering, and a simple operating system we provide an instrument capable of executing complex organic reactions with prepacked capsules. The machine conducts coupling reactions and delivers the purified products with minimal user involvement. Two desirable reaction classes – the synthesis of saturated N-heterocycles and reductive amination – were implemented, along with multi-step sequences that provide drug-like organic molecules in a fully automated manner. We envision that this system will serve as a console for developers to provide synthetic methods as integrated, user-friendly packages for conducting organic synthesis in a safe and convenient fashion.Using a combination of reagent design, hardware engineering, and a simple operating system we provide an instrument capable of executing complex organic reactions using prepacked capsules with minimal user involvement. 相似文献
4.
Steffen Wolf Benedikt Sohmen Bjrn Hellenkamp Johann Thurn Gerhard Stock Thorsten Hugel 《Chemical science》2021,12(9):3350
We report on a study that combines advanced fluorescence methods with molecular dynamics (MD) simulations to cover timescales from nanoseconds to milliseconds for a large protein. This allows us to delineate how ATP hydrolysis in a protein causes allosteric changes at a distant protein binding site, using the chaperone Hsp90 as test system. The allosteric process occurs via hierarchical dynamics involving timescales from nano- to milliseconds and length scales from Ångstroms to several nanometers. We find that hydrolysis of one ATP is coupled to a conformational change of Arg380, which in turn passes structural information via the large M-domain α-helix to the whole protein. The resulting structural asymmetry in Hsp90 leads to the collapse of a central folding substrate binding site, causing the formation of a novel collapsed state (closed state B) that we characterise structurally. We presume that similar hierarchical mechanisms are fundamental for information transfer induced by ATP hydrolysis through many other proteins.We report on a study that combines advanced fluorescence methods with molecular dynamics simulations to cover timescales from nanoseconds to milliseconds for a large protein, the chaperone Hsp90. 相似文献
5.
van Swieten PF Leeuwenburgh MA Kessler BM Overkleeft HS 《Organic & biomolecular chemistry》2005,3(1):20-27
The chemical labeling of biomolecules continues to be an important tool for the study of their function and cellular fate. Attention is increasingly focused on labeling of biomolecules in living cells, since cell lysis introduces many artefacts. In addition, with the advances in biocompatible synthetic organic chemistry, a whole new field of opportunity has opened up, affording high diversity in the nature of the label as well as a choice of ligation reactions. In recent years, several different two-step labeling strategies have emerged. These rely on the introduction of a bioorthogonal attachment site into a biomolecule, then ligation of a reporter molecule to this site using bioorthogonal organic chemistry. This Perspective focuses on these techniques, their implications and future directions. 相似文献
6.
Analysis of the beta-blockers oxprenolol, atenolol, timolol, propranolol, metoprolol, and acebutolol in human urine by a combination of isotachophoresis (ITP) and zone electrophoresis (ZE) was investigated. Methods were developed with a conventional capillary electrophoresis (CE) apparatus and a poly(methyl methacrylate) (PMMA) microchip system. With CE the separation of oxprenolol, atenolol, timolol, and acebutolol from a standard solution containing 5 microg/mL of each compound was accomplished by performing ZE with transient ITP. The electrolyte system consisted of 10 mM sodium morpholinoethane sulfonate (pH 5.5) and 0.1% methylhydroxyethylcellulose as the leading electrolyte and 30 mM ortho-phosphoric acid (pH 2.0) as both the terminating and the ZE background electrolyte. With the microchip system the separation of oxprenolol and acebutolol from a standard solution containing 10 microg/mL of each compound was accomplished by a coupled-channel ITP-ZE device using the same leading electrolyte solution as the CE system but 5 mM glutamic acid (pH 3.4) as terminating and background electrolytes. The systems were used for analyses of patient urine samples. Water-soluble hydrophilic matrix compounds were removed from the urine samples by solid-phase extraction (SPE). Limits of quantification below 5 microg/mL could be achieved. The PMMA ITP-ZE chip has not earlier been used for analyses of any drugs from urine samples. 相似文献
7.
Unexpected reactivity of pyridinium salts toward alkynyl Fischer complexes to produce oxo‐heterocycles 下载免费PDF全文
María Inés Flores‐Conde Fabiola N. de la Cruz Julio López J. Óscar C. Jiménez‐Halla Eduardo Peña‐Cabrera Marcos Flores‐Álamo Francisco Delgado Miguel A. Vázquez 《应用有机金属化学》2018,32(3)
The unprecedented reaction of ketone‐containing aromatic pyridinium salts 3a ‐ e and alkynyl Fischer complexes 1a ‐ f proceeds via a mild domino process to provide 4,6‐disubstituted pyran‐2‐ones 5a ‐ k and 2,3,5‐trisubstituted furans 6a ‐ h (45‐97%). According of the results of isotopic labeling experiments, a mechanism involving an initial Michael addition appears to be the key step, obtaining a mesomeric structure responsible for the formation of both products. 相似文献
8.
Enrique Castillo Rosa Eva Pruneda MÓnica Esquivel IV 《International Journal of Mathematical Education in Science & Technology》2013,44(2):209-232
The paper presents a method for generating random linear programming problems with a previously selected type of solution. The user can choose a problem whose solution is unbounded, bounded for minima, maxima or both, unique or multiple, with given structure, at wish. Initially, the feasible solution of the LPP is generated as the sum of a linear space, a cone, and a polytope, depending on the desired properties of the solution. With the aim of obtaining a simple set of constraints, the generators of these three structures are selected as random vectors with integer simple components, the range of which can be given. Next, an objective function that satisfies the required conditions, i.e. leads to a solution of the desired type, is obtained. The generating algorithms have been implemented in Mathematica and some illustrative examples are given to clarify the generation process. With this tool, a LPP can be generated, according to the instructor requirements, where this is a human or an expert system. They can control student progress and generate a sequence of problems covering all possible cases, in steps of increasing difficulty. Combining this tool with another (also produced by the same authors) that solves the problems and explains the whole process, step by step, a computer aided module for learning LPP, which is completely autonomous, can be easily obtained. 相似文献
9.
10.
An matrix is Butson–Hadamard if its entries are th roots of unity and it satisfies . Write for the set of such matrices.Suppose that where and are primes and . A recent result of Östergård and Paavola uses a matrix to construct . We simplify the proof of this result and remove the restriction on the number of prime divisors of . More precisely, we prove that if , and each prime divisor of divides , then we can construct a matrix from any . 相似文献