全文获取类型
收费全文 | 5233篇 |
免费 | 239篇 |
国内免费 | 8篇 |
专业分类
化学 | 3861篇 |
晶体学 | 44篇 |
力学 | 78篇 |
数学 | 652篇 |
物理学 | 845篇 |
出版年
2023年 | 38篇 |
2022年 | 32篇 |
2021年 | 92篇 |
2020年 | 95篇 |
2019年 | 79篇 |
2018年 | 98篇 |
2017年 | 86篇 |
2016年 | 181篇 |
2015年 | 166篇 |
2014年 | 168篇 |
2013年 | 330篇 |
2012年 | 389篇 |
2011年 | 458篇 |
2010年 | 205篇 |
2009年 | 179篇 |
2008年 | 349篇 |
2007年 | 346篇 |
2006年 | 310篇 |
2005年 | 278篇 |
2004年 | 252篇 |
2003年 | 209篇 |
2002年 | 195篇 |
2001年 | 104篇 |
2000年 | 110篇 |
1999年 | 63篇 |
1998年 | 34篇 |
1997年 | 41篇 |
1996年 | 78篇 |
1995年 | 37篇 |
1994年 | 34篇 |
1993年 | 40篇 |
1992年 | 36篇 |
1991年 | 29篇 |
1990年 | 22篇 |
1989年 | 20篇 |
1988年 | 17篇 |
1987年 | 16篇 |
1986年 | 23篇 |
1985年 | 21篇 |
1984年 | 21篇 |
1983年 | 18篇 |
1982年 | 23篇 |
1981年 | 12篇 |
1980年 | 19篇 |
1979年 | 18篇 |
1978年 | 17篇 |
1977年 | 12篇 |
1976年 | 19篇 |
1974年 | 13篇 |
1973年 | 10篇 |
排序方式: 共有5480条查询结果,搜索用时 78 毫秒
1.
Experimental and Theoretical Studies on the Rearrangement of 2‐Oxoazepane α,α‐Amino Acids into 2′‐Oxopiperidine β2,3,3‐Amino Acids: An Example of Intramolecular Catalysis 下载免费PDF全文
Dr. Diego Núñez‐Villanueva Dr. M. Ángeles Bonache Laura Lozano Dr. Lourdes Infantes Prof. José Elguero Prof. Ibon Alkorta Prof. M. Teresa García‐López Dr. Rosario González‐Muñiz Dr. Mercedes Martín‐Martínez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2489-2500
Enantiopure β‐amino acids represent interesting scaffolds for peptidomimetics, foldamers and bioactive compounds. However, the synthesis of highly substituted analogues is still a major challenge. Herein, we describe the spontaneous rearrangement of 4‐carboxy‐2‐oxoazepane α,α‐amino acids to lead to 2′‐oxopiperidine‐containing β2,3,3‐amino acids, upon basic or acid hydrolysis of the 2‐oxoazepane α,α‐amino acid ester. Under acidic conditions, a totally stereoselective synthetic route has been developed. The reordering process involved the spontaneous breakdown of an amide bond, which typically requires strong conditions, and the formation of a new bond leading to the six‐membered heterocycle. A quantum mechanical study was carried out to obtain insight into the remarkable ease of this rearrangement, which occurs at room temperature, either in solution or upon storage of the 4‐carboxylic acid substituted 2‐oxoazepane derivatives. This theoretical study suggests that the rearrangement process occurs through a concerted mechanism, in which the energy of the transition states can be lowered by the participation of a catalytic water molecule. Interestingly, it also suggested a role for the carboxylic acid at position 4 of the 2‐oxoazepane ring, which facilitates this rearrangement, participating directly in the intramolecular catalysis. 相似文献
2.
3.
4.
Monomeric sarcosine oxidase (mSOx) fusion with the silaffin peptide, R5, designed previously for easy protein production in low resource areas, was used in a biosilification process to form an enzyme layer electrode biosensor. mSOx is a low activity enzyme (10–20 U/mg) requiring high amounts of enzyme to obtain an amperometric biosensor signal, in the clinically useful range <1 mM sarcosine, especially since the Km is >10 mM. An amperometric biosensor model was fitted to experimental data to investigate dynamic range. mSOx constructs were designed with 6H (6×histidine) and R5 (silaffin) peptide tags and compared with native mSOx. Glutaraldehyde (GA) cross‐linked proteins retained ~5 % activity for mSOx and mSOx‐6H and only 0.5 % for mSOx‐R5. In contrast R5 catalysed biosilification on (3‐mercaptopropyl) trimethoxysilane (MPTMS) and tetramethyl orthosilicate (TMOS) particles created a ‘self‐immobilisation’ matrix retaining 40 % and 76 % activity respectively. The TMOS matrix produced a thick layer (>500 μm) on a glassy carbon electrode with a mediated current due to sarcosine in the clinical range for sarcosinemia (0–1 mM). The mSOx‐R5 fusion protein was also used to catalyse biosilification in the presence of creatinase and creatininase, entrapping all three enzymes. A mediated GC enzyme linked current was obtained with dynamic range available for creatinine determination of 0.1–2 mM for an enzyme layer ~800 nm. 相似文献
5.
6.
Highly Selective Copper‐Catalyzed Asymmetric [3+2] Cycloaddition of Azomethine Ylides with Acyclic 1,3‐Dienes 下载免费PDF全文
María González‐Esguevillas Ana Pascual‐Escudero Dr. Javier Adrio Prof. Dr. Juan C. Carretero 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(12):4561-4565
The first examples of the catalytic asymmetric 1,3‐dipolar cycloaddition of azomethine ylides with acyclic activated 1,3‐dienes (and 1,3‐enynes) are described. Under copper catalysis, a selective cycloaddition at the terminal γ,δ‐C?C bond is observed. In addition, depending on the ligand used, either the exo or the endo adduct can be obtained with high selectivity. Under appropriate reaction conditions, the acyclic 1,6‐addition product is detected, suggesting a stepwise mechanism. The resulting C4‐alkenyl‐substituted pyrrolidines are suitable substrates for further access to polycyclic systems, as highlighted by the preparation of hexahydrochromeno[4,3‐b]pyrrole and the tetracyclic core of the alkaloid gracilamine. 相似文献
7.
Elizabeth S. Senger 《School science and mathematics》1997,97(3):139-149
Thirteen fifth graders were given an assignment to invent their own numeration systems, following a unit on bases and a look at early events in the history of numbers. The task presented options that required the students to make decisions (such as whether to use a base, which base to use, design of symbols, etc.), and build a rationale for the elements of their system. Analyses of patterns embedded in their invented systems provided an assessment of student understanding of numeration. The progression of more and less complex thinking related to the student's choice of a base other than 10, consistency of logic throughout the system in words and symbols, rationale for change, and perception of real life examples that would change if the system was adopted. The invention task is presented as another way to make connections. 相似文献
8.
Lithium (10–150 ng ml?1) in wine is determined by atomic absorption spectrometry by direct nebulization and after digestion with mixed acids. The results of methods are similar. Thirty-four wines from various Spanish provinces are analysed. 相似文献
9.
Accreditation and Quality Assurance - 相似文献
10.
P. González D. Fernández J. Pou E. García J. Serra B. León M. Pérez-Amor T. Szörényi 《Applied Physics A: Materials Science & Processing》1993,57(2):181-185
A study of the gas-phase parameters involved in ArF laser induced chemical vapour deposition of silicon-oxide thin films is presented. A complete set of experiments has been performed showing the influence of the concentration of the precursor gases, N2O and SiH4, and their influence on total and partial pressures on film growth and properties. In this paper we demonstrate the ability of this LCVD method to deposit silicon oxide films of different compositions and densities by appropriate control of gas composition and total pressure. Moreover, a material specific calibration plot comprising data obtained using different preparation techniques is presented, allowing determination of the stoichiometry of SiO
x
films by using FTIR spectroscopy independently of the deposition method. For the range of processing conditions examined, the experimental results suggest that chemical processes governing deposition take place mainly in the gas phase. 相似文献