全文获取类型
收费全文 | 868篇 |
免费 | 27篇 |
国内免费 | 2篇 |
专业分类
化学 | 735篇 |
晶体学 | 6篇 |
力学 | 2篇 |
数学 | 47篇 |
物理学 | 107篇 |
出版年
2022年 | 4篇 |
2021年 | 5篇 |
2020年 | 16篇 |
2019年 | 10篇 |
2018年 | 5篇 |
2017年 | 8篇 |
2016年 | 14篇 |
2015年 | 17篇 |
2014年 | 14篇 |
2013年 | 42篇 |
2012年 | 44篇 |
2011年 | 52篇 |
2010年 | 31篇 |
2009年 | 31篇 |
2008年 | 58篇 |
2007年 | 59篇 |
2006年 | 53篇 |
2005年 | 49篇 |
2004年 | 57篇 |
2003年 | 36篇 |
2002年 | 53篇 |
2001年 | 22篇 |
2000年 | 17篇 |
1999年 | 11篇 |
1998年 | 14篇 |
1997年 | 10篇 |
1996年 | 19篇 |
1995年 | 4篇 |
1994年 | 8篇 |
1993年 | 7篇 |
1992年 | 12篇 |
1989年 | 7篇 |
1988年 | 7篇 |
1987年 | 3篇 |
1986年 | 8篇 |
1985年 | 11篇 |
1984年 | 10篇 |
1983年 | 6篇 |
1982年 | 4篇 |
1981年 | 12篇 |
1980年 | 4篇 |
1979年 | 15篇 |
1978年 | 3篇 |
1977年 | 4篇 |
1975年 | 7篇 |
1966年 | 2篇 |
1943年 | 2篇 |
1930年 | 1篇 |
1929年 | 2篇 |
1889年 | 1篇 |
排序方式: 共有897条查询结果,搜索用时 718 毫秒
91.
92.
93.
C‐Selective and Diastereoselective Alkyl Addition to β,γ‐Alkynyl‐α‐imino Esters with Zinc(II)ate Complexes
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Manabu Hatano Kenji Yamashita Mai Mizuno Orie Ito Prof. Dr. Kazuaki Ishihara 《Angewandte Chemie (International ed. in English)》2015,54(9):2707-2711
Since umpolung α‐imino esters contain three electrophilic centers, regioselective alkyl addition with traditional organometallic reagents has been a serious problem in the practical synthesis of versatile chiral α‐amino acid derivatives. An unusual C‐alkyl addition to α‐imino esters using a Grignard reagent (RMgX)‐derived zinc(II)ate was developed. Zinc(II)ate complexes consist of a Lewis acidic [MgX]+ moiety, a nucleophilic [R3Zn]? moiety, and 2 [MgX2]. Therefore, the ionically separated [R3Zn]? selectively attacks the imino carbon atom ,which is most strongly activated by chelation of [MgX]+. In particular, chiral β,γ‐alkynyl‐α‐imino esters can strongly promote highly regio‐ and diastereoselective C‐alkylation because of structural considerations, and the corresponding optically active α‐quaternary amino acid derivatives are obtained within 5 minutes in high to excellent yields. 相似文献
94.
Identification and Purification of the CPD Photolyase in Vibrio parahaemolyticus RIMD2210633
下载免费PDF全文
![点击此处可从《Photochemistry and photobiology》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Kazuaki Mawatari Ping Tang Shuya He Takaaki Shimohata Yimou Wu Weidong Yin Akira Takahashi 《Photochemistry and photobiology》2015,91(5):1165-1172
Photoreactivation is an error‐free mechanism of DNA repair, utilized by prokaryotes and most eukaryotes and is catalyzed by specific enzymes called DNA photolyases. Photoreactivation has been reported in Vibrio parahaemolyticus WP28; however, information on photolyases in V. parahaemolyticus (V.p) strains has not been reported. This study examined the photoreactivation in V.p RIMD2210633. The photolyase responsible for repairing cyclobutane pyrimidine dimer (CPD) in DNA was identified, and the corresponding gene was determined as VPA1471. The protein was overexpressed in Escherichia coli and was purified for functional assessment in vitro. The mRNA level and protein expression level of this gene increased after ultraviolet A (UVA) illumination following ultraviolet C (UVC) irradiation. In vitro experiments confirmed that the protein encoded by VPA1471 could reduce the quantity of CPD in DNA. We designated the corresponding gene and protein of VPA1471 phr and Phr, respectively, although the function of two other photolyase/cryptochrome family members, VPA0203 and VPA0204, remains unclear. UV (ultraviolet) irradiation experiments suggest that these two genes possess some photorepairing ability. Therefore, we hypothesize that VPA0203 and VPA0204 encode (6‐4) photolyase in V. parahaemolyticus RIMD2210633. 相似文献
95.
Oligosaccharides in therapeutic recombinant antibodies play important roles in regulation of various biological functions. To monitor the glycosylation profiles of antibody pharmaceuticals in the manufacturing process, a highly sensitive and specific method is required. We extended partial-filling techniques using lectins and exoglycosidases in capillary electrophoresis for the characterization of 8-aminopylene-1,3,6-trisulfonic acid labeled N-linked oligosaccharides derived from the therapeutic antibody rituximab. In the lectin-filling method, Galb1–4GlcNAc-specific Erythrina cristagali agglutinin, a1, 6-linked Fuc-specific Aleuria aurantia lectin and Neu5Aca2–3Gal-specific Maackia amurensis lectin were used. The oligosaccharides migrated through the lectin plug during separation; the changes in separation profiles were observed according to the interaction with the lectins. The glycosidase-filling method allowed rapid digestion as suggested by the electropherograms. Partial-filling CE methods can avoid tedious hands-on procedures such as overnight incubation and optimization reaction condition with lectins and exoglycosidases. Combination of these partial-filling capillary electrophoresis methods makes the characterization of oligosaccharide profiles of therapeutic antibodies easier and faster. 相似文献
96.
We report on the fabrication of a microarray of supported lipid bilayers (SLBs) with different chemical compositions and demonstrate its biosensing application. The technique utilizes the phenomenon of lipid self-spreading on a patterned surface, which offers complete positional selectivity for a supported lipid bilayer. We describe the fabrication of parallel 10-μm-wide lines, each filled with an SLB with a unique composition, at 5 μm intervals. Structures obtained with our new technique are finer and more highly integrated than previously reported structures that employ the vesicle fusion technique on patterned surfaces. We also detected specific binding between biotin and streptavidin with high contrast, indicating that the microarray is valuable for biosensing applications. 相似文献
97.
98.
Doi T Shibata K Yoshida M Takagi M Tera M Nagasawa K Shin-ya K Takahashi T 《Organic & biomolecular chemistry》2011,9(2):387-393
Total synthesis of the (S)-stereoisomer of telomestatin (1) was accomplished. (S)-Telomestatin exhibited potency four times that of the natural product, (R)-telomestatin, which was the most potent telomerase inhibitor previously reported. In the circular dichroism spectral analysis of the complexes possessing randomly structured single-stranded d[TTAGGG](4) oligonucleotide, (S)-telomestatin, like (R)-telomestatin, induced an antiparallel G-quadruplex structure. The melting temperature (T(m)) value of the (S)-isomer complex was greater than that of the (R)-telomestatin complex. Therefore, it is concluded that the stereochemistry of the thiazoline of telomestatin is important to the binding ability of a G-quadruplex binder, and (S)-telomestatin as a G-quadruplex binder is more potent than the natural product. 相似文献
99.
Thermal [2+2] cycloaddition of morpholinoenamines with C60 via a single electron transfer 总被引:1,自引:0,他引:1
The thermal reaction of C(60) with five- and six-membered morpholinocycloalkenes in refluxing toluene exclusively gave the [2+2] cycloadducts in high yields. However, a seven-membered homologue sluggishly reacted with C(60) because of the increasing steric hindrance. This cycloaddition reaction is likely to proceed via a single electron transfer (SET), a radical-coupling, and subsequent ion cyclization rather than the prior proton transfer between the radical ions. 相似文献
100.
Kazuaki Taira 《Mathematische Nachrichten》2011,284(1):105-123
The purpose of this paper is to study a class of semilinear elliptic boundary value problems with degenerate boundary conditions which include as particular cases the Dirichlet problem and the Robin problem. The approach here is based on the super‐sub‐solution method in the degenerate case, and is distinguished by the extensive use of an Lp Schauder theory elaborated for second‐order, elliptic differential operators with discontinuous zero‐th order term. By using Schauder's fixed point theorem, we prove that the existence of an ordered pair of sub‐ and supersolutions of our problem implies the existence of a solution of the problem. The results extend an earlier theorem due to Kazdan and Warner to the degenerate case. © 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim 相似文献