全文获取类型
收费全文 | 1581篇 |
免费 | 56篇 |
国内免费 | 2篇 |
专业分类
化学 | 1332篇 |
晶体学 | 23篇 |
力学 | 10篇 |
数学 | 74篇 |
物理学 | 200篇 |
出版年
2023年 | 11篇 |
2022年 | 15篇 |
2021年 | 27篇 |
2020年 | 21篇 |
2019年 | 25篇 |
2018年 | 20篇 |
2017年 | 17篇 |
2016年 | 35篇 |
2015年 | 25篇 |
2014年 | 40篇 |
2013年 | 88篇 |
2012年 | 76篇 |
2011年 | 105篇 |
2010年 | 49篇 |
2009年 | 49篇 |
2008年 | 118篇 |
2007年 | 117篇 |
2006年 | 107篇 |
2005年 | 141篇 |
2004年 | 97篇 |
2003年 | 67篇 |
2002年 | 71篇 |
2001年 | 23篇 |
2000年 | 20篇 |
1999年 | 10篇 |
1998年 | 24篇 |
1997年 | 15篇 |
1996年 | 27篇 |
1995年 | 11篇 |
1994年 | 12篇 |
1993年 | 7篇 |
1992年 | 5篇 |
1991年 | 7篇 |
1989年 | 8篇 |
1988年 | 5篇 |
1987年 | 4篇 |
1986年 | 9篇 |
1985年 | 12篇 |
1984年 | 15篇 |
1983年 | 7篇 |
1982年 | 20篇 |
1981年 | 10篇 |
1980年 | 17篇 |
1979年 | 5篇 |
1978年 | 11篇 |
1977年 | 8篇 |
1976年 | 5篇 |
1975年 | 5篇 |
1974年 | 6篇 |
1973年 | 3篇 |
排序方式: 共有1639条查询结果,搜索用时 31 毫秒
161.
Koji Umeda Takahiro Hanamuro Kunimi Yamada Yoshimitsu Negishi Hideki Iwano Tohru Danhara 《Radiation measurements》2007,42(10):1647-1654
162.
Hideki Shimura Ryota Tanaka Yoshiaki Shimada Kazuo Yamashiro Nobutaka Hattori Takao Urabe 《BMC biochemistry》2017,18(1):14
Background
Peptides with cytoprotective functions, including antioxidants and anti-infectives, could be useful therapeutics. Carnosine, β-alanine-histidine, is a dipeptide with anti-oxidant properties. Tripeptides of Ala-His-Lys, Pro-His-His, or Tyr-His-Tyr are also of interest in this respect.Results
We synthesized several histidine-containing peptides including glycine or alanine, and tested their cytoprotective effects on hydrogen peroxide toxicity for PC12 cells. Of all these peptides (Gly-His-His, Ala-His-His, Ala-His-Ala, Ala-Ala-His, Ala-Gly-His, Gly-Ala-His (GAH), Ala-His-Gly, His-Ala-Gly, His-His-His, Gly-His-Ala, and Gly-Gly-His), GAH was found to have the strongest cytoprotective activity. GAH decreased lactate dehydrogenase (LDH) leakage, apoptosis, morphological changes, and nuclear membrane permeability changes against hydrogen peroxide toxicity in PC12 cells. The cytoprotective activity of GAH was superior to that of carnosine against hydrogen peroxide toxicity in PC12 cells. GAH also protected PC12 cells against damage caused by actinomycin D and staurosporine. Additionally, it was found that GAH also protected SH-SY5Y and Jurkat cells from damage caused by hydrogen peroxide, as assessed by LDH leakage.Conclusion
Thus, a novel tripeptide, GAH, has been identified as having broad cytoprotective effects against hydrogen peroxide-induced cell damage.163.
Prof. Dr. Hideki Yorimitsu 《Chemical record (New York, N.Y.)》2017,17(11):1156-1167
A new class of Pummerer chemistry has emerged as a powerful tool in organic synthesis. The new technology consists of a beautiful cascade of an interrupted Pummerer reaction and the subsequent [3,3] sigmatropic rearrangement. The interrupted Pummerer reactions of alkenyl or aryl sulfoxides with unsaturated nucleophiles such as allylic silanes, ketones, and phenols provide sulfonium intermediates, which are ready to undergo smooth charge‐accelerated [3,3] sigmatropic rearrangement with excellent to exclusive regioselectivity. Some of the transformations proceed with transient loss of aromaticity. The reactions afforded five‐membered heterocycles, benzofurans, and biaryls of importance, depending on the sulfoxides and nucleophiles used. The reactions are unique and game‐changing because they are efficient, robust, redox‐neutral, regioselective, and metal‐free, which perfectly fits the need of modern organic synthesis. This chemistry also underscores the synthetic potential of organosulfur chemistry. 相似文献
164.
Ghosh A Yusa S Matsuoka H Saruwatari Y 《Langmuir : the ACS journal of surfaces and colloids》2011,27(15):9237-9244
Cationic amphiphilic diblock copolymers of poly(n-butylacrylate)-b-poly(3-(methacryloylamino)propyl)trimethylammonium chloride) (PBA-b-PMAPTAC) with various hydrophobic and hydrophilic chain lengths were synthesized by a reversible addition-fragmentation chain transfer (RAFT) process. Their molecular characteristics such as surface activity/nonactivity were investigated by surface tension measurements and foam formation observation. Their micelle formation behavior and micelle structure were investigated by fluorescence probe technique, static and dynamic light scattering (SLS and DLS), etc., as a function of hydrophilic and hydrophobic chain lengths. The block copolymers were found to be non-surface active because the surface tension of the aqueous solutions did not change with increasing polymer concentration. Critical micelle concentration (cmc) of the polymers could be determined by fluorescence and SLS measurements, which means that these polymers form micelles in bulk solution, although they were non-surface active. Above the cmc, the large blue shift of the emission maximum of N-phenyl-1-naphthylamine (NPN) probe and the low micropolarity value of the pyrene probe in polymer solution indicate the core of the micelle is nonpolar in nature. Also, the high value of the relative intensity of the NPN probe and the fluorescence anisotropy of the 1,6-diphenyl-1,3,5-hexatriene (DPH) probe indicated that the core of the micelle is highly viscous in nature. DLS was used to measure the average hydrodynamic radii and size distribution of the copolymer micelles. The copolymer with the longest PBA block had the poorest water solubility and consequently formed micelles with larger size while having a lower cmc. The "non-surface activity" was confirmed for cationic amphiphilic diblock copolymers in addition to anionic ones studied previously, indicating the universality of non-surface activity nature. 相似文献
165.
166.
Kuwamura N Kitano K Hirotsu M Nishioka T Teki Y Santo R Ichimura A Hashimoto H Wright LJ Kinoshita I 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(38):10708-10715
Interchange between the nickel +2 and +3 oxidation states precisely controls the reversible rearrangement of the tris(2-pyridylthio)methanide (tptm) ligand in the organometallic nickel(II) complex [{Ni(μ-Br)-(tptm)}(2)] (2). Oxidation of 2 first gives the corresponding Ni(III) complex [{Ni(μ-Br)(tptm)}(2)][PF(6)](2) (4). However, in solution the tptm ligand in 4 slowly undergoes a rearrangement, in which the N and S atoms of one of the pyridylthiolate arms exchange Ni and C bonding partners, thereby resulting in an "N,S-confused" isomer of tptm in the product, [NiBr(bpttpm)]PF(6) (5; bpttpm= bis(2-pyridylthio)(2-thiopyridinium)-methyl). Reduction of 5 reverses this ligand rearrangement and 2 is reformed quantitatively. The individual steps involved in these unusual ligand rearrangements were investigated by a number of methods, including voltammetric analysis, and a mechanism for this process is proposed. X-ray crystal structure determinations of the key compounds 2, 4 and 5 have been obtained. 相似文献
167.
Palladium-catalyzed arylative cyclization of propargyl-substituted malonate esters with aryl halides offers a stereoselective approach to alkylidenecyclopropanes. The reaction proceeds by an anti-carbopalladation pathway, which guarantees the exclusive stereocontrol of the resulting double bond. The highly strained as well as densely substituted skeletons of the products facilitate further versatile transformations, which underscores the importance of the products as synthetic intermediates. 相似文献
168.
Touge T Hakamata T Nara H Kobayashi T Sayo N Saito T Kayaki Y Ikariya T 《Journal of the American Chemical Society》2011,133(38):14960-14963
Newly developed oxo-tethered Ru amido complexes (R,R)-1 and their HCl adducts (R,R)-2 exhibited excellent catalytic performance for both asymmetric transfer hydrogenation and the hydrogenation of ketonic substrates under neutral conditions without any cocatalysts to give chiral secondary alcohols with high levels of enantioselectivity. 相似文献
169.
Urita K Shiga Y Fujimori T Iiyama T Hattori Y Kanoh H Ohba T Tanaka H Yudasaka M Iijima S Moriguchi I Okino F Endo M Kaneko K 《Journal of the American Chemical Society》2011,133(27):10344-10347
An outstanding compression function for materials preparation exhibited by nanospaces of single-walled carbon nanohorns (SWCNHs) was studied using the B1-to-B2 solid phase transition of KI crystals at 1.9 GPa. High-resolution transmission electron microscopy and synchrotron X-ray diffraction examinations provided evidence that KI nanocrystals doped in the nanotube spaces of SWCNHs at pressures below 0.1 MPa had the super-high-pressure B2 phase structure, which is induced at pressures above 1.9 GPa in bulk KI crystals. This finding of the supercompression function of the carbon nanotubular spaces can lead to the development of a new compression-free route to precious materials whose syntheses require the application of high pressure. 相似文献
170.
Sodium or lithium ion-binding-induced structural changes in the K-ring of V-ATPase from Enterococcus hirae revealed by ATR-FTIR spectroscopy 总被引:1,自引:0,他引:1
V-ATPase from Enterococcus hirae forms a large supramolecular protein complex (total molecular weight ~700,000) and physiologically transports Na(+) and Li(+) across a hydrophobic lipid bilayer. Stabilization of these cations in the binding site has been discussed on the basis of X-ray crystal structures of a membrane-embedded domain, the K-ring (Na(+)- and Li(+)-bound forms). Here, sodium or lithium ion-binding-induced difference IR spectra of the intact V-ATPase have for the first time been measured at physiological temperature under a sufficient amount of hydration. The results suggest that sodium or lithium ion binding induces the deprotonation of Glu139, a hydrogen-bonding change in the tyrosine residue, and a small conformational change in the K-ring. These structural changes, especially the deprotonation of Glu139, are considered to be important for reducing energetic barriers to the transport of cations through the membrane. 相似文献