全文获取类型
收费全文 | 1250篇 |
免费 | 53篇 |
国内免费 | 21篇 |
专业分类
化学 | 675篇 |
晶体学 | 9篇 |
力学 | 57篇 |
数学 | 279篇 |
物理学 | 304篇 |
出版年
2023年 | 4篇 |
2021年 | 7篇 |
2020年 | 24篇 |
2019年 | 12篇 |
2018年 | 13篇 |
2017年 | 6篇 |
2016年 | 19篇 |
2015年 | 22篇 |
2014年 | 44篇 |
2013年 | 69篇 |
2012年 | 91篇 |
2011年 | 73篇 |
2010年 | 61篇 |
2009年 | 57篇 |
2008年 | 71篇 |
2007年 | 65篇 |
2006年 | 78篇 |
2005年 | 58篇 |
2004年 | 52篇 |
2003年 | 55篇 |
2002年 | 37篇 |
2001年 | 31篇 |
2000年 | 32篇 |
1999年 | 13篇 |
1998年 | 20篇 |
1997年 | 11篇 |
1996年 | 17篇 |
1995年 | 25篇 |
1994年 | 10篇 |
1993年 | 20篇 |
1992年 | 9篇 |
1991年 | 17篇 |
1990年 | 13篇 |
1989年 | 11篇 |
1988年 | 10篇 |
1987年 | 9篇 |
1986年 | 8篇 |
1985年 | 20篇 |
1984年 | 11篇 |
1983年 | 10篇 |
1982年 | 9篇 |
1981年 | 9篇 |
1980年 | 13篇 |
1979年 | 11篇 |
1978年 | 7篇 |
1977年 | 14篇 |
1976年 | 15篇 |
1975年 | 15篇 |
1973年 | 4篇 |
1970年 | 3篇 |
排序方式: 共有1324条查询结果,搜索用时 31 毫秒
51.
Gary N. W. Leung Francis P. W. Tang Terence S. M. Wan Colton H. F. Wong Kenneth K. H. Lam Brian D. Stewart 《Biomedical chromatography : BMC》2010,24(7):744-751
This paper describes the application of gas chromatography–mass spectrometry (GC‐MS) for in vitro and in vivo studies of 6‐OXO in horses, with a special aim to identify the most appropriate target metabolite to be monitored for controlling the administration of 6‐OXO in racehorses. In vitro studies of 6‐OXO were performed using horse liver microsomes. The major biotransformation observed was reduction of one keto group at the C3 or C6 positions. Three in vitro metabolites, namely 6α‐hydroxyandrost‐4‐ene‐3,17‐dione (M1), 3α‐hydroxyandrost‐4‐ene‐6,17‐dione (M2a) and 3β‐hydroxyandrost‐4‐ene‐6,17‐dione (M2b) were identified. For the in vivo studies, two thoroughbred geldings were each administered orally with 500 mg of androst‐4‐ene‐3,6,17‐trione (5 capsules of 6‐OXO®) by stomach tubing. The results revealed that 6‐OXO was extensively metabolized. The three in vitro metabolites (M1, M2a and M2b) identified earlier were all detected in post‐administration urine samples. In addition, seven other urinary metabolites, derived from a further reduction of either one of the remaining keto groups or one of the remaining keto groups and the olefin group, were identified. These metabolites included 6α,17β‐dihydroxyandrost‐4‐en‐3‐one (M3a), 6,17‐dihydroxyandrost‐4‐en‐3‐one (M3b and M3c), 3β,6β‐dihydroxyandrost‐4‐en‐17‐one (M4a), 3,6‐dihydroxyandrost‐4‐en‐17‐one (M4b), 3,6‐dihydroxyandrostan‐17‐one (M5) and 3,17‐dihydroxyandrostan‐6‐one (M6). The longest detection time observed in urine was up to 46 h for the M6 metabolite. For blood samples, the peak 6‐OXO plasma concentration was observed 1 h post administration. Plasma 6‐OXO decreased rapidly and was not detectable 12 h post administration. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
52.
A Facile Synthesis of 1,4-Diketones from Organolithium Reagents and N,N,N′,N′-Tetramethylsuccinamide
The reaction of organolithium reagents (alkyl, aryl, heteroaryl) with N,N,N′,N′-tetramethylsuccinamide at 0 °C gives good yields of the corresponding 1,4-diketones. 相似文献
53.
The automorphism group AutFn of a free group Fn of rank n acts on the product of n copies of a group G by substituting n elements of G into the words defining an automorphism of the free group. This gives rise to an antihomomorphism from AutFnto a permutation group. We determine this antihomomorphic image of AutFn when G is the semidirect product Zp x Zq 相似文献
54.
Container ports are a major component of international trade and the global supply chain. Hence, the improvement of port efficiency can have a significant impact on the wider maritime economy. This paper deconstructs a representation in the existing literature that neglects the heterogeneity of individual and group-specific terminal operators. In its place, we present a hierarchical model to make a connection between efficiency and terminal operator group characteristics. The paper develops a stochastic frontier model that controls not only individual heterogeneity but also group-specific variations. The model decomposes the total stochastic derivation from the frontier into inefficiency, individual heterogeneity, group-specific variations, and noise components, with the estimation being performed using Markov chain Monte Carlo simulations. The validity of the model is tested with a panel of container terminal operator data from 1997-2004. Our findings show that terminal operator groups are important in promoting terminal efficiency at the global level, and that the operators with stevedore backgrounds show a higher efficiency than carriers. 相似文献
55.
Yen‐Chung Chen Jonathan T. B. Huang Kee‐Ching G. Jeng Robin C. K. Yang Mo‐Kai Liao Chee‐Shan Chen Wei‐Jyun Chien Ming‐Tsair Wey Lou‐Sing Kan Leung Sheh 《中国化学会会志》2010,57(2):266-274
To study DNA allostery, quantitative DNase I footprinting studies were carried out on a newly designed peptide His‐Hyp‐Lys‐Lys‐(Py)4‐Lys‐Lys‐NH2 (HypKK‐10) containing the XHypKK (Hyp = hydroxyproline) and polyamide motifs. The interconnection of DNA footprints of peptides HypKK‐10 and the parent peptide PyPro‐12 supports the proposal that interaction network cooperativity is preferred in DNA‐peptide interactions between multiple recognition sites. A simple method of determining interstrand bidentate interactions between the peptide moieties and DNA bases is introduced. It is envisaged that interstrand bidentate interactions also participate in the relay of conformational changes to recognition sites on the complementary strands. Circular dichroism studies of the titration of peptide HypKK‐10 with an oligonucleotide duplex indicate that this peptide binds in a dimeric fashion to DNA in the minor groove. This work may prompt the design of new DNA binding ligands for the study of DNA‐peptide allosteric interactions and DNA interaction network. 相似文献
56.
Raymond Wai‐Yin Sun Dr. Carrie Ka‐Lei Li Dr. Dik‐Lung Ma Dr. Jessie Jing Yan Chun‐Nam Lok Dr. Chung‐Hang Leung Dr. Nianyong Zhu Dr. Chi‐Ming Che Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(10):3097-3113
In the design of physiologically stable anticancer gold(III) complexes, we have employed strongly chelating porphyrinato ligands to stabilize a gold(III) ion [Chem. Commun. 2003 , 1718; Coord. Chem. Rev. 2009 , 253, 1682]. In this work, a family of gold(III) tetraarylporphyrins with porphyrinato ligands containing different peripheral substituents on the meso‐aryl rings were prepared, and these complexes were used to study the structure–bioactivity relationship. The cytotoxic IC50 values of [Au(Por)]+ (Por=porphyrinato ligand), which range from 0.033 to >100 μM , correlate with their lipophilicity and cellular uptake. Some of them induce apoptosis and display preferential cytotoxicity toward cancer cells than to normal noncancerous cells. A new gold(III)–porphyrin with saccharide conjugation [Au(4‐glucosyl‐TPP)]Cl ( 2 a ; H2(4‐glucosyl‐TPP)=meso‐tetrakis(4‐β‐D ‐glucosylphenyl)porphyrin) exhibits significant cytostatic activity to cancer cells (IC50=1.2–9.0 μM ) without causing cell death and is much less toxic to lung fibroblast cells (IC50>100 μM ). The gold(III)–porphyrin complexes induce S‐phase cell‐cycle arrest of cancer cells as indicated by flow cytometric analysis, suggesting that the anticancer activity may be, in part, due to termination of DNA replication. The gold(III)–porphyrin complexes can bind to DNA in vitro with binding constants in the range of 4.9×105 to 4.1×106 dm3 mol?1 as determined by absorption titration. Complexes 2 a and [Au(TMPyP)]Cl5 ( 4 a ; [H2TMPyP]4+=meso‐tetrakis(N‐methylpyridinium‐4‐yl)porphyrin) interact with DNA in a manner similar to the DNA intercalator ethidium bromide as revealed by gel mobility shift assays and viscosity measurements. Both of them also inhibited the topoisomerase I induced relaxation of supercoiled DNA. Complex 4 a , a gold(III) derivative of the known G‐quadruplex‐interactive porphyrin [H2TMPyP]4+, can similarly inhibit the amplification of a DNA substrate containing G‐quadruplex structures in a polymerase chain reaction stop assay. In contrast to these reported complexes, complex 2 a and the parental gold(III)–porphyrin 1 a do not display a significant inhibitory effect (<10 %) on telomerase. Based on the results of protein expression analysis and computational docking experiments, the anti‐apoptotic bcl‐2 protein is a potential target for those gold(III)–porphyrin complexes with apoptosis‐inducing properties. Complex 2 a also displays prominent anti‐angiogenic properties in vitro. Taken together, the enhanced stabilization of the gold(III) ion and the ease of structural modification render porphyrins an attractive ligand system in the development of physiologically stable gold(III) complexes with anticancer and anti‐angiogenic activities. 相似文献
57.
58.
Various composites have been proposed in the literature for the fabrication of bioscaffolds for bone tissue engineering. These materials include poly(ε‐caprolactone) (PCL) with hydroxyapatite (HA). Since the biomaterial acts as the medium that transfers mechanical signals from the body to the cells, the fundamental properties of the biomaterials should be characterized. Furthermore, in order to control the processing of these materials into scaffolds, the characterization of the fundamental properties is also necessary. In this study, the physical, thermal, mechanical, and viscoelastic properties of the PCL‐HA micro‐ and nano‐composites were characterized. Although the addition of filler particles increased the compressive modulus by up to 450%, the thermal and viscoelastic properties were unaffected. Furthermore, although the presence of water plasticized the polymer, the viscoelastic behavior was only minimally affected. Testing the composites under various conditions showed that the addition of HA can strengthen PCL without changing its viscoelastic response. The results found in this study can be used to further understand and approximate the time‐dependent behavior of scaffolds for bone tissue engineering. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
59.
Two novel amphiphilic BAB-type block copolymers, ADN-PEG3400-ADN and Py-PEG3400-Py containing deep blue and bluish-green fluorescent moieties were prepared using atom transfer radical polymerization (ATRP) (where, ADN = poly(9,10-di(1-naphthalenyl)-2-vinylanthracene), Py = poly(1-vinyl pyrene) and PEG3400 = poly(ethylene glycol) with Mn = 3400 g/mol). The GPC number averaged molecular weights (MW) of the block copolymers were Mn = 9600 and 13,800 g/mol, respectively, based on polystyrene MW standards. The PEG3400 segment has a melting temperature (Tm peak) at 64–65 °C, whereas the glass transition temperatures (Tg midpoint) of the ADN and Py segments were found to be 230 °C and 193 °C, respectively, and are similar to their respective homopolymers indicating complete microphase segregration. The photoluminescence (PL) emission of the copolymers ADN-PEG3400-ADN exhibited two maxima at 423.5 nm and 441.5 nm while Py-PEG3400-Py has a maximum at 488.5 nm. Both copolymers form individual spherical micelles with diameter from 30 to 90 nm for Py-PEG3400-Py and 40–160 nm for ADN-PEG3400-ADN. The micelles, however, transform into cross-linked pearl-necklace-like aggregates at polymer concentrations above 1000 ppm, which may be attributed to the physical cross-linking between adjacent spherical micelles caused by the PEG3400 segments. 相似文献
60.
Lamellarin K is a complex pyrrole natural product and member of the lamellarin family – a group of natural products known for their potent biological activities, such as, antiproliferative activity and inhibition of P-gp mediated drug efflux pumps. We herein describe the synthesis of the N-benzyl-des-D ring analogue of lamellarin K using a route that centres on an acyl-Claisen reaction to eventually prepare a highly-functionalised 1-aryl-4-methyl-1,4-diketone. Paal-Knorr pyrrole formation using this diketone undergoes auto-oxidation to give a fully-substituted 5-formyl pyrrole which was converted into the natural lactone B ring. Antiproliferative testing of the N-benzyl-des-D ring analogue gave an IC50 of 2.63 μM against the MDA-MB-231 breast cancer cell line. 相似文献