全文获取类型
收费全文 | 164篇 |
免费 | 6篇 |
专业分类
化学 | 99篇 |
力学 | 1篇 |
数学 | 28篇 |
物理学 | 42篇 |
出版年
2023年 | 2篇 |
2020年 | 3篇 |
2019年 | 3篇 |
2017年 | 1篇 |
2016年 | 8篇 |
2015年 | 2篇 |
2014年 | 5篇 |
2013年 | 9篇 |
2012年 | 15篇 |
2011年 | 6篇 |
2010年 | 7篇 |
2009年 | 3篇 |
2008年 | 6篇 |
2007年 | 9篇 |
2006年 | 6篇 |
2005年 | 9篇 |
2004年 | 4篇 |
2003年 | 4篇 |
2002年 | 8篇 |
2001年 | 2篇 |
2000年 | 1篇 |
1999年 | 3篇 |
1998年 | 2篇 |
1997年 | 1篇 |
1996年 | 3篇 |
1995年 | 3篇 |
1994年 | 1篇 |
1993年 | 2篇 |
1992年 | 4篇 |
1991年 | 3篇 |
1990年 | 6篇 |
1989年 | 3篇 |
1988年 | 3篇 |
1987年 | 1篇 |
1986年 | 3篇 |
1985年 | 1篇 |
1984年 | 1篇 |
1981年 | 2篇 |
1980年 | 1篇 |
1979年 | 3篇 |
1977年 | 1篇 |
1975年 | 2篇 |
1973年 | 1篇 |
1972年 | 1篇 |
1970年 | 1篇 |
1968年 | 2篇 |
1967年 | 1篇 |
1966年 | 1篇 |
1938年 | 1篇 |
排序方式: 共有170条查询结果,搜索用时 11 毫秒
91.
92.
93.
The construction of homogeneous glycoproteins presents a formidable challenge to the synthetic chemist. Over the past few years there has been an explosion in the number of methods developed to address this problem. These methods include the development of novel ligation technologies for the synthesis of the protein backbone, as well chemical and enzymatic approaches for introducing complex glycans into the peptide backbone. This tutorial review discusses the application of these techniques to the synthesis of peptides and proteins possessing well defined glycans. 相似文献
94.
Lo HC Entwistle R Guo CJ Ahuja M Szewczyk E Hung JH Chiang YM Oakley BR Wang CC 《Journal of the American Chemical Society》2012,134(10):4709-4720
Meroterpenoids are a class of fungal natural products that are produced from polyketide and terpenoid precursors. An understanding of meroterpenoid biosynthesis at the genetic level should facilitate engineering of second-generation molecules and increasing production of first-generation compounds. The filamentous fungus Aspergillus nidulans has previously been found to produce two meroterpenoids, austinol and dehydroaustinol. Using targeted deletions that we created, we have determined that, surprisingly, two separate gene clusters are required for meroterpenoid biosynthesis. One is a cluster of four genes including a polyketide synthase gene, ausA. The second is a cluster of 10 additional genes including a prenyltransferase gene, ausN, located on a separate chromosome. Chemical analysis of mutant extracts enabled us to isolate 3,5-dimethylorsellinic acid and 10 additional meroterpenoids that are either intermediates or shunt products from the biosynthetic pathway. Six of them were identified as novel meroterpenoids in this study. Our data, in aggregate, allow us to propose a complete biosynthetic pathway for the A. nidulans meroterpenoids. 相似文献
95.
Chun-Jun Guo Wei-Wen Sun Kenneth S. Bruno Berl R. Oakley Nancy P. Keller Clay C. C. Wang 《Chemical science》2015,6(10):5913-5921
In secondary metabolite biosynthesis, core synthetic genes such as polyketide synthase genes usually encode proteins that generate various backbone precursors. These precursors are modified by other tailoring enzymes to yield a large variety of different secondary metabolites. The number of core synthesis genes in a given species correlates, therefore, with the number of types of secondary metabolites the organism can produce. In our study, heterologous expression of all the A. terreus NRPS-like genes showed that two NRPS-like proteins, encoded by atmelA and apvA, release the same natural product, aspulvinone E. In hyphae this compound is converted to aspulvinones whereas in conidia it is converted to melanin. The genes are expressed in different tissues and this spatial control is probably regulated by their own specific promoters. Comparative genomics indicates that atmelA and apvA might share a same ancestral gene and the gene apvA is located in a highly conserved region in Aspergillus species that contains genes coding for life-essential proteins. Our data reveal the first case in secondary metabolite biosynthesis in which the tissue specific production of a single compound directs it into two separate pathways, producing distinct compounds with different functions. Our data also reveal that a single trans-prenyltransferase, AbpB, prenylates two substrates, aspulvinones and butyrolactones, revealing that genes outside of contiguous secondary metabolism gene clusters can modify more than one compound thereby expanding metabolite diversity. Our study raises the possibility of incorporation of spatial, cell-type specificity in expression of secondary metabolites of biological interest and provides new insight into designing and reconstituting their biosynthetic pathways. 相似文献
96.
GYÖRGY TARCZAY ATTILA G. CSÁSZÁR WIM KLOPPER HARRY M. QUINEY 《Molecular physics》2013,111(21):1769-1794
Relativistic energy corrections which arise from the use of the Dirac-Coulomb Hamiltonian, and the Gaunt and Breit interaction operators, plus Lamb-shift effects have been determined for the global minima of the ground electronic states of C2H6, NH3, H2O, [H,C,N], HNCO, HCOOH, SiC2, SiH? 3, and H2S, and for barrier characteristics for these molecular systems (inversion barrier of NH3 and SiH? 3, barrier to linearity of H2O, H2S, and HNCO, rotational barrier of C2H6, difference between conformations of HCOOH (Z/E) and SiC2 (linear/T-shaped), and isomerization barrier of HCN/HNC). The relativistic calculations performed at the Hartree-Fock and the highly correlated CCSD(T) levels employed a wide variety of basis sets. Comparison of the perturbational and the four-component fully variational results indicate that the Coulomb-Pauli Hamiltonian and the lowest order Hamiltonian of direct perturbation theory (DPT(2)) are highly successful for treating the relativistic energy effects in light molecular systems both at a single point on the potential energy hypersurface and along the surface. Electron correlation contributions to the relativistic corrections are relatively small for the systems studied, and are comparable with the 2-electron Darwin correction. Corrections beyond the Dirac-Coulomb treatment are usually rather small, but may become important for high accuracy ab initio calculations. 相似文献
97.
Ahuja M Chiang YM Chang SL Praseuth MB Entwistle R Sanchez JF Lo HC Yeh HH Oakley BR Wang CC 《Journal of the American Chemical Society》2012,134(19):8212-8221
Genome sequencing has revealed that fungi have the ability to synthesize many more natural products (NPs) than are currently known, but methods for obtaining suitable expression of NPs have been inadequate. We have developed a successful strategy that bypasses normal regulatory mechanisms. By efficient gene targeting, we have replaced, en masse, the promoters of nonreducing polyketide synthase (NR-PKS) genes, key genes in NP biosynthetic pathways, and other genes necessary for NR-PKS product formation or release. This has allowed us to determine the products of eight NR-PKSs of Aspergillus nidulans, including seven novel compounds, as well as the NR-PKS genes required for the synthesis of the toxins alternariol (8) and cichorine (19). 相似文献
98.
Over the course of developing a multigram scale preparation of epoxy quinol 1 via asymmetric transfer hydrogenation (ATH) using the Noyori Ru(arene)(S,S-TsDPEN) catalysts, we observed several unexpected phenomena, including (i) chemoselective alkene vs ketone reduction of an enedione, (ii) a significant arene ligand effect (p-cymene vs. mesitylene) on the reaction pathway, and (iii) solvent-based reversal of the sense of enantioinduction. 相似文献
99.
Dehydrative glycosylation reactions using 2-deoxy- and 2,6-dideoxy-sugar donors promoted by a combination of 3,3-dichloro-1,2-diphenylcyclopropene and tetrabutylammonium iodide (TBAI) are described. The reactions are α-selective and proceed under mild conditions at room temperature without the need for special dehydrating agents. The reaction is shown to be effective with a number of glycosyl acceptors, including those possessing acid and base sensitive functionality. 相似文献
100.
Cleveland D Long SE Sander LC Davis WC Murphy KE Case RJ Rimmer CA Francini L Patri AK 《Analytical and bioanalytical chemistry》2010,398(7-8):2987-2995
Speciation measurements of gadolinium in liposomal MRI contrast agents (CAs) are complicated by the presence of emulsifiers, surfactants, and therapeutic agents in the formulations. The present paper describes two robust, hyphenated chromatography methods for the separation and quantification of gadolinium in nanoemulsion-based CA formulations. Three potential species of gadolinium, free gadolinium ion, gadolinium chelated by diethylenetriamine pentaacetic acid, and gadolinium chelated by 1,2-dimyristoyl-sn-glycero-3-phosphoethanolamine-N-diethylenetriaminepentaacetic acid, were present in the CA formulations. The species were separated by reversed-phase chromatography (reversed phase high-performance liquid chromatography, RP-HPLC) or by high-pressure size-exclusion chromatography (HPSEC). For RP-HPLC, fluorescence detection and post-column online isotope dilution inductively coupled plasma mass spectrometry (ID-ICP-MS) were used to measure the amount of gadolinium in each species. Online ID-ICP-MS and species-specific isotope dilution (SID)-ICP-MS were used in combination with the HPSEC column. The results indicated that some inter-species conversions and degradation had occurred within the samples and that SID-ICP-MS should be used to provide the most reliable measurements of total and speciated gadolinium. However, fluorescence and online ID-ICP-MS might usefully be applied as qualitative, rapid screening procedures for the presence of free gadolinium ions. 相似文献