全文获取类型
收费全文 | 1439篇 |
免费 | 31篇 |
国内免费 | 1篇 |
专业分类
化学 | 883篇 |
晶体学 | 15篇 |
力学 | 37篇 |
数学 | 133篇 |
物理学 | 403篇 |
出版年
2020年 | 14篇 |
2019年 | 11篇 |
2018年 | 7篇 |
2017年 | 8篇 |
2016年 | 17篇 |
2015年 | 13篇 |
2014年 | 23篇 |
2013年 | 66篇 |
2012年 | 56篇 |
2011年 | 80篇 |
2010年 | 46篇 |
2009年 | 29篇 |
2008年 | 59篇 |
2007年 | 67篇 |
2006年 | 68篇 |
2005年 | 61篇 |
2004年 | 83篇 |
2003年 | 45篇 |
2002年 | 49篇 |
2001年 | 42篇 |
2000年 | 46篇 |
1999年 | 27篇 |
1998年 | 26篇 |
1997年 | 12篇 |
1996年 | 21篇 |
1995年 | 21篇 |
1994年 | 25篇 |
1993年 | 42篇 |
1992年 | 27篇 |
1991年 | 18篇 |
1990年 | 15篇 |
1989年 | 12篇 |
1988年 | 16篇 |
1987年 | 8篇 |
1986年 | 19篇 |
1985年 | 18篇 |
1984年 | 15篇 |
1983年 | 11篇 |
1982年 | 16篇 |
1981年 | 10篇 |
1980年 | 10篇 |
1979年 | 16篇 |
1978年 | 20篇 |
1977年 | 13篇 |
1976年 | 22篇 |
1975年 | 15篇 |
1974年 | 11篇 |
1973年 | 10篇 |
1972年 | 8篇 |
1971年 | 10篇 |
排序方式: 共有1471条查询结果,搜索用时 31 毫秒
71.
Thomas W. Gero Larry W. Jaques Richard P. Mays Debra H. Reid Dwight A. Shamblee Young S. Lo 《合成通讯》2013,43(3-4):553-559
A convenient method to prepare 5-halo-2-hydroxy-nicotinic acid is described. 相似文献
72.
Sudarsanan Varaprath Mark Seaton Debra McNett Lin Cao Kathleen P. Plotzke 《International journal of environmental analytical chemistry》2013,93(3):203-219
Abstract A method was developed and validated to measure octamethylcyclotetrasiloxane (D4)? quantitatively by gas chromatography-mass spectrometry (GC-MS) at low level in extracts of several biological matrices that include plasma, liver, lung, feces and fat from rats. The key to the successful determination lay in the use of extracts dried with anhydrous magnesium sulfate. This was necessary in view of the propensity of the methyl siloxane based GC-stationary phase to generate D4 by its reaction with water present in the extracts. To enable quantiiation of D4 at parts per billion (μg/L) levels, the base ion m/z 281 resulting from the loss of a methyl group from the parent molecule was selected for monitoring by SIM mode in GC-MS. The recovery of D4 from any of the biological matrices was determined to be greater than 90% in three extractions. The D4 response for the standards in GC-MS was linear (R2 > 0.9900) and reproducible at concentrations ranging from 1—16,000 ng D4/g solvent. Precision was less than 5%. 相似文献
73.
74.
Ryan M. Tipker Jake A. Muldoon Daniel H. Pham Balazs R. Varga Russell P. Hughes David S. Glueck Gary J. Balaich Arnold L. Rheingold 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2022,134(1):e202110753
Tetrahedral main-group compounds are normally configurationally stable, but P-epimerization of the chiral phosphiranium cations syn- or anti-[Mes*P(Me)CH2CHPh][OTf] (Mes*=2,4,6-(t-Bu)3C6H2) occurred under mild conditions at 60 °C in CD2Cl2, resulting in isomerization to give a syn-enriched equilibrium mixture. Ion exchange with excess [NBu4][Δ-TRISPHAT] (Δ-TRISPHAT=Δ-P(o-C6Cl4O2)3) followed by chromatography on silica removed [NBu4][OTf] and gave mixtures of syn- and anti-[Mes*P(Me)CH2CHPh][Δ-TRISPHAT]?x[NBu4][Δ-TRISPHAT]. NMR spectroscopy showed that isomerization proceeded with epimerization at P and retention at C. DFT calculations are consistent with a mechanism involving P-C cleavage to yield a hyperconjugation-stabilized carbocation, pyramidal inversion promoted by σ-interaction of the P lone pair with the neighboring β-carbocation, and ring closure with inversion of configuration at P. 相似文献
75.
Ricardo G. Alvim Petrina Georgala Lucas Nogueira Alexander J. Somma Karan Nagar Jasmine Thomas Laura Alvim Amelia Riegel Christopher Hughes Jie Chen Augusto B. Reis Souhil Lebdai Avigdor Scherz Steven Zanganeh Rui Gardner Kwanghee Kim Jonathan A. Coleman 《Molecules (Basel, Switzerland)》2021,26(12)
Purpose: Vascular targeted photodynamic therapy (VTP) is a nonsurgical tumor ablation approach used to treat early-stage prostate cancer and may also be effective for upper tract urothelial cancer (UTUC) based on preclinical data. Toward increasing response rates to VTP, we evaluated its efficacy in combination with concurrent PD-1 inhibitor/OX40 agonist immunotherapy in a urothelial tumor-bearing model. Experimental design: In mice allografted with MB-49 UTUC cells, we compared the effects of combined VTP with PD-1 inhibitor/OX40 agonist with those of the component treatments on tumor growth, survival, lung metastasis, and antitumor immune responses. Results: The combination of VTP with both PD-1 inhibitor and OX40 agonist inhibited tumor growth and prolonged survival to a greater degree than VTP with either immunotherapeutic individually. These effects result from increased tumor infiltration and intratumoral proliferation of cytotoxic and helper T cells, depletion of Treg cells, and suppression of myeloid-derived suppressor cells. Conclusions: Our findings suggest that VTP synergizes with PD-1 blockade and OX40 agonist to promote strong antitumor immune responses, yielding therapeutic efficacy in an animal model of urothelial cancer. 相似文献
76.
Chen X Zhang L Zhou K Davies E Sugden K Bennion I Hughes M Hine A 《Optics letters》2007,32(17):2541-2543
Using an optical biosensor based on a dual-peak long-period fiber grating, we have demonstrated the detection of interactions between biomolecules in real time. Silanization of the grating surface was successfully realized for the covalent immobilization of probe DNA, which was subsequently hybridized with the complementary target DNA sequence. It is interesting to note that the DNA biosensor was reusable after being stripped off the hybridized target DNA from the grating surface, demonstrating a function of multiple usability. 相似文献
77.
“CLASSIC NMR”: An In‐Situ NMR Strategy for Mapping the Time‐Evolution of Crystallization Processes by Combined Liquid‐State and Solid‐State Measurements
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. Colan E. Hughes P. Andrew Williams Prof. Kenneth D. M. Harris 《Angewandte Chemie (International ed. in English)》2014,53(34):8939-8943
A new in‐situ NMR strategy (termed CLASSIC NMR) for mapping the evolution of crystallization processes is reported, involving simultaneous measurement of both liquid‐state and solid‐state NMR spectra as a function of time. This combined strategy allows complementary information to be obtained on the evolution of both the solid and liquid phases during the crystallization process. In particular, as crystallization proceeds (monitored by solid‐state NMR), the solution state becomes more dilute, leading to changes in solution‐state speciation and the modes of molecular aggregation in solution, which are monitored by liquid‐state NMR. The CLASSIC NMR experiment is applied here to yield new insights into the crystallization of m‐aminobenzoic acid. 相似文献
78.
Suzanne K. Estok Thomas A. Hughes IV Mary K. Carroll Ann M. Anderson 《Journal of Sol-Gel Science and Technology》2014,70(3):371-377
Silica aerogels were prepared using the precursor tetraethylorthosilicate (TEOS) via a rapid supercritical extraction (RSCE) method. Multiple consistent batches of monolithic TEOS-based aerogels were fabricated via an 8-h RSCE process. Fabricating TEOS-based aerogels with an RSCE method offers some distinct advantages. One advantage is the relative simplicity of the RSCE approach: liquid precursors are mixed and poured into a metal mold in a hydraulic hot-press, where gelation, aging and extraction of liquid from the pores occur. The precursor recipe employs TEOS, ethanol, water, oxalic acid to catalyze hydrolysis, and ammonia to catalyze the subsequent polycondensation reactions. Another advantage is that reaction of TEOS to form sol gels yields ethanol as a byproduct. A process that releases ethanol, rather than methanol (as in tetramethylorthosilicate (TMOS)-based aerogels) may be more appealing for commercial applications, involving scale-up of the process. The significantly lower cost of TEOS, compared to TMOS, is a considerable advantage. The TEOS-based RSCE aerogels are mesoporous and optically translucent, have bulk densities of 0.099(±0.003) g/cm3 and surface areas of 460(±10) m2/g. Signals observed in infrared and Raman spectra of the aerogels are consistent with Si–O framework bonds. Using scanning electron microscopy imaging, the surface morphology of the aerogel samples was imaged at magnifications up to 150 kX. 相似文献
79.
Carlos M. Nuez J. Kaye Whitfield Debra J. Mercurio John R. Ilzhoefer Richard J. Spontak Saad A. Khan 《Macromolecular Symposia》1996,106(1):275-286
Dibenzylidene sorbitol (DBS) is capable of gelling a variety of organic solvents and polymeric materials by forming a rigid, 3-D hydrogen-bonded network. In this work, two poly(siloxane)/poly(propylene oxide) segmented copolymers of equal composition and molecular weight, but different architectures (endblocked vs. pendant), as well as a pure poly(propylene oxide), have been gelled with DBS. We have investigated the dynamic rheological properties of these gels to ascertain the effect of copolymer architecture, PDMS comonomer and DBS concentration on network formation. 相似文献
80.
It is usually assumed that the holding current of an amorphous semiconductor threshold switch is not strongly dependent on the circuit surrounding the switch. This paper shows that the holding current is in fact controlled by both the series resistance and the parallel capacitance, according to two simple inequalities. In order to obtain low holding currents a large series resistor and minimum parallel capacitance are required, and in this way a holding current of 10 μA has been observed. Data are also presented on the effects of device dimensions and temperature on the on-state I-V curves and holding current. 相似文献