全文获取类型
收费全文 | 2235篇 |
免费 | 37篇 |
国内免费 | 144篇 |
专业分类
化学 | 1661篇 |
晶体学 | 7篇 |
力学 | 177篇 |
综合类 | 7篇 |
数学 | 203篇 |
物理学 | 361篇 |
出版年
2024年 | 6篇 |
2023年 | 70篇 |
2022年 | 42篇 |
2021年 | 36篇 |
2020年 | 65篇 |
2019年 | 77篇 |
2018年 | 92篇 |
2017年 | 89篇 |
2016年 | 58篇 |
2015年 | 51篇 |
2014年 | 103篇 |
2013年 | 196篇 |
2012年 | 78篇 |
2011年 | 180篇 |
2010年 | 119篇 |
2009年 | 128篇 |
2008年 | 144篇 |
2007年 | 136篇 |
2006年 | 96篇 |
2005年 | 107篇 |
2004年 | 104篇 |
2003年 | 48篇 |
2002年 | 47篇 |
2001年 | 29篇 |
2000年 | 25篇 |
1999年 | 37篇 |
1998年 | 50篇 |
1997年 | 19篇 |
1996年 | 15篇 |
1995年 | 20篇 |
1994年 | 15篇 |
1993年 | 23篇 |
1992年 | 9篇 |
1991年 | 16篇 |
1990年 | 12篇 |
1989年 | 9篇 |
1988年 | 13篇 |
1987年 | 4篇 |
1986年 | 2篇 |
1985年 | 2篇 |
1984年 | 6篇 |
1983年 | 10篇 |
1981年 | 2篇 |
1980年 | 3篇 |
1979年 | 4篇 |
1977年 | 3篇 |
1974年 | 2篇 |
1973年 | 3篇 |
1969年 | 2篇 |
1968年 | 2篇 |
排序方式: 共有2416条查询结果,搜索用时 328 毫秒
51.
Natural products have been synthesized for billions of years in animals, plants, and microorganisms. As a rule they occur enantiomerically pure. Their chiral character corroborates their use in metabolism or as biologically active agents. Natural products may be insufficient in quality or quantity. They have recently begun to become accessible, either unchanged or modified, by biological synthesis; here, too, they are obtained enantiomerically pure. In the last twenty years chemical synthesis has become a major concern of organic chemists. Their target compounds are primarily enantiomerically pure natural products or biologically active variants thereof. 相似文献
52.
Nguyen Huyen Rao A. Madhusudhan Phillips J. B. John Vijay T. Reed Wayne F. 《Applied biochemistry and biotechnology》1991,(1):843-853
We describe a technique to modify protein solubility and optimize enzyme activity in reversed micellar solutions. The technique
is based on the ability of hydrates of natural gas to form in the micro-aqueous phase. Clathrate hydrates are crystalline
inclusions of water and gas, and their formation in bulk water has traditionally been studied with relevance to natural gas
recovery. We have found that hydrates can form in the environment of the microaqueous pools of reversed micelles, and that
their extent of formation can be well controlled through the thermodynamic variables of temperature and pressure. Additionally,
formation of hydrates affects the size and aggregation number of the micelles, and thus influences the solubility and conformation
of encapsulated proteins. We demonstrate how the concept can be used in two applications: (i) protein extraction into reversed
micelles and subsequent recovery, and (ii) optimization of enzyme activity in reversed micelles. 相似文献
53.
Dominick Maes Silvia Debenedetti Sven Mangelinckx Norbert De Kimpe 《Tetrahedron》2005,61(9):2505-2511
The synthesis of three highly oxygenated naturally occurring coumarins, 8-methoxy-6,7-methylenedioxycoumarin, 5-methoxy-6,7-methylenedioxycoumarin and 5,8-dimethoxy-6,7-methylenedioxycoumarin is described for the first time, together with a new method for the preparation of ayapin (6,7-methylenedioxycoumarin). Comparison of the spectroscopic data of the synthetic tetraoxygenated coumarin 5,8-dimethoxy-6,7-methylenedioxycoumarin with literature reports resulted in the structural revision of several natural coumarins. Two coumarins, both identified as 5,8-dimethoxy-6,7-methylenedioxycoumarin must have other structures, while the structure of another coumarin, described as the isomeric 7,8-dimethoxy-5,6-methylenedioxycoumarin has to be revised to 5,8-dimethoxy-6,7-methylenedioxycoumarin. 相似文献
54.
Highly sensitive catalytic determination of molybdenum 总被引:1,自引:0,他引:1
A novel, highly sensitive, selective, and simple kinetic method was developed for the determination of Mo(VI) based on its catalytic effect on the oxidation of 1-amino-2-naphthol-4-sulfonic acid (ANSA) with H2O2. The reaction was followed spectrophotometrically by tracing the oxidized product at 465 nm after 30 min of mixing the reagents. The optimum reaction conditions were: 10 mmol l−1 ANSA, 50 mmol l−1 H2O2, 100 mmol l−1 acetate buffer of pH 5.0 ± 0.05 and at 40 °C. Addition of 200 μg ml−1 diethylenetriaminepentaacetic acid (DTPA) conferred high selectivity for the proposed method. Following the recommended procedure, Mo(VI) could be determined with a linear calibration graph up to 2.5 ng ml−1 and a detection limit, based on the 3Sb-criterion, of 0.027 ng ml−1. The unique sensitivity and selectivity of the implemented method allowed its direct application to the determination of Mo(VI) in natural and industrial waste water. The method was validated by comparison with the standard ETAAS method. Moreover, published catalytic-spectrophotometric methods for the determination of molybdenum were reviewed. 相似文献
55.
Hai Pham Tuan Hans-Gerd Janssen Ellen M. Kuiper-van Loo Harm Vlap 《Journal of separation science》1995,18(9):525-534
Determination of trace concentrations of sulfur components in natural gas is a true analytical challenge. Only analytical procedures based on gas chromatography can meet the sensitivity and accuracy requirements dictated by environmental regulation institutions and modern chemical industry. In the present contribution the sample pretreatment and chromatographic separation steps have been evaluated and optimized based on the use of a flamebased sulfur chemiluminescence detector (SCD) for target compound detection. The proposed instrument consists of a programmed temperature vaporizing (PTV) injector employing a liner packed with Chromosorb 104, a 4 μm thick film apolar column and a flame-based SCD. Using a 13 mL sample loop the detection limit achievable with the new method is 3 μg S/m3. The precision of replicate measure. ments is generally in the range of 5–15% relative standard deviation. Lower detection limits can be achieved by preconcentrating larger sample volumes, e.g. 100 mL. 相似文献
56.
Amirhossein Nazhand Alessandra Durazzo Massimo Lucarini Maria Alessandra Mobilia Besma Omri 《Natural product research》2020,34(1):110-121
AbstractTaxol is one of the anticancer drugs synthesized naturally in the evergreen Taxus brevifolia forest tree belonging to the yew family (Taxaceae) growing on the Pacific. There are reportedly evidence for treating ovarian, breast and lung cancers through this drug given its unique structural and functional features. Extraction of this drug from yew trees bark is one of the most common ways of producing this drug, but 3000 trees are needed to obtain a kilogram of Taxol. Hence, further attention has recently been attracted to the metabolic engineering strategies, including, engineering cellular metabolism of microorganisms and their optimization. Accordingly, the present paper article was aimed to review recent advances in elevating the production and commercialization of Taxol through metabolic engineering techniques. 相似文献
57.
M. Gastel J.S. Becker G. Küppers H.-J. Dietze 《Spectrochimica Acta Part B: Atomic Spectroscopy》1997,52(14):105-2059
A laser ablation system using a Nd:YAG laser was coupled both to a quadrupole inductively coupled plasma (ICP) mass spectrometer and to a double-focusing sector field ICP mass spectrometer. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was applied for the determination of long-lived radionuclides in a concrete matrix. The investigated samples were two laboratory standards with a concrete matrix, which we doped with different long-lived radionuclides (e.g. 99Tc, 232Th, 233U, 237Np) from the ng g−1 to μ g−1 concentration range and an undoped concrete material (blank). Detection limits for long-lived radionuclides in the 10 ng g−1 range are reached for LA-ICP-MS using the quadrupole mass spectrometer. With double-focusing sector field ICP-MS, the limits of detection are in general one order of magnitude lower and reach the sub ng g−1 range for 233U and 237Np. A comparison of mass spectrometric results with those of neutron activation analysis on undoped concrete sample indicates that a semiquantitative determination of the concentrations of the minor and trace elements in the concrete matrix is possible with LA-ICP-MS without using a standard reference material. 相似文献
58.
A multiresidue method has been developed for the simultaneous determination of sulfadiazine, sulfathiazole, sulfapyridine,
sulfamerazine, sulfamethoxydiazine, sulfamethylthiazole, sulfamethazine, sulfamonomethoxine, sulfamethoxypyridazine, sulfisoxazole,
sulfamethoxazole, sulfadimethoxine and sulfaquinoxaline in natural animal casings by HPLC after solid-phase extraction. The
sulfonamides were extracted with acetonitrile and the extract cleaned up with an Oasis MCX SPE cartridge prior to analysis.
Separation was on a ZOBAX Eclipse XDB-C8 column using gradient elution with acetonitrile/methanol/0.1% acetic acid. The effect of separation conditions on chromatographic
behavior and recovery has been studied. Calibration graphs were linear with very good correlation coefficients (r = 0.9983−0.9996) in the concentration range from 0.02 to 1 μg mL−1. The limits of quantitation (LOQ) for the 13 sulfonamides were in the range of 1.5–2.2 μg kg−1. Decision limits (CCα) and detection capabilities (CCβ) were in the range of 105.2–111.0 and 113.0–120.2 μg kg−1, respectively. The recovery for casings spiked with 1.5–100 μg kg−1 ranged from 65.2 to 85.9%. The relative standard deviations (RSDs) of the sulfonamides for six measurements at 100 μg kg−1 were from 2.2 to 7.7%. The applicability of the method to the analysis of salted swine casings, salted sheep casings and
dry casing samples was demonstrated. 相似文献
59.
60.
Concise construction of the trans-fused 7/7/6/6 tetracyclic ether part of hemibrevetoxin B (1) was achieved by a convergent strategy based on coupling reaction of an acyl anion equivalent, reductive cyclization of an α,ε-dihydroxyketone, and introduction of a methyl group at the central ring junction by the Nicolaou method. The resultant tetracyclic ether was transformed into the known intermediate, which was already converted to 1 by the Yamamoto group, thereby completing the formal total synthesis of 1. 相似文献