全文获取类型
收费全文 | 2086篇 |
免费 | 101篇 |
国内免费 | 15篇 |
专业分类
化学 | 1628篇 |
晶体学 | 36篇 |
力学 | 48篇 |
数学 | 117篇 |
物理学 | 373篇 |
出版年
2024年 | 15篇 |
2023年 | 20篇 |
2022年 | 97篇 |
2021年 | 112篇 |
2020年 | 69篇 |
2019年 | 79篇 |
2018年 | 97篇 |
2017年 | 73篇 |
2016年 | 102篇 |
2015年 | 68篇 |
2014年 | 75篇 |
2013年 | 158篇 |
2012年 | 174篇 |
2011年 | 158篇 |
2010年 | 102篇 |
2009年 | 89篇 |
2008年 | 112篇 |
2007年 | 91篇 |
2006年 | 73篇 |
2005年 | 55篇 |
2004年 | 48篇 |
2003年 | 32篇 |
2002年 | 58篇 |
2001年 | 34篇 |
2000年 | 39篇 |
1999年 | 12篇 |
1998年 | 18篇 |
1997年 | 9篇 |
1996年 | 5篇 |
1995年 | 9篇 |
1994年 | 7篇 |
1993年 | 6篇 |
1992年 | 8篇 |
1991年 | 4篇 |
1990年 | 10篇 |
1989年 | 6篇 |
1988年 | 4篇 |
1987年 | 6篇 |
1986年 | 4篇 |
1985年 | 6篇 |
1984年 | 7篇 |
1983年 | 6篇 |
1982年 | 4篇 |
1981年 | 2篇 |
1980年 | 4篇 |
1979年 | 9篇 |
1978年 | 5篇 |
1977年 | 6篇 |
1974年 | 2篇 |
1937年 | 2篇 |
排序方式: 共有2202条查询结果,搜索用时 218 毫秒
991.
Jaleel CA Gopi R Manivannan P Gomathinayagam M Sridharan R Panneerselvam R 《Colloids and surfaces. B, Biointerfaces》2008,62(2):312-318
The variations in antioxidant potentials and indole alkaloid content were studied in the present investigation, in two varieties (rosea and alba) of Catharanthus roseus, an important herb used in traditional as well as modern medicine, exposed to water deficit stress. The antioxidant and alkaloid profiles were estimated from root, stem, leaf, flowers and pods. The antioxidant potentials were examined in terms of non-enzymatic antioxidant molecules and activities of antioxidant enzymes. The non-enzymatic antioxidant molecules studied were ascorbic acid (AA), -tocopherol (-toc) and reduced glutathione (GSH). The estimated antioxidant enzymes were superoxide dismutase (SOD), ascorbate peroxidase (APX), catalase (CAT), peroxidase (POX) and polyphenol oxidase (PPO). The antioxidant concentrations and activities of antioxidant enzymes were high under water deficit stress in all parts of the plants. Indole alkaloid content was high in the roots of rosea variety in response to stress when compared to alba variety. 相似文献
992.
Liu Z Mutlib AE Wang J Talaat RE 《Rapid communications in mass spectrometry : RCM》2008,22(21):3434-3442
A robust bioanalytical method capable of measuring acetyl and palmitoyl carnitines was developed and validated. Application of hydrophilic interaction chromatography (HILIC) enabled retention of these highly polar and difficult to analyze compounds on a silica HPLC column. The chromatography was conducted with a high percentage of an organic component in the mobile phase, allowing high sensitivity for the pre-existing positively charged quaternary ammonium ions by electrospray ionization mass spectrometry. Successful application of the method to reliably quantify naturally occurring acyl carnitines in mouse plasma depended on the use of corresponding deuterated analogues. The specificity of the method, achieved through the use of stable isotope labeled compounds in combination with a mass spectral multiple reaction monitoring technique, permitted a non-invasive assessment of the overall change in the levels of these acyl carnitines in the plasma of intact animals administered peroxisome proliferator activated receptor (PPAR) agents. These acyl carnitines, as carriers of the corresponding long-chain fatty acids for transport into mitochondria, can be employed as potential biomarkers for significant alteration in the beta-oxidation process in an intact animal. 相似文献
993.
Ayyaz Muhammad M.I. Abdul Mutalib C.D. Wilfred T. Murugesan Amir Shafeeq 《The Journal of chemical thermodynamics》2008,40(9):1433-1438
The thermophysical properties of 1-hexyl-3-methyl imidazolium based hydrophobic room temperature ionic liquids (RTILs); with tetrafluoroborate (BF4), hexafluorophosphate (PF6), and bis(trifluoromethylsulfonyl)imide (Tf2N) anions, namely density ρ (298.15 to 348.15) K, dynamic viscosity η (288.2 to 348.2) K, surface tension σ (298.15 to 338) K, and refractive index nD (302.95 to 332.95) K have been measured. The coefficients of thermal expansion αp values were calculated from the experimental density data using an empirical correlation. The thermal stability of all ILs is also investigated at two different heating rates (10 and 20) °C · min−1) using thermogravimetric analyzer (TGA). The experimental results presented in this study reveal that the choice of anion type shows the most significant effect on the properties of ILs. The chloride and water contents of ILs (as impurities) are also investigated and reported in the present work. 相似文献
994.
The structure of lysozyme-sodium dodecyl sulfate (SDS) complexes in solution is studied using small-angle X-ray scattering (SAXS). The SAXS data cannot be explained by the necklace and bead model for unfolded polypeptide chain interspersed with surfactant micelles. For the protein and surfactant concentrations used in the study, there is only marginal growth of SDS micelles as they complex with the protein. Being a small and rather rigid protein, lysozyme can penetrate the micellar core which is occupied by flexible and disordered paraffin chains and also the shell occupied by the hydrated head groups. A partially embedded swollen micellar model seems appropriate and describes well the scattering data. The SAXS intensity profiles are analyzed by considering the change in the electron scattering length density of the micellar core and shell due to complexation with protein and treating the intermicellar interaction using rescaled mean spherical approximation (RMSA) for charged spheres. 相似文献
995.
An optical fiber biosensor consisting of acetylcholinesterase (AChE) and bromothymol blue (BTB) doped sol-gel film was employed to detect organophosphate pesticide chlorpyrifos. The main advantage of this optical biosensor is the use of a single sol-gel film with immobilized AChE and BTB. The compatibility of this mixture (AChE and BTB) with the sol-gel matrix has prevented leaching of the film. The immobilization of the enzyme and indicator was simple without chemical modification. The biosensing element on single sol-gel film has been placed inside the flow-cell for flow system. In the presence of a constant AChE, a color change of the BTB and the measured reflected signal at wavelength 622nm could be related to the pesticide concentration in the sample solutions. The performance of optical biosensor in the flow system has been optimized, including chemical and physical parameters. The response time of the biosensor is 8min. A linear calibration curve of chlorpyrifos against the percentage inhibition of AChE was obtained from 0.05 to 2.0mg/L of chlorpyrifos (18-80% inhibition, R(2)=0.9869, n=6). The detection limit for chlorpyrifos was 0.04mg/L. The results of the analysis of 0.5-1.5mg/L of chlorpyrifos using this optical biosensor agreed well with chromatographic method. 相似文献
996.
Abdul J. Laghari M. Y. Khuhawar Liaquat A. Zardari Abdul G. Bhatti 《Chromatographia》2008,67(9-10):749-754
A gas chromatographic procedure has been developed for determination of cisplatin from pharmaceutical preparation, serum and urine after chemotherapy of cancer patients as platinum(II) pyrrolidinedithiocarbamate chelate. The elution was carried from the column DB-1701 (30 m × 0.32 mm i.d.) coupled with FID detection. Cu(II), Ni(II), Co(III), Mn(II), Fe(III), Zn(II) and VO(II) when present together with Pt(II) separated completely and did not affect the determination of platinum. The linear calibration curve for platinum (II) was within 1–30 μg mL?1 with a detection limit of 300 ng mL?1. The amount of cisplatin detected from serum and urine was 250–325 and 20–116 ng mL?1 with relative standard deviations (RSD) of 0.8–1.2%, and 0.9–1.2%. The % recovery of Pt from serum and urine by standard addition was 98 and 98.2% with RSD 1.4 and 1.1%. 相似文献
997.
Maji S Sarkar B Mobin SM Fiedler J Urbanos FA Jimenez-Aparicio R Kaim W Lahiri GK 《Inorganic chemistry》2008,47(12):5204-5211
The title complexes were obtained in neutral form (n = 0) as rac (1) and meso isomers (2). 2 was crystallized for X-ray diffraction and its temperature-dependent magnetism studied. It contains two antiferromagnetically coupled ruthenium(III) ions, bridged by the quinizarine dianion QL(2-) (quinizarine = 1,4-dihydroxy-9,10-anthraquinone). The potential of both the ligand (QLo --> QL4-) and the metal complex fragment combination [(acac)2RuII]2 --> ([(acac)2RuIV]2)4+ to exist in five different redox states creates a large variety of combinations, which was assessed for the electrochemically reversibly accessible 2+, 1+, 0, 1-, 2- forms using cyclic voltammetry as well as EPR and UV-vis-NIR spectroelectrochemistry. The results for the two isomers are similar: Oxidation to 1+ or 2+ causes the emergence of a near-infrared band (1390 nm), without revealing an EPR response even at 4 K. Reduction to 1- or 2- produces an EPR signal, signifying metal-centered spin but no near-infrared absorption. Tentatively, we assume metal-based oxidation of [(acac)2RuIII(mu-QL2-)RuIII(acac)2] to a mixed-valent intermediate [(acac)2RuIII(mu-QL2-)RuIV(acac)2]+ and ligand-centered reduction to a radical complex [(acac)2RuIII(mu-QL.3-)RuIII(acac)2 (-) with antiferromagnetic three-spin interaction. 相似文献
998.
A series of new 1-(alkenoyl/hydroxyalkenoyl)-4-benzoyl-thiosemicarbazides 2a-d and 2-benzamide-5-alkenyl/hydroxyalk-enyl-1,3,4-thiadiazoles 3a-d were synthesized from fatty acid hydrazides. Structure of all these compounds was confirmed by IR, 1H NMR, 13C NMR, mass spectra and elemental analysis. The bioassay results indicate that some compounds 2,c, 2d, 3c and 3d have good antibacterial activity. 相似文献
999.
Effect of diluent and reaction parameter on selective oxidation of propane over MoVTeNb catalyst using nanoflow catalytic reactor
下载免费PDF全文
![点击此处可从《天然气化学杂志》网站下载免费的PDF全文](/ch/ext_images/free.gif)
The selective oxidation of propane to acrylic acid over an MoVTeNb mixed oxide catalyst, dried and calcined before reaction has been studied using high-throughput instrumentation, which is called nanoflow catalytic reactor. The effects of catalyst dilution on the catalytic performance of the MoVTeNb mixed oxide catalyst in selective oxidation of propane to acrylic acid were also investigated. The effects of some reaction parameters, such as gas hourly space velocity (GHSV) and reaction temperature, for selective oxidation of propane to acrylic acid over diluted MoVTeNb catalyst have also been studied. The configuration of the nanoflow is shown to be suitable for screen catalytic performance, and its operating conditions were mimicked closely to conventional laboratory as well as to industrial conditions. The results obtained provided very good reproducibility and it showed that preparation methods as well as reaction parameters can play significant roles in catalytic performance of these catalysts. 相似文献
1000.
S. M. T. Shaikh D. H. Manjunatha K. Harikrishna K. C. Ramesh R. Sudhir Kumar J. Seetharamappa 《Journal of Analytical Chemistry》2008,63(7):637-642
A simple and sensitive spectrophotometric method for the determination of four catecholamines viz., adrenaline bitartarate
(ABT), methyldopa (MDP), dopamine hydrochloride (DPH), and levodopa (LDP), in both pure form and in pharmaceutical formulations
is described. The method is based on the reaction of diazotized sulphanillic acid (DSA) with catecholamines in a basic medium
to yield orange-red colored products having absorption maxima at 507 nm for MDP and at 475 nm for others analytes. The colored
species obeyed Beer’s law in the range of 1–27, 0.5–17, 0.6–15, and 1.5–19.2 μg/mL for ABT, MDP, DPH, and LDP, respectively.
The molar absorptivity values as obtained from Beer’s law data were found to be 0.812 × 104, 0.947 × 104, 0.927 × 104, and 0.709 × 104 L/(mol cm), while Sandell’s sensitivity values were observed to be 412.03, 25.15, 20.44, and 27.81 ng/cm2 for ABT, MDP, DPH, and LDP, respectively. Common excipients did not interfere with the proposed method. The results of the
proposed methods compare favorably with those of official methods. The proposed method offers a simplicity, reliability, rapidity,
and accuracy compared to the existing methods.
The text was submitted by the author in English. 相似文献