全文获取类型
收费全文 | 45961篇 |
免费 | 3206篇 |
国内免费 | 2351篇 |
专业分类
化学 | 22938篇 |
晶体学 | 441篇 |
力学 | 2394篇 |
综合类 | 115篇 |
数学 | 10731篇 |
物理学 | 14899篇 |
出版年
2024年 | 45篇 |
2023年 | 406篇 |
2022年 | 440篇 |
2021年 | 657篇 |
2020年 | 770篇 |
2019年 | 730篇 |
2018年 | 1805篇 |
2017年 | 2001篇 |
2016年 | 1551篇 |
2015年 | 1364篇 |
2014年 | 1451篇 |
2013年 | 1896篇 |
2012年 | 4693篇 |
2011年 | 3823篇 |
2010年 | 2843篇 |
2009年 | 2510篇 |
2008年 | 1627篇 |
2007年 | 1604篇 |
2006年 | 1520篇 |
2005年 | 5245篇 |
2004年 | 4498篇 |
2003年 | 2806篇 |
2002年 | 987篇 |
2001年 | 677篇 |
2000年 | 442篇 |
1999年 | 595篇 |
1998年 | 453篇 |
1997年 | 409篇 |
1996年 | 362篇 |
1995年 | 318篇 |
1994年 | 268篇 |
1993年 | 220篇 |
1992年 | 326篇 |
1991年 | 287篇 |
1990年 | 292篇 |
1989年 | 217篇 |
1988年 | 174篇 |
1987年 | 108篇 |
1986年 | 101篇 |
1985年 | 95篇 |
1984年 | 64篇 |
1983年 | 57篇 |
1982年 | 51篇 |
1976年 | 79篇 |
1975年 | 37篇 |
1974年 | 41篇 |
1973年 | 49篇 |
1972年 | 39篇 |
1969年 | 37篇 |
1966年 | 37篇 |
排序方式: 共有10000条查询结果,搜索用时 265 毫秒
991.
Peng Lu Xueli Hu Yujie Li Yazhou Peng Meng Zhang Xue Jiang Youzhou He Min Fu Fan Dong Zhi Zhang 《Journal of Saudi Chemical Society》2019,23(8):1109-1118
A novel CaCO3/graphitic carbon nitride (g-C3N4) photocatalyst was synthesized for the first time via a facile calcination method using CaCO3 and melamine as precursors. The as-prepared samples were characterized using various techniques, such as scanning and transmission electron microscopy, X-ray diffraction, Brunauer-Emmett-Teller analysis, as well as Fourier-transform infrared, X-ray photoelectron, photoluminescence, and UV–vis diffuse reflectance spectroscopy. The results of the experiments confirm the successful coupling of CaCO3 to g-C3N4. The photocatalytic activity of the synthesized CaCO3/g-C3N4 composites was evaluated by assessing their performance in the photocatalytic degradation of crystal violet (CV) in water under visible light irradiation. The analysis shows that CaCO3/g-C3N4 exhibits higher photocatalytic activity towards CV degradation (76.0%) than pristine g-C3N4 (21.6%) and CaCO3 (23.2%). Radical trapping and electron spin resonance experiments show that hydroxyl radicals (OH) and holes (h+) are the key reactive species in the photocatalytic process. The enhanced photocatalytic activity of the composite is mainly attributed to the efficient separation rate of electron-hole pairs achieved through the incorporation of CaCO3. 相似文献
992.
The influence of newly synthesized N-alkanoyl-N-methyllactitolamines (decanoyl [C10MELA], lauoroyl [C12MELA] and miristoyl [C14MELA]) on the thermotropic phase transition of phosphatidylcholine bilayer was compared with common sugar-based surfactants N-dodecyl-β-d-glucopyranoside [C12G1] and decanoyl-N-methyl glucamide [MEGA-10]. The results indicate that CnMELA are very active at the membrane surface and disturb the phospholipid bilayer structure less than commercially used MEGA-10 and C12G1. 相似文献
993.
Vidal E Palomeque ME Lista AG Fernández Band BS 《Analytical and bioanalytical chemistry》2003,376(1):38-41
A novel flow injection analysis (FIA) method with Rayleigh light scattering (RLS) detection was developed for the determination of total protein concentrations. This method is based on the weak intensity of RLS of bromothymol blue (BB) (3',3"-dibromothymolsulfonephthalein) which can be enhanced by the addition of protein in weakly acidic solution. A common spectrofluorimeter was used as a detector. It was proved that the application of this method to quantify the total proteins in real samples by using bovine serum albumin was possible. The RLS signal was detected at lambda(ex)= lambda(em)=572 nm. The linear range was 7.0-70.0 microg mL(-1), the detection limit was 3.75 microg mL(-1), the reproducibility was 5.5% (n=7), and the sample throughput was 26 h(-1). 相似文献
994.
995.
The electric conduction in the fibrous medium constructed by a homogeneous array of parallel, identical, charged, circular cylinders having an arbitrary zeta potential filled with the solution of a symmetrically charged electrolyte is analytically examined. The thickness of the electric double layers surrounding the dielectric cylinders is assumed to be small relative to the radius of each cylinder and to the gap width between two neighboring cylinders, but the polarization of the mobile ions in the diffuse layers is allowed. The effect of interactions among individual cylinders is taken into explicit account by employing a unit cell model. The appropriate equations of conservation of electrochemical potential energies of ionic species are solved for each cell, in which a cylinder is envisaged to be surrounded by a coaxial cylindrical shell of the fluid solution. Analytical expressions for the effective electric conductivity are obtained in closed forms as functions of the porosity of the fiber matrix and other characteristics of the porous system. Comparisons of the results of the cell model with different conditions at the outer boundary of the cell are made. Under an otherwise identical condition, the electric conductivity in a porous medium composed of an array of parallel cylinders in the transverse direction is smaller than that of a suspension of spheres. The effect of interactions among the cylinders or spheres on the effective conductivity can be quite significant under appropriate conditions. 相似文献
996.
Biosensors based on enzyme field-effect transistors for determination of some substrates and inhibitors 总被引:3,自引:0,他引:3
Dzyadevych SV Soldatkin AP Korpan YI Arkhypova VN El'skaya AV Chovelon JM Martelet C Jaffrezic-Renault N 《Analytical and bioanalytical chemistry》2003,377(3):496-506
This paper is a review of the authors' publications concerning the development of biosensors based on enzyme field-effect transistors (ENFETs) for direct substrates or inhibitors analysis. Such biosensors were designed by using immobilised enzymes and ion-selective field-effect transistors (ISFETs). Highly specific, sensitive, simple, fast and cheap determination of different substances renders them as promising tools in medicine, biotechnology, environmental control, agriculture and the food industry.The biosensors based on ENFETs and direct enzyme analysis for determination of concentrations of different substrates (glucose, urea, penicillin, formaldehyde, creatinine, etc.) have been developed and their laboratory prototypes were fabricated. Improvement of the analytical characteristics of such biosensors may be achieved by using a differential mode of measurement, working solutions with different buffer concentrations and specific agents, negatively or positively charged additional membranes, or genetically modified enzymes. These approaches allow one to decrease the effect of the buffer capacity influence on the sensor response in an aim to increase the sensitivity of the biosensors and to extend their dynamic ranges.Biosensors for the determination of concentrations of different toxic substances (organophosphorous pesticides, heavy metal ions, hypochlorite, glycoalkaloids, etc.) were designed on the basis of reversible and/or irreversible enzyme inhibition effect(s). The conception of an enzymatic multibiosensor for the determination of different toxic substances based on the enzyme inhibition effect is also described.We will discuss the respective advantages and disadvantages of biosensors based on the ENFETs developed and also demonstrate their practical application. 相似文献
997.
The feasibility of using Zr(IV)-porphyrins as novel ionophores for preparing anion-selective polymeric membrane electrodes is examined. Electrodes constructed using o-nitrophenyl octyl ether plasticized poly(vinyl chloride) membranes containing Zr(IV)-octaethylporphyrin (OEP) dichloride (Zr(IV)[OEP]Cl2) or Zr(IV)-tetraphenylporphyrin (TPP) dichloride (Zr(IV)[TPP]Cl2) were found to exhibit enhanced potentiometric selectivity toward fluoride compared to electrodes based on a typical anion-exchanger (e.g. tridodecylmethylammonium chloride). At pH 5.5, the electrodes displayed the following selectivity sequences: ClO4− > SCN− > I− > F− > NO3− > Br− > NO2− > Cl− and F− > ClO4− > SCN− > I− > NO2− > NO3− > Br− > Cl− for membranes doped with Zr(IV)[OEP]Cl2) and Zr(IV)[TPP]Cl2, respectively. Both ionophores are shown to operate via a charged carrier mechanism, with 10 mol% of lipophilic tetraphenylborate derivative in the membrane phase required to achieve optimal selectivity. Electrodes prepared with both metalloporphyrin species display super-Nernstian response toward fluoride with slopes typically greater than −100 mV per decade. It is shown, via UV-VIS spectroscopy of the membrane phase, that this behavior occurs due to spontaneous formation of hydroxide ion bridged porphyrin dimers in the membrane in the presence of the lipophilic anionic additive. The dimers are easily converted to monomeric species upon increasing the concentration of fluoride in the sample solution. Decreasing the pH of sample buffer background solution (from pH 5.5 to pH 3) decreases the lower detection limit (DL) of the electrode response toward fluoride (by two-order of magnitude) and improves the electrodes’ selectivity. 相似文献
998.
The method describes the use of a piezoelectric quartz crystal (PQC) as a substitute for ion-selective electrodes. The approach is feasible when the membrane materials are electrically non-conductive and membrane potential measurements are consequently not possible. An ion-selective piezoelectric sensor sensitive to atropine sulfate was constructed by coating a PVC membrane containing activant on one the side of a PQC. On the basis of selective adsorption of atropine ions across the modified film and the sensitive mass response of PQC, the method exhibits a sensitive, rapid response and is easy to operate without pretreatment of the sample. The logarithm of the frequency shift gave a linear relationship with the logarithm of atropine sulfate concentration in the 1.0 x 10(-8)-1.0 x 10(-3) M range with a detection limit of 5.0 x 10(-9) M at pH 7.0. Recoveries were from 98.7-102.2%. Two activants, atropine tetraphenylborate and atropine dipicrylaminate, were synthesized and investigated. Influencing factors were also examined and optimized. The results for real samples obtained by the proposed method agreed with those obtained by conventional methods. 相似文献
999.
We present a method for simultaneous determination of the aminopolycarboxylic acids DTPA, EDTA and NTA in dishwashing detergents, paper mill waters, and natural waters by capillary electrophoresis (CE). The complexing agents were examined as their copper(II) complexes and separated by conventional CE with reversed polarity of the applied voltage. The optimum separation conditions were established by varying the pH and phosphate and tetradecyltrimethylammonium bromide (TTAB) concentrations in the run buffer. The separations were carried out in a fused-silica capillary (61 cm×75 m i.d.) filled with phosphate buffer (80 mmol L–1, TTAB concentration 0.5 mmol L–1, pH 7.1, voltage –20 kV) using direct UV detection at 191 and 254 nm. With this CE method all the peaks in the electropherograms were properly separated, the calibration plots gave good correlation coefficients and all three complexing agents could be detected in less than 4 min. Linear calibration plots were obtained for CuDTPA, CuEDTA and CuNTA; limits of detection were 0.03 mmol L–1 for all complexing agents and recoveries for all tested samples were within the range 104±7%. Results obtained from dishwashing detergent samples were found to be reliable and comparable with those from HPLC (R2=0.989) and UV–Vis (R2=0.985) methods. 相似文献
1000.
Masumi?Sato Masahiro?Nobe Toshiaki?DobashiEmail author Takao?Yamamoto Akira?Konno 《Colloid and polymer science》2005,284(3):293-300
We have found that the dialysis of curdlan dissolved in alkaline solution into aqueous solutions of metal salts yielded multifold gel structures. Aqueous sodium chloride and potassium chloride as well as pure water induced isotropic gels. Aqueous calcium salts induced liquid crystalline gel with refractive index gradient/amorphous gel alternative structure. Aqueous salts of trivalent aluminum and ferric cations induced a rigid liquid crystalline gel, which shrank above a threshold concentration of each salt. On the other hand, Liesegang ring-like pattern was observed with aqueous solutions of mixed salts of calcium chloride and magnesium chloride. The patterns have been classified to discuss the mechanism of forming the variety of structures. 相似文献