全文获取类型
收费全文 | 9717篇 |
免费 | 1038篇 |
国内免费 | 886篇 |
专业分类
化学 | 8333篇 |
晶体学 | 44篇 |
力学 | 939篇 |
综合类 | 151篇 |
数学 | 477篇 |
物理学 | 1697篇 |
出版年
2024年 | 33篇 |
2023年 | 128篇 |
2022年 | 368篇 |
2021年 | 351篇 |
2020年 | 441篇 |
2019年 | 361篇 |
2018年 | 360篇 |
2017年 | 359篇 |
2016年 | 505篇 |
2015年 | 438篇 |
2014年 | 482篇 |
2013年 | 1054篇 |
2012年 | 590篇 |
2011年 | 537篇 |
2010年 | 396篇 |
2009年 | 447篇 |
2008年 | 425篇 |
2007年 | 535篇 |
2006年 | 456篇 |
2005年 | 432篇 |
2004年 | 379篇 |
2003年 | 323篇 |
2002年 | 308篇 |
2001年 | 220篇 |
2000年 | 225篇 |
1999年 | 198篇 |
1998年 | 182篇 |
1997年 | 161篇 |
1996年 | 137篇 |
1995年 | 125篇 |
1994年 | 78篇 |
1993年 | 108篇 |
1992年 | 92篇 |
1991年 | 63篇 |
1990年 | 51篇 |
1989年 | 34篇 |
1988年 | 35篇 |
1987年 | 33篇 |
1986年 | 28篇 |
1985年 | 27篇 |
1984年 | 24篇 |
1983年 | 8篇 |
1982年 | 13篇 |
1981年 | 13篇 |
1980年 | 15篇 |
1979年 | 14篇 |
1978年 | 10篇 |
1976年 | 9篇 |
1973年 | 10篇 |
1972年 | 6篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
111.
《Electroanalysis》2006,18(1):35-43
A new method is presented for the determination of electrochemically labile iron in estuarine and coastal seawater. The method is based on differential pulse anodic stripping voltammetry (DPASV) at a rotating silver‐alloy disk electrode. The voltammetric parameters include a plating potential of ?1.5 V and an activation potential of ?5 V for 10s; the seawater is at the original sample pH. The main finding is the presence of a peak for low nmol L?1 levels of iron at ?0.55 V ascribed to elemental iron deposited on the bare silver alloy electrode. The peak increased linearly with the iron concentration between <1 and 14 nmol L?1 using a 900 s plating time. At higher concentrations an additional iron peak appeared at ?0.7 V which was also found to increase linearly with the iron concentration but at a higher concentration range from ca. 15 to 90 nmol L?1 using a 300 s plating time. The second peak was ascribed to iron deposited on iron. Additions of chelating agents (EDTA and a siderophore) to seawater caused the iron peak to be masked indicating that this method is suitable for iron speciation as only the electrochemically labile fraction is determined. The detection limit was 0.3 nmol L?1 using a 900 s plating time. The method was used to determine iron in the range of 5 to 50 nmol L?1 in samples from the Mersey estuary near Liverpool and its potential use for in situ monitoring was demonstrated by using it to monitor labile iron (at 2–3 nmol L?1) over a period of 4 days at 1 h intervals in coastal waters in the Trondheim fjord, Norway. 相似文献
112.
A stochastic method of optimization, which combines simulated annealing with simplex, is implemented to fit the parameters of a simple model potential. The main characteristic of the method is that it explores the whole space of the parameters of the model potential, and therefore it is very efficient in locating the global minimum of the cost function, in addition to being independent of the initial guess of the parameters. The method is employed to fit the complex intermolecular potential energy surface of the dimer of water, using as a reference the spectroscopic quality anisotropic site-site potential of Feller et al. The simple model potential chosen for its reparameterization is the MCY model potential of Clementi et al. The quality of the fit is assessed by comparing the geometry of the minimum, the harmonic frequencies, and the second virial coefficients of the parameterized potential with the reference one. Finally, to prove more rigorously the robustness of this method, it is compared with standard nonstochastic methods of optimization. 相似文献
113.
114.
S. Korhammer Rolf Herzig Peter Schramel Jorma Kumpulainen Bernd Markert Herbert Muntau Philippe Quevauviller 《Accreditation and quality assurance》2000,5(6):238-242
Cabbage is frequently used in environmental monitoring and food control, and, hence, cabbage reference materials (RMs) are
required for ensuring quality assurance. A cabbage RM was prepared in view of certification of specific elements from the
"black list" of high toxicological interest and nutritive importance. All tasks of the RM production (production of the plant
material, cutting and freeze-drying, determination of the residual water content, preparation of the RM, homogeneity testing,
stability testing, certification measurements) are described in detail.
Received: 12 November 1999 / Accepted: 29 January 2000 相似文献
115.
V. G. Berezkin V. R. Alishoyev E. N. Victorova V. S. Gavrichev V. M. Fateeva 《Chromatographia》1982,16(1):126-131
Summary The use of crystallohydrates, crystallohydrate solutions and melts as stationary phases in gas chromatography has been proposed. Crystallohydrates have been shown to display high selectivity in the separation of polar organic compounds when use is made of water vapours as the mobile phase. Some aspects of gas-liquid chromatography in water vapours and with the stationary phase comprising crystallohydrates have been studied, and the preliminary results obtained point to the desirability of further progress in this field.Presented at the 14th International Symposium on Chromatography London, September, 1982 相似文献
116.
Samuel Melaku Rita Cornelis Frank Vanhaecke Richard Dams Luc Moens 《Mikrochimica acta》2005,150(3-4):225-231
A simple, sensitive and inexpensive method for the speciation of Cr(VI) and Cr(III) in river and industrial wastewater was developed, optimized and validated. Samples were collected, filtered and then chromium species were determined in the filtrate. In the filtrate, total Cr was determined directly by Graphite Furnace Atomic Absorption Spectrometry (GFAAS). A portion of the filtered sample was buffered to pH 6.4, extracted with Amberlite LA-2/MIBK and finally Cr(VI) was determined in the organic extract and Cr(III) in the aqueous phase using GFAAS. The method was evaluated by analysis of the certified reference material, CRM 544, and good accuracy was obtained. The limit of detection for Cr(VI) and Cr(tot)/Cr(III) was found to be 0.30 and 0.08 µg L−1, respectively, and a precision expressed as relative standard deviation of better than 11% was achieved for nine replicates. A number of water samples from the Tinishu Akaki River, Ethiopia, and wastewater samples from a chemical plant in Germany, were analysed. In addition to the GFAAS method, Cr(tot) was also determined using ICP-MS (in CRM 544, lyophilized water, and Tinishu Akaki River water samples) and Cr(tot) and Cr(VI) using UV-VIS spectrophotometry (in CRM 544 and industrial wastewater samples). Good agreement between the different methods was found. 相似文献
117.
Y. Marcus 《Journal of solution chemistry》1994,23(7):831-848
The water-structural contributions to the entropies and heat capacities of hydration of over 120 ions and the viscosity B-coefficients of nearly 80 aqueous ions are tabulated and correlated. B-coefficients for many more ions are predicted from this relationship and from their dependence on ionic size and charge. The structural entropies determine a unique scale of water structure making and breaking by the ions. 相似文献
118.
The heats of solution at 25°C for a number of hydrocarbon gases are reported as measured by a calorimetric method. There is excellent agreement between the standard enthalpy changes of solution measured calorimetrically and those derived from high precision temperature dependent solubility measurements. However the calorimetrically determined standard enthalpies of solution of a number of gases are greatly improved over values obtained from low precision temperature dependent solubility measurements. A method is presented to readily estimate the standard errors in the standard enthalpy change for any process derived from the temperature dependence of the equilibrium constant for the process. Comparison of the standard enthalpies and entropies of solution of hydrocarbon gases in water shows that the standard free energies of solution for all hydrocarbon gases investigated are dominated by unfavorable entropy contributions. A strong linear correlation between the standard entropy of solution and the number of hydrogens in the hydrocarbon molecule is found. This correlation suggests that the hydrocarbon hydrophobic effect is regulated by the number of allowable configurations of a water molecule in contact with each C–H group. 相似文献
119.
Electrochemical and electrocatalytic properties of thin films Au(111-25 nm), which are quasi-single-crystal electrodes 25
nm thick made of gold with the (111) preferential orientation, and same electrodes modified with a monolayer (ML) of palladium
are studied in 0.1 M solutions of HClO4 and H2SO4 employing voltammetric techniques and surface enhanced infrared reflection absorption spectroscopy (ATR-SEIRAS). Spectroscopic
experiments demonstrate strong adsorption of electrolyte species (H2O, OHads, anions) on the Pd surface. The weak and reversible adsorption of CO on Au(111-25 nm) does not change the interfacial-water
structure. Adsorption of CO on the Pd-modified film results in an irreversibly adsorbed CO adlayer stabilized by co-adsorbed
isolated water species. Various electrooxidation mechanisms are discussed. Electrochemical and spectroscopic investigations
on the adsorption and electrooxidation of HCOOH on bare and 1 ML Pd-Au(111-25 nm) electrodes reveal that electrooxidation
proceeds in both cases via a direct or dehydrogenation pathway. This mechanism involves the formation of formate as intermediate,
which is detected by in situ ATR-SEIRAS. The reactivity on Pd-modified surfaces is higher than on bare gold. The specifically
adsorbed anions (sulfate/bisulfate) and the oxide formation on the substrate surface lower the reactivity for CO and HCOOH
on both surfaces.
Published in Russian in Elektrokhimiya, 2006, Vol. 42, No. 11, pp. 1312–1329.
Based on the report delivered at the 8th International Frumkin Symposium “Kinetics of the Electrode Processes,” October 18–22,
2005, Moscow.
The text was submitted by the authors in English. 相似文献
120.
Chemical conversion of various celluloses to glucose and its derivatives in supercritical water 总被引:16,自引:0,他引:16
The supercritical water biomass conversion system was designed and developed in our laboratory. The reaction vessel with cellulose sample was treated with this system at supercritical state of water for a designated period (3–105s) under the conditions of a tin bath temperature of 500°C and pressure of 35MPa. The recovered products of hydrolysates were then analyzed by high performance liquid chromatography. The obtained results indicated that a high amount of glucose and levoglucosan can be achieved from both celluloses I and II for 5–10s supercritical treatment, while that from starch for 3–5s treatment. Although this difference could be due to a difference in the molecular structure between cellulose and starch, a difference between celluloses I and II was not significant. Instead, an accessibility of the water towards cellulose molecules seemed to be significant for their chemical conversion. With the longer treatment, amounts of these compounds observed were decreased due to decomposition. Therefore, it may be concluded that, compared with acid hydrolysis or enzymatic saccharification, cellulose may be hydrolyzed to glucose and its derivatives more or less to the same degree as in corn starch under supercritical state. This finding suggests that the supercritical treatment can overcome the difficulties in hydrolyzing cellulose to glucose, found in the acid hydrolysis or enzymatic saccharification techniques. 相似文献