全文获取类型
收费全文 | 4354篇 |
免费 | 269篇 |
国内免费 | 484篇 |
专业分类
化学 | 4008篇 |
晶体学 | 35篇 |
力学 | 144篇 |
综合类 | 29篇 |
数学 | 76篇 |
物理学 | 815篇 |
出版年
2024年 | 15篇 |
2023年 | 106篇 |
2022年 | 97篇 |
2021年 | 107篇 |
2020年 | 98篇 |
2019年 | 67篇 |
2018年 | 67篇 |
2017年 | 89篇 |
2016年 | 185篇 |
2015年 | 177篇 |
2014年 | 186篇 |
2013年 | 268篇 |
2012年 | 275篇 |
2011年 | 342篇 |
2010年 | 250篇 |
2009年 | 268篇 |
2008年 | 229篇 |
2007年 | 287篇 |
2006年 | 234篇 |
2005年 | 232篇 |
2004年 | 242篇 |
2003年 | 188篇 |
2002年 | 170篇 |
2001年 | 133篇 |
2000年 | 111篇 |
1999年 | 111篇 |
1998年 | 79篇 |
1997年 | 90篇 |
1996年 | 89篇 |
1995年 | 74篇 |
1994年 | 43篇 |
1993年 | 37篇 |
1992年 | 30篇 |
1991年 | 27篇 |
1990年 | 26篇 |
1989年 | 20篇 |
1988年 | 12篇 |
1987年 | 11篇 |
1986年 | 4篇 |
1985年 | 4篇 |
1984年 | 6篇 |
1983年 | 3篇 |
1982年 | 2篇 |
1981年 | 6篇 |
1980年 | 1篇 |
1978年 | 2篇 |
1977年 | 1篇 |
1976年 | 3篇 |
1974年 | 2篇 |
1973年 | 1篇 |
排序方式: 共有5107条查询结果,搜索用时 484 毫秒
111.
Predicting the performance of molecularly imprinted polymers: Selective extraction of caffeine by molecularly imprinted solid phase extraction 总被引:2,自引:0,他引:2
A rational design approach was taken to the planning and synthesis of a molecularly imprinted polymer capable of extracting caffeine (the template molecule) from a standard solution of caffeine and further from a food sample containing caffeine. Data from NMR titration experiments in conjunction with a molecular modelling approach was used in predicting the relative ratios of template to functional monomer and furthermore determined both the choice of solvent (porogen) and the amount used for the study. In addition the molecular modelling program yielded information regarding the thermodynamic stability of the pre-polymerisation complex. Post-polymerisation analysis of the polymer itself by analysis of the pore size distribution by BET yielded significant information regarding the nature of the size and distribution of the pores within the polymer matrix. Here is proposed a stepwise procedure for the development and testing of a molecularly imprinted polymer using a well-studied compound—caffeine as a model system. It is shown that both the physical characteristics of a molecularly imprinted polymer (MIP) and the analysis of the pre-polymerisation complex can yield vital information, which can predict how well a given MIP will perform. 相似文献
112.
A capillary zone electrophoresis (CZE) method with ultraviolet-visible detection has been established and validated for the determination of five phenothiazines: thiazinamium methylsulfate, promazine hydrochloride, chlorpromazine hydrochloride, thioridazine hydrochloride, and promethazine hydrochloride in human urine. Optimum separation was obtained on a 64.5 cm x 75 microm bubble cell capillary using a buffer containing 150 mM tris(hydroxymethyl)aminomethane and 25% acetonitrile at pH 8.2, with temperature and voltage of 25 degrees C and 20 kV, respectively. Naphazoline hydrochloride was used as an internal standard. Field-amplified sample injection (FASI) has been applied to improve the sensitivity of the detection. Considering the influence of parameters affecting the on-line preconcentration (nature of preinjection plug, sample solvent composition, injection times, and injection voltage) and due to the significant interactions among them, in this paper we propose for the first time the application of a multivariate approach to carry out the study. The optimized conditions were as follows: preinjection plug of water for 7 s at 50 mbar, electrokinetic injection for 40 s at 6.2 kV, and 32 microm of H3PO4 in the sample solvent. Also, a solid-phase extraction (SPE) procedure is developed to obtain low detection limits and an adequate selectivity for urine samples. The combination of SPE and FASI-CZE-UV allows adequate linearities and recoveries, low detection limits (from 2 to 5 ng/mL), and satisfactory precisions (3.0-7.2% for an intermediate RSD %). 相似文献
113.
高分子固体电解质研究进展 总被引:6,自引:0,他引:6
高分子固体电解质具有质轻、粘弹性了、易成膜等许多无机电解质和有机溶剂电解质所不可比拟的优点,近年来得到了很大的发展,这种新型材料的应用主要集中开发全固态锂电池和锂离子电池。本文对SPE的电性能,离子传导特性以及提高SPE性能的途径等作了综述,并对其发展前景作了简要探讨。 相似文献
114.
蛋白质在固体表面的吸附有多种理论模型和实验分析.蛋白质吸附主要包括分子传递、吸附、重排、交换、解吸等步骤.蛋白质在表面的状态由表面性能、静电作用及蛋白质自身性质等因素决定.蛋白质分子在界面吸附后发生构象改变,引起熵增. 相似文献
115.
垃圾在流化床中焚烧NO排放特性研究 总被引:2,自引:3,他引:2
在Ф150 mm流化床上,研究了六类典型组分垃圾NO转化率与床温和过量空气系数(excess air简称EA)的关系。研究发现,纸渣与木块NO转化率最高,橡胶与塑料最低;织物、纸张、厨余、木块、塑料NO均具有中温生成特性,一般在800 ℃~850 ℃时即接近最大值,之后温度升高对NO的生成影响不大;橡胶与无烟煤由于含N化合物结构稳定,其NO转化率随床温升高而增大;由于挥发分析出的相互影响,较低的火焰温度,混合垃圾NO转化率一般低于单组分垃圾的线性叠加;少量水分不会对垃圾NO转化率造成很大影响,相反还会促进NO的转化,但过量水分会抑制NO的生成。 相似文献
116.
Subratanath Koner Masaru TsutakeIsoroku Nagasawa Ryuichi IkedaPratap K. Saha Alok K. MukherjeeSurajit Banerjee 《Journal of Molecular Structure》2002,608(1):63-69
The complex bis-(N,N-dimethyl-1,2-ethanediamine) nickel(II) perchlorate undergoes a first-order thermochromic phase transition at ca. 476 K, changing its color from orange to red. The room temperature X-ray crystal structure determination showed that the nickel ion possesses a square-planar geometry with two five membered chelate rings, in the δλ conformation, forming the NiN4 chromophore. The broad-line 1H NMR indicates the onset of a dynamic disorder of diamine chelate rings at the phase transition temperature region, while T1 measurement of 1H affords the activation energy of the puckering metal chelate rings to be 26 kJ mol−1. The electronic spectrum revealed that a weakening of ligand field around the nickel is associated with the phase transition. 相似文献
117.
A.?H.?Naik N.?V.?Thakkar S.?R.?DharwadkarEmail author K.?D.?Singh Mudher V.?Venugopal 《Journal of Thermal Analysis and Calorimetry》2004,78(3):707-713
Sodium zirconium phosphate [NaZr2P3O12], a potential ceramic matrix for fixation of high level nuclear waste, was synthesized by heating the mixture of sodium carbonate [Na2CO3], zirconyl nitrate hydrate [ZrO(NO3)2·5H2O] and ammonium dihydrogen phosphate [NH4H2PO4] in air, in a resistance heated furnace and a microwave heating system respectively in the temperature range 450 to 650°C. The mixture heated for 1 h in a resistance furnace at 450°C yielded a poorly crystalline NaZr2P3O12 [NZP]. Increasing the temperature to 650°C produced a highly crystalline product. The same mixture heated in a microwave oven at 450°C for 1 h however, yielded the most crystalline NZP.In an alternate method, the mixture of sodium dihydrogen phosphate (NaH2PO4), zirconium dioxide (ZrO2) and diammonium hydrogen phosphate [(NH4)2HPO4] heated in resistance furnace at 650°C for the same period did not react in air. It also did not yield the pure product at 450°C when heated in microwave assembly for 1 h.The authors thank the Board of Research in Nuclear Sciences (BRNS) of the Department of Atomic Energy (DAE) for the financial support for this work under the project No. 2000/37/19/BRNS/1959 dtd09-02-02. 相似文献
118.
A simple and versatile protocol, based on use of solid phase extraction on strong ion exchangers and off-line detection by flame atomic absorption spectrometry, was devised to fractionate iron and zinc in common dietary food and beverages products, i.e., bee honeys, fruit juices and tea infusions. In the procedure proposed, cation exchanger Dowex 50Wx4 and anion exchanger Dowex 1x4 were used separately for distinguishing broadly meant the cationic metal fraction and the fraction of stable anionic metal complexes, respectively, after retention of metal species and their exhaustive elution by means of a 4.0 mol l−1 HCl solution. The third fraction, referred to the residual metal species, was retrieved by difference between total soluble metal contents and sum of metal quantities in separated cationic and anionic fractions. The fractionation pattern observed for both metals was described and discussed. 相似文献
119.
用低温陈化的方法制得V(V)促进型SO4^2-/ZrO2固体超强酸(SZV),用流动指示剂法测定其酸强度,用IR,XRD和XPS进行结构表征,并将制得的催化剂用于催化乙酸和丙三醇的酯化反应.结果表明,低温陈化样品比常温陈化有更强的酸性和更高的催化活性,IR谱图中S—O键的伸缩振动峰显著增强,在600~650℃的焙烧温度下,低温陈化样品的晶体结构为ZrO2四方相,XPS图中Zx3d峰位出现较大的化学位移,表明低温陈化使SZV样品具有较高的酸性. 相似文献
120.
《Electroanalysis》2006,18(15):1493-1498
Titanium nitride was used as pH‐sensitive material to fabricate all solid‐state pH electrode. The fabrication and the response performance of the pH electrode were described in the paper. The TiN film electrode showed a linear response in the pH range of 2–12 with a near‐Nenstian response (?55 mV/pH). The response time was within 1 min, and the electrode had good reproducibility, stability and low sensitivities for different species. Compared with the glass pH electrode, the electrode exhibited some advantages, for example, without activation, rapid response and high mechanical strength. In addition, the electrode performed excellently in a corrosion medium containing F?(1 M). Electrochemical behaviors of TiN electrode in Britton‐Robinson buffers were studied with Electrochemical Impedance Spectroscopy (EIS). 相似文献