全文获取类型
收费全文 | 48160篇 |
免费 | 2539篇 |
国内免费 | 6562篇 |
专业分类
化学 | 37530篇 |
晶体学 | 779篇 |
力学 | 851篇 |
综合类 | 375篇 |
数学 | 9095篇 |
物理学 | 8631篇 |
出版年
2024年 | 39篇 |
2023年 | 333篇 |
2022年 | 580篇 |
2021年 | 795篇 |
2020年 | 1049篇 |
2019年 | 1022篇 |
2018年 | 899篇 |
2017年 | 1370篇 |
2016年 | 1330篇 |
2015年 | 1136篇 |
2014年 | 1620篇 |
2013年 | 3783篇 |
2012年 | 3406篇 |
2011年 | 2378篇 |
2010年 | 1947篇 |
2009年 | 2865篇 |
2008年 | 3026篇 |
2007年 | 3106篇 |
2006年 | 2819篇 |
2005年 | 2522篇 |
2004年 | 2408篇 |
2003年 | 1952篇 |
2002年 | 2802篇 |
2001年 | 1815篇 |
2000年 | 1631篇 |
1999年 | 1632篇 |
1998年 | 1351篇 |
1997年 | 1032篇 |
1996年 | 831篇 |
1995年 | 823篇 |
1994年 | 731篇 |
1993年 | 579篇 |
1992年 | 617篇 |
1991年 | 387篇 |
1990年 | 352篇 |
1989年 | 360篇 |
1988年 | 243篇 |
1987年 | 199篇 |
1986年 | 214篇 |
1985年 | 168篇 |
1984年 | 177篇 |
1983年 | 86篇 |
1982年 | 154篇 |
1981年 | 120篇 |
1980年 | 139篇 |
1979年 | 124篇 |
1978年 | 112篇 |
1977年 | 60篇 |
1976年 | 41篇 |
1973年 | 28篇 |
排序方式: 共有10000条查询结果,搜索用时 640 毫秒
991.
As part of a programme directed towards the synthesis of the marine toxins, the spirolides and gymnodimine, a convenient synthesis of the key bicyclic spiroimine ring systems has been developed. The method involves double alkylation of a simple lactam, Grubbs ring closing metathesis of the resultant dialkylated lactam then reduction of the lactam to an imine. 相似文献
992.
Incineration methods are becoming increasingly important from the view point of the need to minimize the environmental impact of waste tyre disposal. Combustion of waste tyre, one high ash coal and tyre-coal blends with 10, 30 and 50% waste tyre were investigated by means of thermogravimetric analysis (TGA) carried out at 20 K min−1 in the temperature range from ambient temperature to 1273 K. And effects of the mixed proportion between coal and waste tyre on the combustion process, ignition and burnout characteristics were also studied. The results indicate that the combustion of waste tyre is controlled by the emission of volatile matter, the regions are more complex for waste tyre (three or more peaks) than for coal (one peak). Also as compared with the case of burning only high ash coal, the incorporation of waste tyre can improve the combustion characteristics of high ash coal, especially the ignition performance and the peak weight loss compared with the separate burning of waste tyre and coal. Moreover, comparisons of the TG-DTG profiles between experimental and calculational results, it is indicate that there is a comparatively important difference, the co-combustion characteristics is the coupling effect between waste tyre and coal. The data resulting also showed that the co-combustion of waste tyre and low quanlitied coal as fuel is feasible. 相似文献
993.
固体超强酸(SO4^2-/ZrO2)的异丁烷/1-丁烯烷基化反应性能和失活研究 总被引:3,自引:0,他引:3
研究了固体超强酸(SO4^2-/ZrO2)催化剂的酸性及异丁烷-1-丁烯烷基化反应性能,结果表明,固体超强酸的酸性与焙烧温度有关,适当提高焙烧温度有利于样品酸强度的提高,但焙烧温度过高会导致脱硫,使样品酸强度和酸量降低,固体超强酸的异丁烷/1-丁烯烷基化催化反应活性与其酸性相对应,酸性强,反应活性高,但催化剂的活性衰减很快,这是催化剂表面的快速积炭所致。 相似文献
994.
A new high-performance liquid chromatographic (HPLC) method for measuring low molecular weight (LMW) thiol-containing compounds, including cysteine (CysH), glutathione (GSH), N-acetylcysteine (Nac), penicillamine (PA), and 2-mercaptoethanol (2-ME), has been developed by using 5-methyl-(2-(m-iodoacetylaminophenyl)benzoxazole (MIPBO) as fluorescence-labeling reagent. The derivatization and separation conditions have been investigated in detail. Detection limits ranging from 3.5 to 15.0 fmol were achieved for the thiols investigated in a 16 min separation with detection wavelengths 310 and 375 nm for the excitation and emission, respectively. The utility of the proposed method has been validated by measuring CysH in human urine samples. 相似文献
995.
The oxidative polycondensation of 4-[(pyridin-3-ylimino)methyl]phenol (4-PIMP) with O2, H2O2, and NaOCl was studied in an aqueous alkaline medium between 50°C and 90°C. Oligo-4-[(pyridin-3-ylimino)methyl]phenol (O-4-PIMP)
prepared was characterized by 1H-NMR, 13C-NMR, FT-IR, UV-VIS, size-exclusion chromatography, and elemental and thermal analyses techniques. At the optimum reaction
conditions, the yield of O-4-PIMP was 18.9%, 39.4%, and 46.8% using H2O2, O2, and NaOCl oxidant, respectively. According to the TG analysis, the initial degradation temperature of O-4-PIMP was 218°C,
which was by 50°C higher than that of 4-PIMP. Thermal analyses of 4-PIMP and O-4-PIMP were carried out in N2 atmosphere at 15–1000°C. The highest occupied molecular orbital, the lowest unoccupied molecular orbital, and electrochemical
energy gaps of 4-PIMP and O-4-PIMP were determined from the onset potentials for n-doping and p-doping, respectively. Also, optical band gaps of 4-PIMP and O-4-PIMP were determined according to UV-VIS measurements. 相似文献
996.
AbstractHerein the bioaccessibility of Mn, Cu, Zn, Cd, and Pb, selected from essential and toxic elements, was determined in commercially sold vegetable purees intended for infant and toddler consumption. Chemical fractionation studies using water, acetone, diethyl ether, chloroform:methanol, and n-hexane were employed to predict the importance of the protein and lipid parts of a matrix to assess the bioaccessibility data. In addition, in-vitro gastrointestinal digestion was performed to determine the bioaccessibility of the elements using a five level, three factor central composite design (CCD) to maximize the elemental solubility. The total elemental concentrations in all of the fractions were determined by inductively coupled plasma – mass spectrometry (ICP-MS). Based on the consumption of one jar of vegetable/rice-based baby food, Zn was 1.3% of the recommended dietary allowance and Mn was 4.2% of the adequate intake level, while Cu was almost 100% of the adequate intake level. Additionally, Pb was always below the detection limit and Cd was sometimes under the detection limit for the percent bioaccessibility. However, in some samples, Cd was as high as 80% of the tolerable weekly intake level depending on the body weight. 相似文献
997.
Antonino Mazzaglia Domenico Garozzo Raffaello Romeo 《Journal of organometallic chemistry》2005,690(8):1978-1985
MALDI and ESI-MS have been applied to the characterization of the reaction products between the labile cis-[Pt(DMSO)2Cl2] (1) and trans-[Pt(DMSO)2Cl(CH3)] (2) complexes with the simplest poly(amidoamine) ligand (PAMAM, G = 0, 1,2-diaminoethane as core). The comparison of the mass spectra of the starting G0 and those of the metallo-dendrimers formed upon mixing of the reagents in an equimolecular ratio, and the analysis of the isotopic distribution in the ESI spectra, have revealed the formation of cationic and neutral mononuclear complexes with PAMAM as ligand, e.g., cis-[Pt(DMSO)(PAMAM)Cl]Cl or trans-(C,N)[Pt(DMSO)(PAMAM)Cl(CH3)], together with various minor components, which have been identified as derivatives from defective structures of PAMAM. The geometry of the main products has been deduced from the values of the protons coupling constants with the isotopically abundant 195Pt. The metal-to-ligand bond is restricted to the peripheral amino groups of PAMAM which shows sufficient flexibility to involve either one or two branches in the coordination bonding. 相似文献
998.
Papaverine (1-(3,4-dimethoxybenzyl)-6,7-dimethoxyisoquinoline, PAP) is a member of the benzylisoquinoline sub-group of the opium alkaloids. It has been widely used for treating diseases like pulmonary arterial embolism and renal or biliary colic. In this paper, a specific conjugate of mono-demethylated papaverine-O-carboxylmethyl ether (MDMPAP-O-CME) and bovine serum albumin (BSA) was synthesized and used as the complete antigen (PAP-BSA), with which we successfully obtained a high-titer anti-PAP polyclonal antibody (pAb) by immunization of rabbits. The anti-PAP pAb showed high affinity to papaverine with an affinity constant (Kaff) of 7.3 × 107 L/mol. With this antibody, we established a sensitive immunochemical method for the determination of papaverine based on indirect competitive enzyme-linked immunosorbent assay (ELISA). The optimal concentrations of the coated antigen (PAP-OVA) and purified pAb used in the ELISA were 5 and 1.2 μg/mL, respectively. The cross reactivity of other benzylisoquinoline derived substances, including 1-(3,4-dihydroxybenzyl)-7-hydroxy-6-methoxy-isoquinoline (6-methoxy-papaveroline, MPAPO), morphine (MP) and codeine (CD) were all lower than 1%. The linear range of the calibration curve was 0.1-1000 ng/mL. Normal human serum samples were spiked with known amount of papaverine and measured by the ELISA. Recoveries were between 102% and 105%. Papaverine content in a commercial papaverine hydrochloride injection sample was also determined using the established ELISA. Compared with the results given by the control experiment of HPLC, the recoveries of ELISA to detect injection samples were 102-110%. The limits of detection for synthetic serum samples and injection samples of papaverine hydrochloride were 0.25 and 0.06 ng/mL, respectively. 相似文献
999.
Darko P. Aanin Sneana Rajkovi Dora Molnar-Gabor Milos I. Djuran 《Monatshefte für Chemie / Chemical Monthly》2004,135(12):1445-1453
Summary. Hydrolytic reactions between various palladium(II) complexes of the type cis-[Pd(L)(H2O)2]2+ in which L is ethylenediamine (en), 1,2-propylenediamine (1,2-pn), isobutylenediamine (ibn), 1,2-diaminocyclohexane (1,2-dach), N-methylethylenediamine (Meen), N,N,N,N-tetramethylethylenediamine (Me4en), S-methyl L-cysteine (MeS-L-HCys), L-methionine (L-HMet), and 2,5-dithiahexane (dth) and dipeptide N-acetylated L-methionylglycine (MeCOMet-Gly) were studied by 1H NMR spectroscopy. The reactions were carried out in the pH range 2.0–2.5 and at 50°C. In all these reactions, palladium(II) complex bound to a methionine residue effects the regioselective cleavage of the amide bond involving the carboxylic group of methionine. We found that the rate of hydrolysis and mechanism of this reaction are strongly dependent from the nature of the chelate ligand L in palladium(II) complexes of the type cis-[Pd(L)(H2O)2]2+. 相似文献
1000.
采用XAFS方法研究浸渍法制备并于低温焙烧的CuO/γ-Al2O3催化剂的局域结构.对于CuO负载量小于单层分散阈值的CuO/γ-Al2O3(0.4 mmol/100 m2),结果表明,CuO物种是以层状分散的孤立原子簇存在于γ-Al2O3载体表面,其第一近邻Cu-O配位环境的结构与晶态CuO的相似,键长和配位数分别为0.195 nm和4.对于CuO负载量等于单层分散阈值的CuO/γ-Al2O3(0.8 mmol/100 m2),已有少量的CuO纳米颗粒生成.对于CuO负载量大于单层分散阈值的CuO/γ-Al2O3(1.2 mmol/100 m2),其结构与多晶CuO的相近.基于CuO在γ-Al2O3载体上的三种不同分散状态的结构特点,我们提出了CuO/γ-Al2O3催化剂的结构模型. 相似文献