全文获取类型
收费全文 | 41579篇 |
免费 | 5318篇 |
国内免费 | 4162篇 |
专业分类
化学 | 11250篇 |
晶体学 | 963篇 |
力学 | 9772篇 |
综合类 | 564篇 |
数学 | 14741篇 |
物理学 | 13769篇 |
出版年
2024年 | 102篇 |
2023年 | 465篇 |
2022年 | 836篇 |
2021年 | 951篇 |
2020年 | 1203篇 |
2019年 | 1038篇 |
2018年 | 1062篇 |
2017年 | 1495篇 |
2016年 | 1681篇 |
2015年 | 1326篇 |
2014年 | 2146篇 |
2013年 | 2971篇 |
2012年 | 2541篇 |
2011年 | 2919篇 |
2010年 | 2467篇 |
2009年 | 2731篇 |
2008年 | 2645篇 |
2007年 | 2629篇 |
2006年 | 2411篇 |
2005年 | 2237篇 |
2004年 | 1922篇 |
2003年 | 1722篇 |
2002年 | 1537篇 |
2001年 | 1292篇 |
2000年 | 1212篇 |
1999年 | 1089篇 |
1998年 | 1010篇 |
1997年 | 857篇 |
1996年 | 703篇 |
1995年 | 592篇 |
1994年 | 546篇 |
1993年 | 440篇 |
1992年 | 451篇 |
1991年 | 346篇 |
1990年 | 281篇 |
1989年 | 215篇 |
1988年 | 178篇 |
1987年 | 128篇 |
1986年 | 86篇 |
1985年 | 116篇 |
1984年 | 108篇 |
1983年 | 53篇 |
1982年 | 71篇 |
1981年 | 51篇 |
1980年 | 26篇 |
1979年 | 44篇 |
1978年 | 31篇 |
1977年 | 38篇 |
1976年 | 13篇 |
1957年 | 11篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
971.
972.
973.
Qiang‐Gen Li Chao Deng Yi Ren Ning‐Bew Wong San‐Yan Chu Xin Wang 《International journal of quantum chemistry》2008,108(1):142-150
Computational investigations by an ab initio molecular orbital method (HF and MP2) with the 6‐311+G(d,p) and 6‐311++G(2df, 2pd) basis sets on the tautomerism of three monochalcogenosilanoic acids CH3Si(?O)XH (X = S, Se, and Te) in the gas phase and a polar and aprotic solution tetrahydrofuran (THF) was undertaken. Calculated results show that the silanol forms CH3Si(?X)OH are much more stable than the silanone forms CH3Si(?O)XH in the gas‐phase, which is different from the monochalcogenocarboxylic acids, where the keto forms CH3C(?O)XH are dominant. This situation may be attributed to the fact that the Si? O and O? H single bonds in the silanol forms are stronger than the Si? X and X? H single bonds in the silanone forms, respectively, even though the Si?X (X = S, Se, and Te) double bonds are much weaker than the Si?O double bond. These results indicate that the stability of the monochalcogenosilanoic acid tautomers is not determined by the double bond energies, contrary to the earlier explanation based on the incorrect assumption that the Si?S double bond is stronger than the S?O double bond for the tautomeric equilibrium of RSi(?O)SH (R?H, F, Cl, CH3, OH, NH2) to shift towards the thione forms [RSi(?S)OH]. The binding with CH3OCH3 enhances the preference of the silanol form in the tautomeric equilibrium, and meanwhile significantly lowers the tautomeric barriers by more than 34 kJ/mol in THF solution. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008 相似文献
974.
A new four‐way multiblock method is proposed to study the links between more than two sets of data tables (several multiblocks) measured on the same observations. This method, called STATIS‐4, generalizes the STATIS method to more than one set of matrices. In its first step, STATIS‐4 is searching for one consensus for each multiblock and a global consensus summarizing all the previous ones as good as possible. Some graphical representations can be made to visualize the proximities between the tables within a multiblock and to visualize those between all the multiblocks. Moreover, plots of the observations for each table, each multiblock and global observations can be made. The theory of STATIS‐4 and the algorithm used to obtain the optimal solutions are presented. Moreover, a real sensory dataset is studied with STATIS‐4. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
975.
研究了N-乙酰-L-半胱氨酸(N-acetyl-L-cysteine,NAC)在咖啡酸(CFA)修饰碳糊电极(CFA/CPE)上的电催化行为。结果表明,NAC在裸碳糊电极(CPE)上的直接电化学氧化过程十分迟缓,而CFA/CPE对NAC的电化学氧化具有良好的催化作用。用循环伏安法(CV)、计时电流法(CA)测定了NAC在CFA/CPE上的电极过程动力学参数。电荷传递系数α=0.79,电催化氧化反应速率常数k=(4.40±0.10)×10^3(mol.L^-1)^-1.s^-1。用微分脉冲伏安法(DPV)测得催化氧化峰电流与NAC浓度在1.0×10^-6~7.5×10^-4mol.L^-1范围内呈良好的线性关系,线性回归方程为Ipa(μA)=4.075c(mmol.L^-1)+2.671,r=0.9988,检出限为1.7×10^-7mol.L^-1。用该方法对市售药品富露施中的NAC含量进行测定,结果令人满意。 相似文献
976.
化学提取方法快速评估污染土壤中生物可消化性铅 总被引:1,自引:0,他引:1
为建立一种简单的方法鉴定污染土壤中的铅在消化系统中被人体消化吸收的潜力(即生物可消化性或生物可接受性),采用连续提取法和7种单一化学提取法比较研究了13个污染土壤中铅的化学形态及其可提取性,以模拟胃液提取法为参比,选择和比较了7种化学提取剂,包括:CaCl2稀盐、NH4OAc、DTPA—TEA、Mehlich Ⅰ、Mehlich Ⅲ、草酸铵缓冲液和盐酸羟铵溶液。结果表明,土壤中铅的平均提取率由高至低依次为:草酸铵缓冲液,盐酸羟铵溶液,MehlichⅠ、MehlichⅢ,DTPA—TEA,NH4OAc,CaCl2相关分析表明,氧化物结合态铅是污染土壤中生物可消化铅的主要组分,用盐酸羟铵溶液提取的铅可很好地表征污染土壤中铅的生物可消化性,其提取量与模拟胃液提取的铅接近,两者之间具有显著的相关性。 相似文献
977.
In this study density functional theory (DFT) calculations at B3LYP/6-31G(d), B3LYP/6-31+G(d) and B3LYP/6-311+G(2df,2p) levels for geometry optimization and total energy calculation were applied for investigation of the important energy-minimum conformations and transition-state of 1,2-, 1,3-, and 1,4-dithiepanes. Moreover, ab initio calculations at HF/6-31G(d) level of theory for geometry optimization and MP2/6-311G(d)//HF/ 6-31G(d) level for a single-point total energy calculation were reported for different conformers. The obtained results reveal that, the twist-chair conformer is a global minimum for all of these compounds. Also, two local minimum were found in each case, which are twisted-chair and twisted-boat conformers. The boat and chair geometries are transition states. The minimum energy conformation of 1,2-dithiepane is more stable than the lowest energy forms of 1,3-dithiepane and 1,4-dithiepane. Furthermore, the anomeric effect was investigated for 1,3-dithiepane by the natural bond orbital method. The computational results of this study shows that all conformers of 1,3-dithiepane have a hypercojugation system. Finally, the 13C NMR chemical shifts for the conformers of 1,4-dithiepane were calculated, which have good correlation with their experimental values. 相似文献
978.
Azido-protected Fmoc-Lys-OH (Fmoc-Lys(N3)-OH) was synthesized from Fmoc-Lys-OH by the copper(II)-catalyzed diazo transfer method, and introduced to a peptide by the ordinary Fmoc-based solid-phase peptide synthesis. This azido peptide could be condensed with a peptide thioester by the Ag+-free thioester method without any significant side reactions. The azido group was easily reduced to an amino group by Zn powder after peptide condensation. 相似文献
979.
Polymer materials used in railway field are degraded by environmental factors such as thermal, oxidative, photolytic, hydrolytic, and mechanical. The expected service life of the polymer materials used in railway field is approximately 20 years that is relatively long period for the polymer material; therefore, respective degradation factors should be well considered. Some of the degradation conditions indicate similar mechanism. The oxidative reaction was seen in every degradation conditions under air atmosphere. The hydrolytic reaction was mainly observed in chemical and biological degradations. The degradation behavior of the polymer material was analyzed by various methods. FTIR, thermal analysis (TG, DSC), and molecular weight determination were mainly applied for its purpose. However, the degradation mechanism of practical products made of polymer material was insufficiently studied and the exchange criteria of the products depended on the visual inspection without the suitable degradation analysis not only in the railway field but also in other commercial and industrial fields. In addition, most of the methods to analyze degradation of polymer material are performed on the standard specimen forms. For the installed product, some kinds of damage are generated through the sample collection process; therefore, the damaged products have to be exchanged for brand new ones or repaired totally to be used for more period. Moreover, it is hard to suspend the railway service for the degradation analysis of polymer products. From these backgrounds, the prospect of degradation analysis related to polymer materials used in railway field was proposed. 相似文献
980.
A new adsorbent is proposed for the solid-phase extraction of phenol and 1-naphthol from polluted water. The adsorbent (TX-SiO2) is an organosilica composite made from a bifunctional immobilized layer comprising a major fraction (91%) of hydrophilic
diol groups and minor fraction (9%) of the amphiphilic long-chain nonionic surfactant Triton X-100 (polyoxyethylated isooctylphenol)
(TX). Under static conditions phenol was quantitatively extracted onto TX-SiO2 in the form of a 4-nitrophenylazophenolate ion associate with cetyltrimethylammonium bromide. The capacity of TX-SiO2 for phenol is 2.4 mg g−1 with distribution coefficients up to 3.4 × 104 mL g−1; corresponding data for 1-naphthol are 1.5 mg g−1 and 3 × 103 mL g−1. The distribution coefficient does not change significantly for solution volumes of 0.025–0.5 L and adsorbent mass less than
0.03 g; 1–90 μg analyte can be easily eluted by 1–3 mL acetonitrile with an overall recovery of 98.2% and 78.3% for phenol
and 1-naphthol, respectively. Linear correlation between acetonitrile solution absorbance (A
540) and phenol concentration (C) in water was found according to the equation A
540 = (6 ± 1) × 10−2 + (0.9 ± 0.1)C (μmol L−1) with a detection range from 1 × 10−8 mol L−1 (0.9 μL g−1) to 2 × 10−7 mol L−1 (19 μL g−1), a limit of quantification of 1 μL g−1 (preconcentration factor 125), correlation coefficient of 0.936, and relative standard deviation of 2.5%. A solid-phase colorimetric
method was developed for quantitative determination of 1-naphthol on adsorbent phase using scanner technology and RGB numerical
analysis. The detection limit of 1-naphthol with this method is 6 μL g−1 while the quantification limit is 20 μL g−1. A test system was developed for naked eye monitoring of 1-naphthol impurities in water. The proposed test kit allows one
to observe changes in the adsorbent color when 1-naphthol concentration in water is 0.08–3.2 mL g−1. 相似文献