全文获取类型
收费全文 | 14943篇 |
免费 | 2610篇 |
国内免费 | 2528篇 |
专业分类
化学 | 11832篇 |
晶体学 | 194篇 |
力学 | 658篇 |
综合类 | 260篇 |
数学 | 1579篇 |
物理学 | 5558篇 |
出版年
2024年 | 45篇 |
2023年 | 275篇 |
2022年 | 480篇 |
2021年 | 488篇 |
2020年 | 604篇 |
2019年 | 637篇 |
2018年 | 530篇 |
2017年 | 509篇 |
2016年 | 791篇 |
2015年 | 836篇 |
2014年 | 895篇 |
2013年 | 1183篇 |
2012年 | 1312篇 |
2011年 | 1389篇 |
2010年 | 994篇 |
2009年 | 1009篇 |
2008年 | 1077篇 |
2007年 | 949篇 |
2006年 | 933篇 |
2005年 | 839篇 |
2004年 | 661篇 |
2003年 | 582篇 |
2002年 | 620篇 |
2001年 | 458篇 |
2000年 | 414篇 |
1999年 | 316篇 |
1998年 | 200篇 |
1997年 | 179篇 |
1996年 | 170篇 |
1995年 | 136篇 |
1994年 | 119篇 |
1993年 | 97篇 |
1992年 | 71篇 |
1991年 | 51篇 |
1990年 | 43篇 |
1989年 | 36篇 |
1988年 | 23篇 |
1987年 | 27篇 |
1986年 | 23篇 |
1985年 | 19篇 |
1984年 | 9篇 |
1983年 | 9篇 |
1982年 | 5篇 |
1981年 | 6篇 |
1980年 | 4篇 |
1975年 | 3篇 |
1974年 | 4篇 |
1973年 | 4篇 |
1957年 | 5篇 |
1936年 | 3篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
231.
Yuan Yuan Wang Wei Li Li Yi Dai 《中国化学快报》2007,18(10):1187-1190
Cationic ring-opening polymerization of 3,3-bis(chloromethyl)oxacyclobutane catalyzed by BF_3·OEt_2 was carried out in ionic liquids [bmim]BF_4 and [bmim]PF_6.The influences of BCMO concentration and molar ratio of BCMO/BF_3·OEt_2 on the molecular weights and yield of PBCMO were investigated.The polymerization in ionic liquids proceed to high conversions,although molecular weights are limited,similar to polymerization in organic solvent such as CH_2Cl_2.Follow a viewpoint of green chemistry, we feel ionic liquid [bmim]BF_4 is superior to [bmim]PF_6.Extracting [bmim]PF_6 from the product using organic solvent as extractant limits its advantage as a green reaction media. 相似文献
232.
Fine particle superacidic sulfated zirconia (SO42−/ZrO2, S-ZrO2) was synthesized by ameliorated method, and composite membranes with different S-ZrO2 contents were prepared by a recasting procedure from a suspension of S-ZrO2 powder and Nafion solution. The physico-chemical properties of the membranes were studied by ion exchange capacity (IEC) and liquid water uptake measurements, scanning electron microscopy (SEM) and X-ray diffraction (XRD) analysis, thermogravimetry–mass spectrometry (TG–MS) and Fourier transform infrared (FT-IR) spectroscopy. The results showed that the IEC of composite membrane increased with the content of S-ZrO2, S-ZrO2 was compatible with the Nafion matrix, the incorporation of the S-ZrO2 could increase the crystallinity and also improve the initial degradation temperature of the composite membrane. The performance of single cell was the best when the S-ZrO2 content was 15 wt.%, and achieved 1.35 W/cm2 at 80 °C and 0.99 W/cm2 at 120 °C based on H2/O2 and at a pressure of 2 atm, the performance of the single cell with optimized S-ZrO2 was far more than that of the Nafion at the same condition (e.g. 1.28 W/cm2 at 80 °C, 0.75 W/cm2 at 120 °C). The 15 wt.% S-ZrO2/Nafion composite membrane showed lower fuel cell internal resistance than Nafion membranes at high temperature and low relative humidity (RH). 相似文献
233.
Pil Kim Younghun Kim Taewook Kang In Kyu Song Jongheop Yi 《Catalysis Surveys from Asia》2007,11(1-2):49-58
Mesoporous materials have attracted considerable attention for use as a catalyst or a catalyst support due to their remarkable
textural properties such as high surface area and large pore volume with a narrow pore size distribution. Many efforts have
been made to design mesoporous materials for use in heterogeneous catalyst systems. Recent progress and results regarding
the preparation of nickel-mesoporous materials and their application to the hydrodechlorination of chlorinated organic compounds
were discussed in this review. Mesoporous materials were used as a support for nickel catalyst or a nickel-incorporated mesoporous
catalytic material in this work. Two research areas were described and discussed in this review. One is the preparation of
mesoporous alumina-supported nickel catalysts and their application to the hydrodechlorination of 1,2-dichloropropane and
o-dichlorobenzene. The other is the preparation of mesoporous silica-supported nickel catalysts and their application to the
hydrodechlorination of 1,1,2-trichloroethane and chlorobenzene. 相似文献
234.
The cleavage of a disulfide bond and the redox equilibrium of thiol/disulfide are strongly related to the levels of glutathione (GSH)/oxidized glutathione (GSSG) or mixed disulfides in vivo. In this work, the cleavage of a disulfide bond in GSSG induced by a platinum(II) complex [Pt(Met)Cl2] (where Met = methionine) was studied and the cleavage fragments or their platinated adducts were identified by means of electrospray mass spectrometry, high-performance liquid chromatography, and ultraviolet techniques. The second-order rate constant for the reaction between [Pt(Met)Cl2] and GSSG was determined to be 0.4 M(-1) s(-1) at 310 K and pH 7.4, which is 100- and 12-fold faster than those of cisplatin and its monoaqua species, respectively. Different complexes were formed in the reaction of [Pt(Met)Cl2] with GSSG, mainly mono- and dinuclear platinum complexes with the cleavage fragments of GSSG. This study demonstrated that [Pt(Met)Cl2] can promote the cleavage of disulfide bonds. The mechanistic insight obtained from this study may provide a deeper understanding on the potential involvement of platinum complexes in the intracellular GSH/GSSG systems. 相似文献
235.
236.
237.
Xingang Kong Jiarui Zhang Jianfeng Huang Jiayin Li Yi Qin Ting Zhao Qi Feng 《中国化学快报》2019,30(3):771-774
SnNb2O6 and Sn2Nb2O7 nanosheets were synthetized via microwave assisted hydrothermal method, and innovatively employed as anode materials for lithium-ion battery. Compared with Sn2Nb2O7 and the previously reported pure Sn-based anode materials, the SnNb2O6 electrode exhibited outstanding cycling performance. 相似文献
238.
Chao Chen Yu-Lin Yang Kun-Lin Huang Zhen-Hua Sun Wei Wang Zhuo Yi Yun-Ling Liu Wen-Qin Pang 《Polyhedron》2004,23(18):3033-3042
With a hydrothermal technique, a layered titanium phosphate with the formula Ti2(H2PO4)(HPO4)(PO4)2 · 0.5C6N2H16 (denoted TP-J2) has been prepared by treating the Ti/H3PO4/H2O/1-methylpiperazine system directly. The as-synthesized products were characterized by powder X-ray diffraction, CP-MAS solid-state 31P NMR spectroscopy, thermogravimetric and differential thermal analyses (TG-DTA). The structure was solved by single-crystal X-ray diffraction analysis and it presents an extended γ-phase intercalated with organic amine. Crystal data: triclinic, , a = 8.106 (2) Å, b = 8.197 (2) Å, c = 11.658 (2) Å. = 78.32 (3)°, β = 80.85 (3)°, γ = 77.90 (3)°, Z = 2. Additionally, the intercalation behavior of TP-J2 with n-alkyl monoamine (n = 2, 3, 4, 6, 8, 10 and 12) was investigated. Owing to the strong brønsted base, N,N′-dimethylpiperazine, resides in the interlayer, it presented unusual features of TP-J2 in contrast with that of γ-Tip. 相似文献
239.
使用了不同密度泛函方法计算X-H (X = C, N, O, Si, P, S) 键离解能,并分析不同密度泛函方法的计算精度。研究发现大多数密度泛函方法包括B3LYP, B3P86, B3PW91, G96LYP, PBE1PBE,和BH&HLYP都明显低估键离解能13-25 kJ/mol。该现象与是否使用无限基组无关,因为即使使用无限基组键离解能仍然被低估。因此密度泛函方法不适合用于键离解能的估算。其中B3P86方法的偏差最小。进一步分析表明,使用限制性开壳层计算并无任何优势,在大多数情况下非限制性开壳层计算实际上比限制性开壳层计算要好。最后,我们发现了密度泛函方法对键离解能的低估是系统的,因此建议利用校准后的UDFT/6-311++G(d, p)方法计算化学键离解能。 相似文献
240.
Chiral separation of 20 pairs of amino acids derivatized with fluoresceine-5-isothiocyanate (FITC) by capillary electrophoresis and laser-induced fluorescence detection was studied using the mixture of beta-cyclodextrin (beta-CD) and sodium taurocholate (STC) as selector. Resolution was considerably superior to that obtained by using either beta-CD or STC alone. The molar ratio of beta-CD to STC of about 2:3 was found to be critical to achieve maximum separation. At this beta-CD-to-STC ratio, chiral separation occurred at really low total concentration of beta-CD and STC (<0.1 mM). Other impacting factors were investigated including the total concentration of beta-CD and STC, pH, and capillary conditioning procedure between two successive runs. Using a running buffer of 80 mM borate containing 20 mM beta-CD and 30 mM STC at pH 9.3, all of the 20 pairs of FITC-amino acid enantiomers were baseline resolved. The resolutions of the most pairs of the amino acid enantiomers (17 of 20) were higher than 3.0, only three pairs gave a resolution lower than 3.0 but higher than 1.90 (beta-phenylserine, pSer). The highest resolution reached 14.58 (Glu). Two derivatives of beta-CD, 2-hydroxypropyl-beta-CD (HP-beta-CD) and heptakis(2,6-di-O-methyl)-beta-CD (DM-beta-CD) were also explored. HP-beta-CD showed similar cooperative effect with STC, while DM-beta-CD together with STC led to poorer chiral separation. 相似文献