全文获取类型
收费全文 | 2989篇 |
免费 | 391篇 |
国内免费 | 562篇 |
专业分类
化学 | 3335篇 |
晶体学 | 129篇 |
力学 | 26篇 |
综合类 | 32篇 |
数学 | 11篇 |
物理学 | 409篇 |
出版年
2024年 | 9篇 |
2023年 | 33篇 |
2022年 | 84篇 |
2021年 | 87篇 |
2020年 | 127篇 |
2019年 | 110篇 |
2018年 | 73篇 |
2017年 | 110篇 |
2016年 | 138篇 |
2015年 | 145篇 |
2014年 | 179篇 |
2013年 | 301篇 |
2012年 | 247篇 |
2011年 | 190篇 |
2010年 | 153篇 |
2009年 | 171篇 |
2008年 | 191篇 |
2007年 | 180篇 |
2006年 | 192篇 |
2005年 | 195篇 |
2004年 | 153篇 |
2003年 | 177篇 |
2002年 | 120篇 |
2001年 | 89篇 |
2000年 | 98篇 |
1999年 | 52篇 |
1998年 | 46篇 |
1997年 | 62篇 |
1996年 | 51篇 |
1995年 | 42篇 |
1994年 | 35篇 |
1993年 | 18篇 |
1992年 | 19篇 |
1991年 | 16篇 |
1990年 | 9篇 |
1989年 | 4篇 |
1988年 | 4篇 |
1987年 | 4篇 |
1986年 | 5篇 |
1985年 | 4篇 |
1984年 | 4篇 |
1983年 | 1篇 |
1982年 | 2篇 |
1981年 | 1篇 |
1980年 | 2篇 |
1979年 | 3篇 |
1978年 | 2篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1972年 | 2篇 |
排序方式: 共有3942条查询结果,搜索用时 15 毫秒
31.
Khodabakhsh NIKNAM Mohammad Ali ZOLFIGOL Zahra HOSSIENINEJAD Nader DANESHVAR 《催化学报》2007,28(7):591-595
以金属硫酸氢盐M(HSO4)n(Ca(HSO4)2,Zn(HSO4)2和过硫酸氢钾制剂oxone○R)为催化剂催化醛、1,3-二羰基化合物和尿素进行缩合反应,在90℃及无溶剂的条件下高收率、一锅法合成了3,4-二氢嘧啶-2(1H)-酮. 相似文献
32.
Fadila Balegroune Pierre Braunstein Laurent Douce Yves Dusausoy Daniel Grandjean Michael Knorr Martin Strampfer 《Journal of Cluster Science》1992,3(3):275-296
The reactions of K[Fe{Si(OMe)3}(CO)3(PY)][PY=Ph2PCH2C(O)Ph, Ph2PCH2C(O)[(-C5H4)FeCp] (Cp=5-C5H5), Ph2P(CH2)2CN] with CdCl2·2.5H2O, ZnX
2 (X=Cl, I) or InCl3 afforded Fe-Cd-Fe or Fe-M(-X)2
M-Fe (M=Cd, Zn, In;X=Cl, I) and Fe-InCl2 complexes. Some of them contain an unusual and labile -2-SiO alkoxysilyl bridge which may be associated with a bridging mode for the ketophosphine ligand (first such example structurally established), thus providing original results in bimetallic chemistry on the intramolecular coordination of oxygendonor functions ofchemically different hemilabile ligands firmly attached to a neighboring metal center. The structures of the trinuclear complex (3), of the chlorobenzene solvate of the tetranuclear complex (4a·C6H5Cl) and of [mer-(OC)3{(EtO)3Si} (4e) have been determined by X-ray diffraction. Crystals of 3 are orthorhombic, space groupPbcn, witha=19.010(4),b=11.766(5),c=26.998(7)Å, andZ=4. Crystals of4a·C6H5Cl are monoclinic, space groupC2/c witha=22.455(3),b=17.680(2),c=16.627(4)Å, =90.80(4)°, andZ=4. Crystals of4e are monoclinic, space groupC2/c witha=25.392(5),b=18.554(6),c=16.28(1)Å, =120.73(3)°, andZ=4. The structures were solved using direct methods and Fourier difference techniques and refined by blocked full-matrix least squares toR=0.035 (R
w
=0.049) for 2719 observed reflections, toR=0.042 (R
w
=0.056) for 3082 observed reflections, and toR=0.057 (R
w
=0.075) for 1850 observed reflections for3, 4a·C6H5Cl and4e, respectively. The Fe-Zn complexes (9a), (9b) and (9c) were prepared and characterized by spectroscopic methods.Part 21 in the Series: Complexes with Functional Phosphines. Part 20: P. Braunstein, S. Coco Cea, A. DeCian, and J. Fischer (1992).Inorg. Chem.
31, 4203. 相似文献
33.
Highly reactive zinc was readily prepared by electrolysis of a DMF solution containing pyrene as a mediator with a platinum cathode and a zinc anode. Preferential reduction of pyrene occurred to generate the corresponding radical anion, which reduced zinc ions generated from anodic dissolution to give zero valent zinc with high reactivity. The reactive zinc was successfully used for an efficient transformation of bromoalkanes into the corresponding organozinc bromides. Organozinc bromides obtained were further used successfully in Pd-catalyzed cross-coupling reaction with various aryl iodides and bromides. 相似文献
34.
The Mg3−xZnxSb2 phases with x=0-1.34 were prepared by direct reactions of the elements in tantalum tubes. According to the X-ray single crystal and powder diffraction, the Mg3−xZnxSb2 phases crystallize in the same P3¯m1 space group as the parent Mg3Sb2 phase. The Mg3−xZnxSb2 structure is different from the other substituted structures of Mg3Sb2, such as (Ca, Sr, Ba) Mg2Sb2 or Mg5.23Sm0.77Sb4, in a way that in Mg3−xZnxSb2 the Mg atoms on the tetrahedral sites are replaced, while in the other structures Mg on the octahedral sites is replaced. Thermoelectric performance for the two members of the series, Mg3Sb2 and Mg2.36Zn0.64Sb2, was evaluated from low to room temperatures through resistivity, Seebeck coefficient and thermal conductivity measurements. In contrast to Mg3Sb2 which is a semiconductor, Mg2.36Zn0.64Sb2 is metallic and exhibits an 18-times larger dimensionless figure-of-merit, ZT, at room temperature. However, thermoelectric performance of Mg2.36Zn0.64Sb2 is still poor and it is mostly due to its large electrical resistivity. 相似文献
35.
Utilization of a spiropyran derivative in a polymeric film optode for selective fluorescent sensing of zinc ion 总被引:1,自引:0,他引:1
ZHANG Ying SHAO Na YANG Ronghua LI Ke’an LIU Feng CHAN Winghong & MO Tian . College of Chemistry Molecular Engineering Peking University Beijing China . Department of Chemistry Hong Kong Baptist University Hong Kong China 《中国科学B辑(英文版)》2006,49(3):246-255
Spiropyrans are the most studied families of func- tional materials due to their reversible structural con- version in response to external optical, chemical, and thermal stimulation[1]. Irradiation with ultraviolet light causes formation of an extended π-conjugation open form (merocyanine form) by heterolytic cleavage of the C (spiro)-O bond, which generates an intense ab- sorption in the visible region. Under the irradiating of visible light, the opened form will come back to the closed spi… 相似文献
36.
合成了新型手性Salen配体(H3L)及新型手性Salen双核锌配合物(主体).通过研究主体对咪唑类客体及氨基酸酯类客体的分子识别行为,测定了这些配位反应的缔合常数.主体对咪唑类客体分子识别的缔合常数顺序为:K(Im) >K(2-MeIm) >K(2-Et-4-MeIm).主体对氨基酸酯类客体分子识别的缔合常数顺序为:K(LeuOCH3) >K(ValOCH3) >K(AlaOCH3) >K(SerOCH3),配位数均为2.主体与D、 L型氨基酸酯分子识别反应在不同温度下的缔合常数结果表明,随着温度的升高,对映选择性下降.实验发现反应体系中存在焓熵补偿关系. CD光谱的研究结果也反映了主体对不同客体识别能力的差异. 相似文献
37.
为观察二硫化碳(CS2)对机体铜,锌水平的影响,对某化纤厂35名接触CS2工人和41名非接触工人的血铜,锌值进行调查,比较,并进行了动物染毒实验。SD大鼠吸入CS2浓度分别为5和50mg/m^3,每日5h,每周6d,连续6个月,于染毒2,4,6个月时测定血浆铜,锌值及染毒6个月时肝脏铜,锌含量。结果显示,CS2接触组工人血铜,锌水平较对照组显著降低(P<0.05)。在CS2染毒6个月时,50mg/m^3 CS2染毒组血浆及肝脏铜水平均较对照组及5mg/m^3 CS2染毒组显著降低(P<0.05)。可见接触CS2能干扰机体铜,锌代谢,导致体内铜,锌含量减少。 相似文献
38.
Bart M. J. M. Suijkerbuijk Dr. Duncan M. Tooke Dr. Anthony L. Spek Prof. Dr. Gerard van Koten Prof. Dr. Robertus J. M. Klein Gebbink Prof. Dr. 《化学:亚洲杂志》2007,2(7):889-903
A series of meso‐tetrakis‐(ERE donor) zinc(II) porphyrins n Zn (ERE donor=4‐R‐3,5‐bis[(E)‐methyl]phenyl; 1 Zn: E=NMe2, R=Br; 2 Zn: E=NMe2, R=H; 3 Zn: E=OMe, R=Br; 4 Zn: E=OMe, R=H) have been synthesized in excellent yields. As a result of the combination of a Lewis acidic site and eight Lewis basic sites within one molecule, monomeric molecules of n Zn self‐assemble to form one‐dimensional porphyrin polymers [ n Zn]∞ in the solid state, as confirmed for 1 Zn and 3 Zn by X‐ray crystallography. The coordination environment around the zinc(II) ions in these polymers is octahedral. They are ligated by four equatorial nitrogen atoms of the porphyrin and two apical E atoms (E=N, O) provided by the EBrE donor groups of adjacent n Zn molecules. Complexes 2 Zn and 4 Zn did not form single crystals, but solid‐state UV/Vis analysis points to the formation of similar structures. Solution UV/Vis and 1H NMR spectroscopy indicated that interactions between 1 Zn and 2 Zn monomers in the polymers are stronger than between 3 Zn and 4 Zn monomers. Interestingly, they also revealed that the presence of a neighboring bromine atom in the EBrE donor groups has a considerable influence on the coordination properties of the benzylic N or O atoms. The zinc(II) ions of the porphyrins most likely adopt only hexacoordination in the solid state, owing to the unique predisposition of Lewis acidic and basic sites in the n Zn molecules. Several parameters of the aggregates, for example, the interplanar separation between porphyrins and the zinc–zinc distances, change as a function of the coordinating E groups. The high degree of modularity in their synthesis makes these zinc(II) porphyrins an interesting new entry in noncovalent multiporphyrin assemblies. 相似文献
39.
《Mendeleev Communications》2020,30(2):192-194
- Download : Download high-res image (135KB)
- Download : Download full-size image
40.
Koushik Dhara Santanu Karan Jagnyeswar Ratha Partha Roy Goutam Chandra Mario Manassero Dr. Biswanath Mallik Dr. Pradyot Banerjee Dr. 《化学:亚洲杂志》2007,2(9):1091-1100
A 2D coordination compound {[Cu2(HL)(N3)]?ClO4}∞ ( 1 ; H3L=2,6‐bis(hydroxyethyliminoethyl)‐4‐methyl phenol) was synthesized and characterized by single‐crystal X‐ray diffraction to be a polymer in the crystalline state. Each [Cu2(HL)(N3)]+ species is connected to its adjacent unit by a bridging alkoxide oxygen atom of the ligand to form a helical propagation along the crystallographic a axis. The adjacent helical frameworks are connected by a ligand alcoholic oxygen atom along the crystallographic b axis to produce pleated 2D sheets. In solution, 1 dissociates into [Cu2(HL)2(H3L)]?2H2O ( 2 ); the monomer displays high selectivity for Zn2+ and can be used in HEPES buffer (pH 7.4) as a zinc ion selective luminescent probe for biological application. The system shows a nearly 19‐fold Zn2+‐selective chelation‐enhanced fluorescence response in the working buffer. Application of 2 to cultured living cells (B16F10 mouse melanoma and A375 human melanoma) and rat hippocampal slices was also studied by fluorescence microscopy. 相似文献