全文获取类型
收费全文 | 5635篇 |
免费 | 708篇 |
国内免费 | 882篇 |
专业分类
化学 | 6778篇 |
晶体学 | 106篇 |
力学 | 5篇 |
综合类 | 25篇 |
数学 | 3篇 |
物理学 | 308篇 |
出版年
2024年 | 7篇 |
2023年 | 40篇 |
2022年 | 103篇 |
2021年 | 206篇 |
2020年 | 326篇 |
2019年 | 250篇 |
2018年 | 202篇 |
2017年 | 194篇 |
2016年 | 332篇 |
2015年 | 297篇 |
2014年 | 313篇 |
2013年 | 558篇 |
2012年 | 536篇 |
2011年 | 325篇 |
2010年 | 299篇 |
2009年 | 301篇 |
2008年 | 314篇 |
2007年 | 322篇 |
2006年 | 288篇 |
2005年 | 254篇 |
2004年 | 305篇 |
2003年 | 231篇 |
2002年 | 273篇 |
2001年 | 133篇 |
2000年 | 101篇 |
1999年 | 110篇 |
1998年 | 81篇 |
1997年 | 90篇 |
1996年 | 84篇 |
1995年 | 82篇 |
1994年 | 42篇 |
1993年 | 39篇 |
1992年 | 60篇 |
1991年 | 16篇 |
1990年 | 24篇 |
1989年 | 10篇 |
1988年 | 22篇 |
1987年 | 5篇 |
1986年 | 13篇 |
1985年 | 7篇 |
1984年 | 5篇 |
1983年 | 2篇 |
1982年 | 8篇 |
1981年 | 5篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1974年 | 2篇 |
1973年 | 2篇 |
1972年 | 2篇 |
排序方式: 共有7225条查询结果,搜索用时 175 毫秒
151.
152.
用原位变温 31P NMR和分子模拟研究了手性氮磷配体与金属钌的配位过程。首先确定了配体及其与金属的配合物的化学位移信号分别在δ=-13.0ppm和δ=48.2ppm。配位过程在293~343K温度范围内,相继生成四配位和五配位中间体。四配位体在 31P NMR上对应于30.8ppm和-15.0ppm的两个信号;五配位中间体对应于35.1ppm和-16.5ppm的两个信号;最后在343K,产物中只有六配位的配合物存在,其信号出现在48.2ppm。为了得到各种中间体的结构,用分子模拟方法进行了结构优化计算,并比较了它们的构象能。计算结果表明,四配位中间体有两种构象,能量相差9kcal·mol-1,它们可能同时存在于平衡状态。而五配位中间体只有一种绝对优势构象,尚有一个磷原子未参与配位。六配位的钌金属配合物的结构优化结果显示,两个氯原子分别位于PNNP原子所构成平面的两侧。其构象能为162.0kcal·mol-1,其中键角能的贡献是112.5kcal·mol-1,而非键静电作用是-41.4kcal·mol-1,这表明分子内的静电吸引力对于形成完全配位产物是十分有利的,但是收敛的配体分子却承受了较大的键角张力。 相似文献
153.
Some new pyridyl alcohols with the cis-bicyclo[3.3.0]octane scaffold were synthesized and used as chiral ligands for the enantioselective addition of diethylzinc to aldehydes. Ligands 4 were found to be far superior to the C2-symmetric ligands 2 in terms of enantioselectivities. Quantitative yields and enantiomeric excesses of up to 92% were obtained when the ligand 4 was used. The carbonyl function in 4 proved to be beneficial for the high enantioselectivities in the addition of diethylzinc to aldehydes. Conversion of the carbonyl group into oxime or oxime ether group led to a sort of more active ligands, which catalyzed the same reaction with rate acceleration. 相似文献
154.
Further studies on dppm-stabilized mixed-metal clusters: X-ray structure of PdPtCoCl(CO)3(μ-dppm)2
1
Pierre Braunstein Claude de Bellefon Yves Dusausoy Daniel Bayeul 《Journal of Cluster Science》1995,6(1):175-185
The metalloligated mixed-metal cluster [PdPtCo2(CO)7(-dppm)2] (2) (dppm = -Ph2PCH2PPh2) possesses numerous potential reaction centers (e.g., metal(s), metal-metal bonds, CO, and dppm ligands) and this has previously led to an investigation of the site selectivity of reactions with nucleophiles. The exocyclic CO(CO)4 fragment was substituted with a chloride ligand and the resulting chiral, triangular cluster PdPtCoCl(CO)3(-dppm)2 (4) has been structurally characterized. The Pd-Co and Pt-Co edges of this almost equilateral triangle are bridged by a dppm ligand, and two of the three carbonyls borne by the Co atom are semi-triply bridging above and below the plane of the metals. The Co(CO)3P fragment behaves as an anionic 4-electron donor organometallic bridging group toward thed
9-d
9 Pd(I)-Pt(I) unit. Crystal data for4, monoclinic space groupP21/n with Z=4 in a unit cell of dimensionsa=12.291(3),b=19.321(4),c=23.680(5) Å,=100.05(2)°. The structure has been solved from diffractometer data by Patterson, Fourier methods and refined by full-matrix least squares on the basis of 3512 observed reflections (l>3) toR(F) andR
w(F) values of 0.059 and 0.061.Dedicated to Professor L. F. Dahl on the occasion of his 65th birthday, with our sincere congratulations and best wishes. 相似文献
155.
离子交换—电感耦合等离子体发射光谱法测定石灰石中的微量磷 总被引:5,自引:0,他引:5
本文介绍一种用ICP-AES法测定难熔材料石灰石中微量磷的方法。样品用HF-HNO_3-HCIO_4混合酸分解后,用阳离子交换树脂分离除去共存的金属离子,含磷溶液经浓缩后用ICP-AES法进行测定。本法用于测定含磷量为数十微克/毫升的石灰石样品,平行测得结果的相对标准偏差在2~3%之间,加入回收率为96~102%。 相似文献
156.
P. L. Patterson 《Chromatographia》1993,36(1):225-233
Summary The selectivities of two flame-based ionization detectors identified as a Remote FID (RFID) and a Flame Thermionic Ionization Detector (FTID) have been improved by introducing methane as a fuel for the flame. Both the RFID and FTID feature a detector struture in which the ionization polarizer and collector are located several centimeters downstream of an oxygen-rich flame, rather than immediately adjacent to the flame as in a flame ionization detector. The RFID detects long-lived negative ions produced in the flame by the combustion of lead, tin, phosphorus, or silicon compounds. The FTID re-ionizes and detects neutral electronegative products generated by combustion of nitrogen, halogen, or phosphorus compounds. An organic-fuelled RFID can detect 1 pg Pb (Sn, P)/sec with a selectivity of the order of 106 versus hydrocarbons. An organic fuelled FTID is applicable to detection of compounds at nanogram and higher levels. FTID selectivity for PCB compounds in a transformer oil matrix is of the order of 1051. The improved selectivity achieved by using an organic-fuelled flame is also applicable to the detection of phospholipid and other non-volatile N, P, or Cl compounds using an FID/FTID detector accessory for a TLC/FID analyser. 相似文献
157.
I. I. Ponomarev Yu. Yu. Rybkin E. I. Goryunov P. V. Petrovskii K. A. Lyssenko 《Russian Chemical Bulletin》2004,53(12):2881-2883
The reaction of 4,4-dimethyldiphenyl ether with phosphorus trichloride in the presence of anhydrous aluminum chloride was studied. This reaction affords 2,8-dimethyl-10H-105-phenoxaphosphine 10-oxide as virtually the only product. In air, the latter in an alkaline solution is quantitatively transformed into 10-hydroxy-2,8-dimethyl-10H-105-phenoxaphosphine 10-oxide.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2762–2765, December, 2004. 相似文献
158.
Yunjie Luo Yingming Yao Jinglei Chen Yong Zhang 《Journal of organometallic chemistry》2003,679(1):125-129
Reactions of [N(C6H3i-Pr2-2,6)(SiMe3)]2LnCl(THF) (Ln=Nd, Yb) with two equivalents of MeLi in a mixture solution of toluene and Et2O gave [N(C6H3i-Pr2-2,6)(SiMe3)]2LnCH3(μ-CH3)Li(THF)3·PhCH3 (Ln=Nd (1), Yb (2)) in good isolated yields as crystalline solids. The single-crystal structural analysis of 2 revealed that the coordination geometry of ytterbium ion is best described as a distorted pseudo-tetrahedron. Both 1 and 2 are active for the polymerization of methyl methacrylate to give syndiotactic-rich and high molecular weight polymers (Mn>104) with relatively narrow molecular weight distributions (Mw/Mn<2). 相似文献
159.
巢湖主要入湖河道磷的污染现状 总被引:6,自引:0,他引:6
为了解巢湖主要入湖河道中总磷的污染状况,进行了为期三年每月一次的污染调查,十五里河、南淝河、双桥河,污染较重,超出了(GH281-1999)《地表水环境质量标准》的V娄标准。污染主要来自工业废水、生活污水、和农业面源。认为只有开展农业面源污染治理,城市环境综合整治,城市环境综合整治,加强和削减农业化肥的使用量,使得入湖河道水质变好,巢湖的富营养化才能得到控制。 相似文献
160.
设计合成了一个新型吡啶基二氮环配体L(N,N'-双(吡啶基-3-亚甲基)-1,5-二氮环辛烷)及其铜配位聚合物{[Cu(滋-H2L)(L)Cl](ClO4)3}∞(1),研究了此配合物的晶体结构、光谱及磁性质。该配合物属正交晶系,Pnma空间群,晶胞参数为a=3.5170(17)nm,b=1.0440(5)nm,c=1.1966(6)nm,V=4.394(4)nm3,Z=4。配体L以顺式螯合和反式桥联两种不同的配位形式将铜离子连接起来形成一维链状阳离子结构。 相似文献