全文获取类型
收费全文 | 11617篇 |
免费 | 1426篇 |
国内免费 | 2343篇 |
专业分类
化学 | 12547篇 |
晶体学 | 172篇 |
力学 | 308篇 |
综合类 | 116篇 |
数学 | 55篇 |
物理学 | 2188篇 |
出版年
2024年 | 55篇 |
2023年 | 179篇 |
2022年 | 428篇 |
2021年 | 566篇 |
2020年 | 776篇 |
2019年 | 597篇 |
2018年 | 422篇 |
2017年 | 470篇 |
2016年 | 513篇 |
2015年 | 515篇 |
2014年 | 563篇 |
2013年 | 1078篇 |
2012年 | 770篇 |
2011年 | 594篇 |
2010年 | 469篇 |
2009年 | 565篇 |
2008年 | 572篇 |
2007年 | 601篇 |
2006年 | 618篇 |
2005年 | 575篇 |
2004年 | 577篇 |
2003年 | 508篇 |
2002年 | 497篇 |
2001年 | 320篇 |
2000年 | 303篇 |
1999年 | 265篇 |
1998年 | 249篇 |
1997年 | 232篇 |
1996年 | 224篇 |
1995年 | 220篇 |
1994年 | 179篇 |
1993年 | 153篇 |
1992年 | 149篇 |
1991年 | 87篇 |
1990年 | 72篇 |
1989年 | 60篇 |
1988年 | 60篇 |
1987年 | 54篇 |
1986年 | 37篇 |
1985年 | 35篇 |
1984年 | 22篇 |
1983年 | 13篇 |
1982年 | 29篇 |
1981年 | 20篇 |
1980年 | 21篇 |
1979年 | 14篇 |
1978年 | 12篇 |
1977年 | 8篇 |
1976年 | 12篇 |
1973年 | 11篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
71.
Dithiocarbamate functions were incorporated into different polyacrylamide matrices crosslinked with a flexible and hydrophilic
crosslinking agent, tetraethyleneglycol diacrylate (TEGDA), and their complexation behaviours were investigated. Crosslinked
polyacrylamides with varying extents of the tetrafunctional TEGDA crosslinks were prepared by free radical solution polymerization
at 60°C using potassium persulphate as initiator in ethanol. The dithiocarbamate functionality was incorporated into these
polyacrylamides by a two-step polymer-analogous reaction involving (i)trans-amidation with ethylenediamine and (ii) dithiocarbamylation of the aminopolyacrylamide with carbon disulphide and alkali.
The complexations of dithiocarbamate with Cu(II), Ni(II), Zn(II), Co(II) and Hg(II) ions were followed under different conditions.
The metal ion intake varied with the extent of the crosslinking agent and the observed trend in complexation is Hg(II) > Cu(II)>
Zn(II)> Co(II)> Ni (II). The time-course of complexation, the possibility of recycling, swelling characteristics, and spectral
and thermal analyses were carried out. The thermal stability increases upon complexation with metal ions. 相似文献
72.
Brad M. Rosen Virgil Percec 《Journal of polymer science. Part A, Polymer chemistry》2007,45(21):4950-4964
Atom transfer radical polymerization (ATRP) and single electron‐transfer living radical polymerization (SET‐LRP) both utilize copper complexes of various oxidation states with N‐ligands to perform their respective activation and deactivation steps. Herein, we utilize DFT (B3YLP) methods to determine the preferred ligand‐binding geometries for Cu/N‐ligand complexes related to ATRP and SET‐LRP. We find that those ligands capable of achieving tetrahedral complexes with CuI and trigonal bipyramidal with axial halide complexes with [CuIIX]+ have higher energies of stabilization. We were able to correlate calculated preferential stabilization of [CuIIX]+ with those ligands that perform best in SET‐LRP. A crude calculation of energy of disproportionation revealed that the same preferential binding of [CuIIX]+ results in increased propensity for disproportionation. Finally, by examining the relative energies of the basic steps of ATRP and SET‐LRP, we were able to rationalize the transition from the ATRP mechanism to the SET‐LRP mechanism as we transition from typical nonpolar ATRP solvents to polar SET‐LRP solvents. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4950–4964, 2007 相似文献
73.
The constants of binding dye molecules with the micelles of sodium dodecyl sulfate are determined using quenching of delayed fluorescence of acridine dyes by sodium iodide in aqueous–micellar solutions. Kinetic equations have been composed that describe the processes of deactivation of the excited states of dyes. By solving these equations at the concentration of the quencher sodium iodide corresponding to the minimum lifetime of triplet states and at the concentration of micelles corresponding to the least value of the delayed fluorescence quenching rate constants, we obtained the constants of binding dyes with micelles equal to 1.3·107, 2.9·107, and 3.1·107 M–1 for trypaflavine, acridine orange, and acridine yellow, respectively. We calculated the rate constants of quenching of the triplet states of the molecules of dyes by iodide ions (I
–) that decreased in transition from trypaflavine to acridine orange and acridine yellow. 相似文献
74.
Jorge F. J. Coelho Ana M. F. P. Silva Anatoliy V. Popov Virgil Percec Mariana V. Abreu Pedro M. O. F. Gonalves M. H. Gil 《Journal of polymer science. Part A, Polymer chemistry》2006,44(9):3001-3008
The synthesis of a block copolymer poly(vinyl chloride)‐b‐poly(n‐butyl acrylate)‐b‐poly(vinyl chloride) is reported. This new material was synthesized by single‐electron‐transfer/degenerative‐chain‐transfer‐mediated living radical polymerization (SET‐DTLRP) in two steps. First, a bifunctional macroinitiator of α,ω‐di(iodo)poly (butyl acrylate) [α,ω‐di(iodo)PBA] was synthesized by SET‐DTLRP in water at 25 °C. The macroinitiator was further reinitiated by SET‐DTLRP, leading to the formation of the desired product. This ABA block copolymer was synthesized with high initiator efficiency. The kinetics of the copolymerization reaction was studied for two PBA macroinitiators with number–average molecular weight of 10 k and 20 k. The relationship between the conversion and the number–average molecular weight was found to be linear. The dynamic mechanical thermal analysis suggests just one phase, indicating that copolymer behaves as a single material with no phase separation. This methodology provides the access to several block copolymers and other complex architectures that result from combinations of thermoplastics (PVC) and elastomers (PBA). From industrial standpoint, this process is attractive, because of easy experimental setup and the environmental friendly reaction medium. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3001–3008, 2006 相似文献
75.
本文用数字散斑相关方法测量了五种不同幂硬化指数韧性金属材料(铝和铜),双边裂纹尖端细观区域内应变场.对所得结果用韧性损伤模型进行了分析.在此法中以金属自然表面结构为散斑场,不同加载状态的散斑场进行比较,得到相对变形与应变.图象之间相关性 C 是变形参数或是位移及其导数的泛函.使其相关性 C 取最大值的试凑变形即为其真实变形场.这一方法在细观测量中应用得到满意的结果. 相似文献
76.
77.
Sahadev R. K. Sharma S. K. Sindhwani 《Monatshefte für Chemie / Chemical Monthly》1992,123(10):883-889
Summary The chelation behaviour of some trivalent lanthanide and yttrium metal ion with biologically active 2-hydroxy-1-naphthaldehyde thiosemicarbazone (HNATS) has been investigated by potentiomotric measurements at 20±0.5°C in 75% (v/v) dioxane-water medium at various ionic strengths of sodium perchlorate. The method of Bjerrum and Calvin, as modified by Irving and Rossotti has been used to find out the values of
(average number of ligand bound per metal ion) andpL (free ligand exponent). The formation constants of metal chelates have been computed on a PC-XT computer, using a program patterned after that of Sullivan et al. to give
n
values using weighted least squares method. TheS
min
values (S
min
=2) have been calculated. The order of formation constants of chelates was found to be: La3+3+3+3+3+3+3+3+3+3+. The formation constants of the chelates formed have been correlated to size and ionization potentials of the metal ions.
Potentiometrische Untersuchungen der Komplexierungsgleichgewichte zwischen einigen trivalenten Metallionen und biologisch aktivem 2-Hydroxy-1-naphthaldehyd-thiosemicarbazon (HNATS)
Zusammenfassung Es wurde das Chelierungsverhalten einiger trivalenter Lanthanidenionen mit biologisch aktivem 2-Hydroxy-1-naphthaldehyd-thiosemicarbazon (HNATS) mittels potentiometrischer Messungen bei 20±0.5°C in 75% (v/v) Dioxan-Wasser bei verschiedener Ionenstärke an Natriumperchlorat untersucht. Die Methode nach Bjerrum und Calvin in der Modifikation nach Irving und Rossotti wurde zur Ermittlung der Werte (mittlere Anzahl an Liganden pro Metallion) undpL (Exponent an freiem Liganden) verwendet. Die Komplexbildungskonstanten wurden in Anlehnung an Sullivan et al. an einem PC-XT Computer errechnet. DieS min-Werte (S min=2) wurden ebenfalls bestimmt. Die Reihung der Chelatbildungskonstanten war: La3+相似文献3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+. Die Bildungskonstanten sind mit der Größe und dem Ionisierungspotential der Metallionen zu korrelieren.
78.
79.
纳米二氧化钛粒子分散性能的研究 总被引:15,自引:0,他引:15
以四氯化钛为原料,采用溶胶-凝胶法技术合成路线,获得了平均粒径为63nm的二氧化钛粉末。采用分散技术,不仅可以改善粒子的分散性能,而且对粒子的生长也起到一定的抑制作用。研究表明:(1)采用SDS作为分散剂时,其极性基团和非极性基团分别与水和纳米TiO2粒子相结合,从而阻隔了TiO2粒子的团聚,起到分散作用。(2)以稀土元素La作为分散剂,其独特的轨道结构,不仅扩大了能量吸收的范围,更重要的是它与TiO2形成的络合物,使其成为相对独立的小团体,而它本身很小的固溶度使其难于形成合金化组元,结果被释放出来,从而形成更小的纳米TiO2粒子,起到分散纳米TiO2粒子的作用,并同时抑制纳米TiO2粒子的生长。 相似文献
80.