全文获取类型
收费全文 | 271篇 |
免费 | 10篇 |
国内免费 | 1篇 |
专业分类
化学 | 194篇 |
晶体学 | 2篇 |
力学 | 3篇 |
数学 | 34篇 |
物理学 | 49篇 |
出版年
2023年 | 3篇 |
2022年 | 4篇 |
2021年 | 6篇 |
2020年 | 6篇 |
2019年 | 4篇 |
2018年 | 3篇 |
2016年 | 11篇 |
2015年 | 5篇 |
2014年 | 8篇 |
2013年 | 15篇 |
2012年 | 16篇 |
2011年 | 28篇 |
2010年 | 10篇 |
2009年 | 14篇 |
2008年 | 21篇 |
2007年 | 19篇 |
2006年 | 8篇 |
2005年 | 12篇 |
2004年 | 11篇 |
2003年 | 5篇 |
2002年 | 8篇 |
2001年 | 6篇 |
2000年 | 9篇 |
1999年 | 1篇 |
1998年 | 4篇 |
1997年 | 4篇 |
1996年 | 5篇 |
1993年 | 3篇 |
1992年 | 5篇 |
1991年 | 5篇 |
1990年 | 3篇 |
1989年 | 3篇 |
1988年 | 1篇 |
1987年 | 1篇 |
1986年 | 1篇 |
1985年 | 3篇 |
1984年 | 4篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1910年 | 1篇 |
1906年 | 1篇 |
排序方式: 共有282条查询结果,搜索用时 31 毫秒
91.
92.
Yuexin Fan Prof. Tuan Liu Prof. Yuzhan Li Dr. Xuepei Miao Dr. Baihang Chen Jian Ding Zhixiang Dong Prof. Orlando Rios Dr. Bingkun Bao Prof. Qiuning Lin Prof. Linyong Zhu 《Angewandte Chemie (International ed. in English)》2023,62(37):e202308793
Liquid-crystal elastomers (LCEs) capable of performing large and reversible deformation in response to an external stimulus are an important class of soft actuators. However, their manufacturing process typically involves a multistep approach that requires harsh conditions. For the very first time, LCEs with customized geometries that can be manufactured by a rapid one-step approach at room temperature are developed. The LCEs are hydrogen bond (H-bond) crosslinked main chain polymers comprising flexible short side chains. Applying a stretching/shear force to the LCE can simultaneously induce mesogen alignment and H-bond exchange, allowing for the formation of well-aligned LCE networks stabilized by H-bonds. Based on this working principle, soft actuators in fibers and 2D/3D objects can be manufactured by mechanical stretching or melt extrusion within a short time (e.g. <1 min). These actuators can perform reversible macroscopic motions with large, controlled deformations up to 38 %. The dynamic nature of H-bonds also provides the actuators with reprocessability and reprogrammability. Thus, this work opens the way for the one-step and custom manufacturing of soft actuators. 相似文献
93.
Fast detection of Piscirickettsia salmonis in Salmo salar serum through MALDI‐TOF‐MS profiling 下载免费PDF全文
Verónica R. Olate Fabiane M. Nachtigall Leonardo S. Santos Alex Soto Macarena Araya Sandra Oyanedel Verónica Díaz Vanessa Marchant Mauricio Rios‐Momberg 《Journal of mass spectrometry : JMS》2016,51(3):200-206
Piscirickettsia salmonis is a pathogenic bacteria known as the aetiological agent of the salmonid rickettsial syndrome and causes a high mortality in farmed salmonid fishes. Detection of P. salmonis in farmed fishes is based mainly on molecular biology and immunohistochemistry techniques. These techniques are in most of the cases expensive and time consuming. In the search of new alternatives to detect the presence of P. salmonis in salmonid fishes, this work proposed the use of MALDI‐TOF‐MS to compare serum protein profiles from Salmo salar fish, including experimentally infected and non‐infected fishes using principal component analysis (PCA). Samples were obtained from a controlled bioassay where S. salar was challenged with P. salmonis in a cohabitation model and classified according to the presence or absence of the bacteria by real time PCR analysis. MALDI spectra of the fish serum samples showed differences in its serum protein composition. These differences were corroborated with PCA analysis. The results demonstrated that the use of both MALDI‐TOF‐MS and PCA represents a useful tool to discriminate the fish status through the analysis of salmonid serum samples. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
94.
Crovetto L Paredes JM Rios R Talavera EM Alvarez-Pez JM 《The journal of physical chemistry. A》2007,111(51):13311-13320
The photophysical behavior of a new fluorescein derivative has been explored by using absorption and steady-state and time-resolved fluorescence measurements. The influence of ionic strength, as well as total buffer concentration, on both the absorbance and fluorescence has been investigated. The apparent acidity constant of the dye determined by absorbance is almost independent of the added buffer and salt concentrations. A semiempirical model is proposed to rationalize the variations in the apparent pKa values. The excited-state proton-exchange reaction around the physiological pH becomes reversible upon addition of phosphate buffer, inducing a pH-dependent change of the steady-state fluorescence and decay times. Fluorescence decay traces, collected as a function of total buffer concentration and pH, were analyzed by global compartmental analysis, yielding the following values of the rate constants describing excited-state dynamics: k01 = 1.29 x 10(10) s(-1), k02 = 4.21 x 10(8) s(-1), k21 approximately 3 x 10(6) M(-1) s(-1), k12B= 6.40 x 10(8) M(-1) s(-1), and k21B = 2.61 x 10(7) M(-1) s(-1). The decay rate constant values of k01, k21, k21B, along with the low molar absorption coefficient of the neutral form, mean that coupled decays are practically monoexponential at buffer concentrations higher than 0.02 M and any pH. Thus, the pH and buffer concentration can modulate the main lifetime of the dye. 相似文献
95.
96.
97.
Rutkowski PX Rios D Gibson JK Van Stipdonk MJ 《Journal of the American Society for Mass Spectrometry》2011,22(11):2042-2048
Electrospray ionization of actinyl perchlorate solutions in H2O with 5% by volume of dimethylformamide (DMF) produced the isolatable gas-phase complexes, [AnVIO2(DMF)3(H2O)]2+ and [AnVIO2(DMF)4]2+, where An = U, Np, and Pu. Collision-induced dissociation confirmed the composition of the dipositive coordination complexes,
and produced doubly- and singly-charged fragment ions. The fragmentation products reveal differences in underlying chemistries
of uranyl, neptunyl, and plutonyl, including the lower stability of Np(VI) and Pu(VI) compared with U(VI). 相似文献
98.
Nickel atoms were inserted into nine-atom deltahedral Zintl ions of E(9)(4-) (E = Ge, Sn) via reactions with Ni(cod)(2) (cod = cyclooctadiene), and [Ni@Sn(9)](3-) was structurally characterized. Both the empty and the Ni-centered clusters react with TlCp (Cp = cyclopentadienyl anion) and add a thallium vertex to form the deltahedral ten-atom closo-species [E(9)Tl](3-) and [Ni@E(9)Tl](3-), respectively. The structures of [Ge(9)Tl](3-) and [Ni@Sn(9)Tl](3-) showed that, as expected, the geometry of the ten-atom clusters is that of a bicapped square antiprism where the Tl-atom occupies one of the two capping vertices. This illustrates that centering a nine-atom cluster with a nickel atom does not change its reactivity toward TlCp. All compounds were characterized by electrospray mass spectrometry. 相似文献
99.
An efficient synthesis of spiropyrazolones based on organocatalysis is described. The reaction between pyrazolones, enolizable aldehydes and enals is catalyzed by secondary amine catalysts and affords the final spiro compounds bearing four contiguous chiral centers in good yields and excellent diastereo- and enantioselectivities. 相似文献
100.
The enantioselective synthesis of fluorinated molecules has drawn much attention within the chemical community due to its unique stereoelectronic properties. The main aim of this review is to cover the most important organocatalytic enantioselective methodologies to obtain them. The review is divided into three parts: first, the direct introduction of a fluorine atom studied in the early 2000s. Second, the later use of Michael reactions to introduce fluorine-containing synthons. Finally, the simultaneously-developed trifluoromethylation reactions, giving the catalysts, mechanisms and reagents that have been used. 相似文献