全文获取类型
收费全文 | 811篇 |
免费 | 19篇 |
国内免费 | 5篇 |
专业分类
化学 | 575篇 |
晶体学 | 7篇 |
力学 | 9篇 |
数学 | 55篇 |
物理学 | 189篇 |
出版年
2022年 | 7篇 |
2021年 | 9篇 |
2020年 | 23篇 |
2019年 | 25篇 |
2018年 | 10篇 |
2017年 | 5篇 |
2016年 | 9篇 |
2015年 | 14篇 |
2014年 | 10篇 |
2013年 | 31篇 |
2012年 | 34篇 |
2011年 | 39篇 |
2010年 | 14篇 |
2009年 | 14篇 |
2008年 | 37篇 |
2007年 | 26篇 |
2006年 | 52篇 |
2005年 | 38篇 |
2004年 | 40篇 |
2003年 | 29篇 |
2002年 | 20篇 |
2001年 | 16篇 |
2000年 | 15篇 |
1999年 | 14篇 |
1997年 | 12篇 |
1996年 | 7篇 |
1995年 | 11篇 |
1994年 | 9篇 |
1993年 | 12篇 |
1992年 | 12篇 |
1990年 | 9篇 |
1989年 | 12篇 |
1988年 | 9篇 |
1987年 | 7篇 |
1986年 | 8篇 |
1985年 | 15篇 |
1984年 | 16篇 |
1983年 | 12篇 |
1982年 | 12篇 |
1981年 | 10篇 |
1980年 | 10篇 |
1979年 | 10篇 |
1978年 | 10篇 |
1977年 | 14篇 |
1976年 | 9篇 |
1975年 | 8篇 |
1974年 | 9篇 |
1973年 | 12篇 |
1972年 | 8篇 |
1966年 | 5篇 |
排序方式: 共有835条查询结果,搜索用时 109 毫秒
1.
Ye Jingyao Al-Jobory Alaa Zhang Qian-Chong Cao Wenqiang Alshehab Abdullah Qu Kai Alotaibi Turki Chen Hang Liu Junyang Ismael Ali K. Chen Zhong-Ning Lambert Colin J. Hong Wenjing 《中国科学:化学(英文版)》2022,65(9):1822-1828
Science China Chemistry - Destructive quantum interference (DQI) provides a unique approach to controlling the leakage current in the OFF state of molecular devices. However, the DQI in... 相似文献
2.
Dr. Clémence Sicard 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2023,135(1):e202213405
Enzyme immobilization is a widely reported method to favor the applicability of enzymes by enhancing their stability and re-usability. Among the various existing solid supports and immobilization strategies, the in situ encapsulation of enzymes within crystalline porous matrices is a powerful tool to design biohybrids with a stable and protected catalytic activity. However, to date, only a few metal–organic frameworks (MOFs) and hydrogen-bonded organic frameworks (HOFs) have been reported. Excitingly, for the first time, Y. Chen and co-workers expanded the in situ bio-encapsulation to a new class of crystalline porous materials, namely covalent organic frameworks (COFs). The enzyme@COF materials not only exhibited high enzyme loading with minimal leaching, high catalytic activity and selectivity, chemical and long-term stability and recyclability but could also be scaled up to a few grams. Undoubtedly, this work opens new striking opportunities for enzymatic immobilization and will stimulate new research on COF-based matrices. 相似文献
3.
Fanni Bede Prof. Dr. László Kollár Dr. Nándor Lambert Prof. Dr. Péter Huszthy Dr. Péter Pongrácz 《European journal of organic chemistry》2023,26(31):e202300571
Palladium-catalyzed hydroaminocarbonylation reactions of olefins using aliphatic amines were performed under carbon monoxide atmosphere. Despite the strong basicity of the applied nucleophiles, the targeted amides were successfully synthesized in the absence of acidic additives. Styrene, oct-1-ene and isoprene were transformed to the corresponding amide isomers in moderate to good isolated yields under optimized reaction conditions. Various aliphatic amines were used as N-nucleophiles. The effect of chiral diphosphines on product distribution, that is, on chemo-, regio- and enantioselectivities was also studied. Plausible explanation was given for the additive-free hydroaminocarbonylation reaction. 相似文献
4.
Christopher B. Kelly Kyle M. Lambert Michael A. Mercadante John M. Ovian Prof. William F. Bailey Prof. Nicholas E. Leadbeater 《Angewandte Chemie (International ed. in English)》2015,54(14):4241-4245
A scalable, high yielding, rapid route to access an array of nitriles from aldehydes mediated by an oxoammonium salt (4‐acetylamino‐2,2,6,6‐tetramethylpiperidine‐1‐oxoammonium tetrafluoroborate) and hexamethyldisilazane (HMDS) as an ammonia surrogate has been developed. The reaction likely involves two distinct chemical transformations: reversible silyl‐imine formation between HMDS and an aldehyde, followed by oxidation mediated by the oxoammonium salt and desilylation to furnish a nitrile. The spent oxidant can be easily recovered and used to regenerate the oxoammonium salt oxidant. 相似文献
5.
Xeroderma pigmentosum (XP) is a rare, recessively transmitted genetic disease characterized by increasingly marked dyspigmentation and xerosis (dryness) of sun‐exposed tissues, especially skin. Skin cancers characteristically develop in sun‐exposed sites at very much earlier ages than in the general population; these are often multiple and hundreds or even thousands may develop. Eight complementation groups have been identified. Seven groups, XP‐A…G, are associated with defective genes encoding proteins involved in the nucleotide excision DNA repair (NER) pathway that recognizes and excises mutagenic changes induced in DNA by sunlight; the eighth group, XP‐V, is associated with defective translesion synthesis (TLS) bypassing such alterations. The dyspigmentation, xerosis and eventually carcinogenesis in XP patients appear to be due to their cells’ failure to respond properly to these mutagenic DNA alterations, leading to mutations in skin cells. A subset of cases, especially those in some complementation groups, may develop neurological degeneration, which may be severe. However, in most XP patients, in the past the multiple skin cancers have led to death at an early age due to either metastases or sepsis. Using either topical 5‐fluorouracil or imiquimod, we have developed a protocol that effectively prevents most skin cancer development in XP patients. 相似文献
6.
Thomas Wiesner Dr. Zhu Wu Dr. Jie Han Prof. Dr. Lei Ji Dr. Alexandra Friedrich Dr. Ivo Krummenacher Michael Moos Prof. Dr. Christoph Lambert Prof. Dr. Holger Braunschweig Benjamin Rudin Dr. Hilmar Reiss Olena Tverskoy Dr. Frank Rominger Prof. Dr. Andreas Dreuw Prof. Dr. Todd B. Marder Dr. Jan Freudenberg Prof. Dr. Uwe H. F. Bunz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(69):e202201919
Tetraiodotetraazapentacene I4TAP , the last missing derivative in the series of halogenated silylated tetraazapentacenes, was synthesized via condensation chemistry from a TIPS-ethynylated diaminobenzothiadiazol in three steps. Single and double reduction furnished its air-stable monoanion and relatively air-stable dianion, both of which were characterized by crystallography. All three species are structurally and spectroscopically compared to non-halogenated TAP and Br4TAP . I4TAP is an n-channel material in thin-film transistors with average electron mobilities exceeding 1 cm2 (Vs)−1. 相似文献
7.
A pure tone phenomenon has been observed at 460 Hz in a piping steam line. The acoustical energy has been identified to be generated in an open gate valve and to be of cavity noise type. This energy is then transmitted to the main pipe by fluid/structure coupling. The objectives here are to display the mechanism of the flow acoustic coupling in the cavity and in the duct through an aeroacoustical analysis and to understand the way of energy transfer from the fluid to the main pipe through a vibroacoustical analysis. Concerning the first objective, an experimental study by means of 2/7 scale models in air is analysed by means of numerical flow simulation. The flow acoustic phenomena are modelled by computing the Euler equations. Two different computations are carried out: in the first one, a pure Euler modelling is used, in the second one, a boundary layer obtained from experimental data is introduced in the computation in order to have a realistic flow profile upstream the cavity. The boundary layer flow profile appears to be essential to recover the experimentally observed coupling between the shear-layer instability and the acoustical transverse mode of the pipe. The numerical results confirm that the second aerodynamic mode is responsible for the oscillation. While the predicted frequency agrees about 1% with the scale model experiments, the predicted amplitude is approximately 15 dB too low. For the second objective, fluid/structure coupling in the main pipe is studied using two fully coupled methods. The first method consists in a modal analysis of the line using a fluid–structure finite element model. The second one is based on the analysis of dispersion diagrams derived from the local equations of cylindrical shells filled with fluid. The way of energy transfer in transverse acoustical waves coupled with flexion-ovalization deformations of the pipe is highlighted using both methods. The dispersion diagrams allow a fast and accurate analysis. The modal analysis using a finite-element model may complete the first one with quantitative data. The link between the fluid/acoustic and the fluid/structure analysis is then the excitation of the transverse acoustical mode of the duct. 相似文献
8.
Patrícia Santiago de Oliveira Patricio Iaci Miranda Pereira Natália Cristina Ferreira da Silva Eliane Ayres Fabiano Vargas Pereira Rodrigo Lambert Oréfice 《European Polymer Journal》2013
Polyurethane waterborne synthesis was performed using a two-step method, commonly referred to as a prepolymer method. Nanocomposites based on waterborne polyurethane and cellulose nanocrystals were prepared by the prepolymer method by altering the mode and step in which the nanofillers were incorporated during the polyurethane formation. The morphology, structural, thermal, and mechanical properties of the resulting nanocomposite films were evaluated by Fourier transform infrared spectroscopy (FTIR), small angle X-ray scattering (SAXS), scanning electron microscopy (SEM), and tensile tests. FTIR results indicated that the degree of interaction between the nanofillers and the WPU through hydrogen bonds could be controlled by the method of cellulose nanocrystal incorporation. Data obtained from SAXS experiments showed that the cellulose nanocrystals as well as the step of the reaction in which they are added influenced the morphology of the polyurethane. The reinforcing effect of CNCs on the nanocomposites depends on their morphology. 相似文献
9.
The 2,5-diketopiperazine (DKP) moiety is a core feature of many natural products and medicinally relevant scaffolds. As part of our efforts directed towards a total synthesis of penicisulfuranol B, we have developed and report herein: (1) the preparation of an N-hydroxy diketopiperazine intermediate accessible via a molybdenum-mediated oxidation of a parent diketopiperazine, and (2) further synthetic studies leading to a novel spirocyclic dihydrobenzofuran-containing diketopiperazine. 相似文献