全文获取类型
收费全文 | 9066篇 |
免费 | 1849篇 |
国内免费 | 963篇 |
专业分类
化学 | 3353篇 |
晶体学 | 21篇 |
力学 | 476篇 |
综合类 | 76篇 |
数学 | 778篇 |
物理学 | 4054篇 |
无线电 | 3120篇 |
出版年
2024年 | 19篇 |
2023年 | 89篇 |
2022年 | 198篇 |
2021年 | 172篇 |
2020年 | 226篇 |
2019年 | 253篇 |
2018年 | 258篇 |
2017年 | 336篇 |
2016年 | 369篇 |
2015年 | 536篇 |
2014年 | 644篇 |
2013年 | 787篇 |
2012年 | 706篇 |
2011年 | 722篇 |
2010年 | 538篇 |
2009年 | 609篇 |
2008年 | 656篇 |
2007年 | 611篇 |
2006年 | 489篇 |
2005年 | 448篇 |
2004年 | 430篇 |
2003年 | 400篇 |
2002年 | 333篇 |
2001年 | 284篇 |
2000年 | 255篇 |
1999年 | 217篇 |
1998年 | 208篇 |
1997年 | 166篇 |
1996年 | 132篇 |
1995年 | 103篇 |
1994年 | 102篇 |
1993年 | 71篇 |
1992年 | 55篇 |
1991年 | 57篇 |
1990年 | 49篇 |
1989年 | 40篇 |
1988年 | 30篇 |
1987年 | 30篇 |
1986年 | 25篇 |
1985年 | 39篇 |
1984年 | 23篇 |
1982年 | 25篇 |
1981年 | 28篇 |
1980年 | 15篇 |
1979年 | 14篇 |
1978年 | 14篇 |
1977年 | 13篇 |
1976年 | 15篇 |
1974年 | 9篇 |
1973年 | 9篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
1.
《Mendeleev Communications》2022,32(4):534-536
Correlation times and diffusion coefficients of water molecules were measured for the first time by 1H spin relaxation and pulsed field gradient NMR in Li+, Na+ and Cs+ ionic forms of Nafion 117 membrane. Hydration numbers of Li+, Na+ and Cs+ cations were calculated. It was shown that at high humidity macroscopic transfer is controlled by the local translational motion of water molecules. 相似文献
2.
Golam Haider Krishna Sampathkumar Tim Verhagen Lukáš Nádvorník Farjana J. Sonia Václav Valeš Jan Sýkora Peter Kapusta Petr Němec Martin Hof Otakar Frank Yang-Fang Chen Jana Vejpravová Martin Kalbáč 《Advanced functional materials》2021,31(29):2102196
Recent advancements in isolation and stacking of layered van der Waals materials have created an unprecedented paradigm for demonstrating varieties of 2D quantum materials. Rationally designed van der Waals heterostructures composed of monolayer transition-metal dichalcogenides (TMDs) and few-layer hBN show several unique optoelectronic features driven by correlations. However, entangled superradiant excitonic species in such systems have not been observed before. In this report, it is demonstrated that strong suppression of phonon population at low temperature results in a formation of a coherent excitonic-dipoles ensemble in the heterostructure, and the collective oscillation of those dipoles stimulates a robust phase synchronized ultra-narrow band superradiant emission even at extremely low pumping intensity. Such emitters are in high demand for a multitude of applications, including fundamental research on many-body correlations and other state-of-the-art technologies. This timely demonstration paves the way for further exploration of ultralow-threshold quantum-emitting devices with unmatched design freedom and spectral tunability. 相似文献
3.
Lei Chen Hui-Qing Yang Cheng-Yu Jin Zhao-Xu Chen 《International journal of quantum chemistry》2020,120(22):e26366
We studied the ring opening of propylene oxide (PO) by salen-M coordinated OH− group [M = Al(III), Sc(III), Cr(III), Mn(III), Fe(III), Co(II), Co(III), Ni(II), Cu(II), Zn(II), Ru(III) and Rh(III)]. The results show that the ring-opening energy barriers for M(II) complexes are much lower than those with M(III) complexes in the gas phase, and the barriers correlate linearly with the negative charges on the OH− group and the Fukui function condensed on the OH− group. The nucleophilicity ordering in the gas phase can be rationalized by the ratio of formal positive charges/radius of M cations. Solvent effect greatly increases the barriers of M(II) complexes but slightly changes the results of M(III) ones, making the barriers similar. Analysis indicates that the reaction heats are linearly proportional to the reverse reaction barriers. The relationships established here can be used to estimate the ring-opening barriers and to screen epoxide ring-opening catalysts. 相似文献
4.
Single Crystal to Single Crystal (SC‐to‐SC) Transformation from a Nonporous to Porous Metal–Organic Framework and Its Application Potential in Gas Adsorption and Suzuki Coupling Reaction through Postmodification
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Rupam Sen Debraj Saha Dr. Subratanath Koner Dr. Paula Brandão Dr. Zhi Lin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(15):5962-5971
A new amino‐functionalized strontium–carboxylate‐based metal–organic framework (MOF) has been synthesized that undergoes single crystal to single crystal (SC‐to‐SC) transformation upon desolvation. Both structures have been characterized by single‐crystal X‐ray analysis. The desolvated structure shows an interesting 3D porous structure with pendent ?NH2 groups inside the pore wall, whereas the solvated compound possesses a nonporous structure with DMF molecules on the metal centers. The amino group was postmodified through Schiff base condensation by pyridine‐2‐carboxaldehyde and palladium was anchored on that site. The modified framework has been utilized for the Suzuki cross‐coupling reaction. The compound shows high activity towards the C?C cross‐coupling reaction with good yields and turnover frequencies. Gas adsorption studies showed that the desolvated compound had permanent porosity and was microporous in nature with a BET surface area of 2052 m2 g?1. The material also possesses good CO2 (8 wt %) and H2 (1.87 wt %) adsorption capabilities. 相似文献
5.
S. D. Campos 《中国物理C(英文版)》2020,44(10):103103-103103-10
This work presents the subtraction procedure and the Regge cut in the logarithmic Regge pole approach. The subtraction mechanism leads to the same asymptotic behavior as previously obtained in the non-subtraction case. The Regge cut, in contrast, introduces a clear role to the non-leading contributions for the asymptotic behavior of the total cross-section. From these results, some simple parameterization is introduced to fit the experimental data for the proton-proton and antiproton-proton total cross-section above some minimum value up to the cosmic-ray. The fit parameters obtained are used to present predictions for the \begin{document}$ \rho(s)$\end{document}
-parameter as well as to the elastic slope \begin{document}$ B(s)$\end{document}
at high energies. 相似文献
6.
One of the major challenges in wireless body area networks (WBANs) is sensor fault detection. This paper reports a method for the precise identification of faulty sensors, which should help users identify true medical conditions and reduce the rate of false alarms, thereby improving the quality of services offered by WBANs. The proposed sensor fault detection (SFD) algorithm is based on Pearson correlation coefficients and simple statistical methods. The proposed method identifies strongly correlated parameters using Pearson correlation coefficients, and the proposed SFD algorithm detects faulty sensors. We validated the proposed SFD algorithm using two datasets from the Multiparameter Intelligent Monitoring in Intensive Care database and compared the results to those of existing methods. The time complexity of the proposed algorithm was also compared to that of existing methods. The proposed algorithm achieved high detection rates and low false alarm rates with accuracies of 97.23% and 93.99% for Dataset 1 and Dataset 2, respectively. 相似文献
7.
《Journal of Saudi Chemical Society》2020,24(10):754-764
A kinetic study of the reactions of potentially bioactive 2-amino-4-arylthiazoles with highly reactive 4,6-dinitrobenzofuroxan (DNBF) is reported herein in acetonitrile solution. The complexation reaction was followed by recording the UV–vis spectra with time at λmax = 482 nm. Electronic effects of substituents influencing the rate of reaction have been studied using structure-reactivity relationships. It is shown that the Hammett plot relative to the reaction of DNBF with 2-amino-4-(4-chlorophenyl)thiazole exhibit positive deviation from the log k1 versus σ correlation, while it showed excellent linear correlation in terms of Yukawa–Tsuno equation. It has be noticed that the nonlinear Hammett plot observed for 2-amino-4-(4-chlorophenyl) thiazole is not attributed to a change in rate-determining step but is due to nature of electronic effect of substituent caused by the resonance of stabilization of substrates. The second-order rate constant (k1) relating to the bond C–C and C-N forming step of the complexation processes of DNBF with 4-substituted-aminothiazoles and 2-amino-5-methyl-4-phenylthiazole, respectively, is fit into the linear relationship log k = sN (N + E), thereby permitting the assessment of the nucleophilicity parameter (N) of the 2-amino-4-arylthiazoles of the range (4.90 < N < 6.85). 2-amino-4-arylthiazoles is subsequently ranked by positioning its reactivity on the general nucleophilicity scale developed recently by Mayr and coworkers (2003) leading an interesting and a direct comparison over a large domain of π-, σ -, and n-nucleophiles. The global electrophilicity/nucleophilicity reactivity indexes of the 2-amino-4-arylthiazoles have been investigated by means of a density functional theory (DFT) method. . 相似文献
8.
HPLC with fluorescence detection assay of perampanel,a novel AMPA receptor antagonist,in human plasma for clinical pharmacokinetic studies
下载免费PDF全文
![点击此处可从《Biomedical chromatography : BMC》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Perampanel (Fycompa®), a novel α‐amino‐3‐hydroxy‐5‐methyl‐4‐isoxazolepropionic acid (AMPA) receptor antagonist, is registered for the adjunctive treatment of patients (aged ≥12 years) with refractory partial‐onset seizures. To support therapeutic drug monitoring, a simple high‐performance liquid chromatography (HPLC) assay with fluorescence detection was developed to determine perampanel concentrations in human plasma and validated to support clinical trials. Human plasma samples (1.0 mL) were processed by liquid extraction using diethyl ether, followed by chromatographic separation on a YMC Pack Pro C18 column (150 × 4.6 mm i.d., 5 µm) with isocratic elution of acetonitrile–water–acetic acid–sodium acetate (840:560:3:1.8, v/v/v/w) at a flow rate of 1.0 mL/min. Column eluent was monitored at excitation and emission wavelengths of 290 and 430 nm, respectively. The assay was linear (range 1.0–500 ng/mL) and this could be extended to 25 µg/mL by 50‐fold dilution integrity. No endogenous peaks were detected in the elution of analytes in drug‐free blank human plasma from six individuals and no interference was observed with co‐medications tested. Intra‐ and inter‐batch reproducibility studies demonstrated accuracy and precision within the acceptance criteria of bioanalytical guidelines. Validation data demonstrated that our assay is simple, selective, reproducible and suitable for therapeutic drug monitoring of perampanel. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
9.
入侵检测是保障网络安全的重要手段,针对现有入侵检测系统中告警数量多、协调性差等问题,论文提出了一种具有告警融合与关联功能的告警处理系统模型,该模型冗余告警量少、整体检测能力强,并能进行攻击企图的预测,能有效提高入侵检测的效率,有助于进一步增强网络的健壮性。 相似文献
10.
Ratnabali Biswas Kaushik Chowdhury Dharma P. Agrawal 《International Journal of Wireless Information Networks》2006,13(4):303-315
Wireless sensor network is an emerging technology that enables remote monitoring of large geographical regions. In this paper, we address the problem of distributing attributes over such a large-scale sensor network so that the cost of data retrieval is minimized. The proposed scheme is a data-centric storage scheme where the attributes are distributed over the network depending on the correlations between them. The problem addressed here is similar to the Allocation Problem of distributed databases. In this paper, we have defined the Allocation Problem in the context of sensor networks and have proposed a scheme for finding a good distribution of attributes to the sensor network. We also propose an architecture for query processing given such a distribution of attributes. We analytically determine the conditions under which the proposed architecture is beneficial and present simulation results to demonstrate the same. To the best of our knowledge, this is the first attempt to determine an allocation of attributes over a sensor network based on the correlations between attributes. 相似文献