全文获取类型
收费全文 | 38548篇 |
免费 | 6425篇 |
国内免费 | 4364篇 |
专业分类
化学 | 26374篇 |
晶体学 | 523篇 |
力学 | 2489篇 |
综合类 | 288篇 |
数学 | 4438篇 |
物理学 | 15225篇 |
出版年
2024年 | 145篇 |
2023年 | 793篇 |
2022年 | 1314篇 |
2021年 | 1395篇 |
2020年 | 1507篇 |
2019年 | 1442篇 |
2018年 | 1269篇 |
2017年 | 1195篇 |
2016年 | 1789篇 |
2015年 | 1781篇 |
2014年 | 2160篇 |
2013年 | 2712篇 |
2012年 | 3279篇 |
2011年 | 3419篇 |
2010年 | 2335篇 |
2009年 | 2294篇 |
2008年 | 2493篇 |
2007年 | 2242篇 |
2006年 | 2137篇 |
2005年 | 1653篇 |
2004年 | 1330篇 |
2003年 | 1120篇 |
2002年 | 1038篇 |
2001年 | 832篇 |
2000年 | 870篇 |
1999年 | 822篇 |
1998年 | 731篇 |
1997年 | 683篇 |
1996年 | 691篇 |
1995年 | 616篇 |
1994年 | 540篇 |
1993年 | 430篇 |
1992年 | 425篇 |
1991年 | 329篇 |
1990年 | 302篇 |
1989年 | 239篇 |
1988年 | 204篇 |
1987年 | 172篇 |
1986年 | 153篇 |
1985年 | 152篇 |
1984年 | 104篇 |
1983年 | 71篇 |
1982年 | 60篇 |
1981年 | 36篇 |
1980年 | 16篇 |
1979年 | 10篇 |
1977年 | 2篇 |
1971年 | 1篇 |
1959年 | 1篇 |
1957年 | 3篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
101.
Yue Sun Aidong Xu Kai Wang Xiufang Zhou Haifeng Guo Xiaojia Han 《Entropy (Basel, Switzerland)》2022,24(7)
One of the biggest challenges for the fault diagnosis research of industrial robots is that the normal data is far more than the fault data; that is, the data is imbalanced. The traditional diagnosis approaches of industrial robots are more biased toward the majority categories, which makes the diagnosis accuracy of the minority categories decrease. To solve the imbalanced problem, the traditional algorithm is improved by using cost-sensitive learning, single-class learning and other approaches. However, these algorithms also have a series of problems. For instance, it is difficult to estimate the true misclassification cost, overfitting, and long computation time. Therefore, a fault diagnosis approach for industrial robots, based on the Multiclass Mahalanobis-Taguchi system (MMTS), is proposed in this article. It can be classified the categories by measuring the deviation degree from the sample to the reference space, which is more suitable for classifying imbalanced data. The accuracy, G-mean and F-measure are used to verify the effectiveness of the proposed approach on an industrial robot platform. The experimental results show that the proposed approach’s accuracy, F-measure and G-mean improves by an average of 20.74%, 12.85% and 21.68%, compared with the other five traditional approaches when the imbalance ratio is 9. With the increase in the imbalance ratio, the proposed approach has better stability than the traditional algorithms. 相似文献
102.
Xingan Cheng Huiqing He Fangyun Dong Chunbao Charles Xu Hanhui Zhang Zhanmei Liu Xiaojing Lv Yuehua Wu Xuhong Jiang Xiangjing Qin 《Molecules (Basel, Switzerland)》2022,27(15)
Matrine is a traditional botanical pesticide with a broad-spectrum biological activity that is widely applied in agriculture. Halopyrazole groups are successfully introduced to the C13 of matrine to synthesize eight new derivatives with a yield of 78–87%. The insecticidal activity results show that the introduction of halopyrazole groups can significantly improve the insecticidal activity of matrine on Plutella xylostella, Mythimna separata and Spodoptera frugiperda with a corrected mortality rate of 100%, which is 25–65% higher than matrine. The fungicidal activity results indicate that derivatives have a high inhibitory effect on Ceratobasidium cornigerum, Cibberella sanbinetti, Gibberrlla zeae and Collectot tichum gloeosporioides. Thereinto, 4-Cl-Pyr-Mat has the best result, with an inhibition rate of 23–33% higher than that of matrine. Therefore, the introduction of halogenated pyrazole groups can improve the agricultural activity of matrine. 相似文献
103.
Yang Ye Xiang Qi Bing Xu Ying Lin Huan Xiang Liang Zou Xiang-Yang Ye Tian Xie 《Chemical science》2022,13(23):6959
Herein, we present a facile and efficient allylation method via Ni-catalyzed cross-electrophile coupling of readily available allylic acetates with a variety of substituted alkenyl bromides using zinc as the terminal reductant. This Ni-catalyzed modular approach displays excellent functional group tolerance and a broad substrate scope, which the creation of a series of 1,4-dienes including several structurally complex natural products and pharmaceutical motifs. Moreover, the coupling strategy has the potential to realize enantiomeric control. The practicality of this transformation is demonstrated through the potent modification of the naturally antitumor active molecule β-elemene.Herein, we present a facile and efficient allylation method via Ni-catalyzed cross-electrophile coupling of readily available allylic acetates with a variety of substituted alkenyl bromides using zinc as the terminal reductant. 相似文献
104.
Chemical Constituents from the Flowers of Carthamus tinctorius L. and Their Lung Protective Activity
Yanling Liu Mengna Wang Yangang Cao Mengnan Zeng Qinqin Zhang Yingjie Ren Xu Chen Chen He Xiling Fan Xiaoke Zheng Weisheng Feng 《Molecules (Basel, Switzerland)》2022,27(11)
A new flavonoid, saffloflavanside (1), a new sesquiterpene, safflomegastigside (2), and a new amide, saffloamide (3), together with twenty-two known compounds (4–25), were isolated from the flowers of Carthamus tinctorius L. Their structures were determined based on interpretation of their spectroscopic data and comparison with those reported in the literature. The protective effects against lipopolysaccharide (LPS)-stimulated damage on human normal lung epithelial (BEAS-2B) cells of the compounds were evaluated using MTT assay and cellular immunofluorescence assay. The results showed that compounds 2–3, 8–11, and 15–19 exhibited protective effects against LPS-induced damage to BEAS-2B cells. Moreover, compounds 2–3, 8–11, and 15–19 can significantly downregulate the level of nuclear translocation of NF-κB p-p65. In summary, this study revealed chemical constituents with lung protective activity from C. tinctorius, which may be developed as a drug for the treatment of lung injury. 相似文献
105.
以Zn(NO3)2· 6H2O和C6H12N4为原材料,采用二步水热法在碳纤维布上合成了形貌尺寸均匀的ZnO超细纳米线阵列。用 X 射线衍射(XRD)和扫描电镜(SEM)对其晶体结构和形貌进行了表征,利用恒流充放电测试等手段对其进行电化学性能测试。测试结果表明,材料表现出优异的电化学性能。在200 mA/g的电流密度下循环150次后,ZnO超细纳米线阵列仍然约有730 mAh/g的充放电比容量,库伦效率保持在95%以上。在1 200 mA/g的大倍率条件下,材料的充放电比容量依旧可达481 mAh/g左右,表现出十分良好的循环稳定性和可逆性能,是一种较为理想的锂离子电池负极复合材料。 相似文献
106.
Shuang-Jing Zhou Xiao Cheng Chun-Xia Hu Guo-Yong Xu Wen-Jing Xiao Jun Xuan 《中国科学:化学(英文版)》2021,(1):61-65
A formal[4+3]-cycloaddition reaction of ortho-hydroxyphenyl-substituted para-quinone methides(p-QMs)with in-situ generated azaoxyallyl cations is reported.The reaction occurs under very mild reaction conditions(transition-metal free,room temperature,cheap inorganic base)and provides a very efficient route to a series of biologically important 1,4-benzoxazepine derivatives in good to excellent yields. 相似文献
107.
Maoji Jiu (MJ) is a kind of medicinal wine that has been widely used by Chinese people for many years to nourish and promote blood circulation. The purpose of this study was to investigate the hematopoietic effect of MJ on the metabolism of blood deficient rats and to explore the underlying hematopoietic regulation mechanisms. Blood deficiency model rats were induced by subcutaneous injection of N-acetylphenylhydrazine (APH) and intraperitoneal injection of cyclophosphamide (CTX). The plasma metabolic fingerprints of blood deficiency model rats with and without MJ treatment were obtained by using metabonomics based on ultra-high-performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry (UHPLC–QTOF/MS). Orthogonal partial least squares-discriminant analysis (OPLS–DA) was used to evaluate the hematopoietic effect of MJ and identify potential biomarkers in the plasma of blood deficiency model rats. The levels of white blood cells (WBC), red blood cells (RBC) and hemoglobin (HGB) and the activity of antioxidant capacity showed a recovery trend to the control group after MJ treatment, while the dose of 10 mL/kg showed the best effect. In this study, thirteen potential biomarkers were identified, which were mainly related to seven metabolic pathways, including linoleic acid metabolism, d-glutamine and d-glutamate metabolism, alanine, aspartate and glutamate metabolism, tryptophan metabolism, pyrimidine metabolism, porphyrin and chlorophyll metabolism and arginine biosynthesis. Metabolomics was applied frequently to reflect the physiological and metabolic state of organisms comprehensively, indicating that the rapid plasma metabonomics may be a potentially powerful tool to reveal the efficacy and enriching blood mechanism of MJ. 相似文献
108.
The age of information (AoI) metric was proposed to measure the freshness of messages obtained at the terminal node of a status updating system. In this paper, the AoI of a discrete time status updating system with probabilistic packet preemption is investigated by analyzing the steady state of a three-dimensional discrete stochastic process. We assume that the queue used in the system is , which represents that the system size is 2 and the packet in the buffer can be preempted by a fresher packet with probability . Instead of considering the system’s AoI separately, we use a three-dimensional state vector to simultaneously track the real-time changes of the AoI, the age of a packet in the server, and the age of a packet waiting in the buffer. We give the explicit expression of the system’s average AoI and show that the average AoI of the system without packet preemption is obtained by letting . When is set to 1, the mean of the AoI of the system with a queue is obtained as well. Combining the results we have obtained and comparing them with corresponding average continuous AoIs, we propose a possible relationship between the average discrete AoI with the queue and the average continuous AoI with the queue. For each of two extreme cases where and , we also determine the stationary distribution of AoI using the probability generation function (PGF) method. The relations between the average AoI and the packet preemption probability , as well as the AoI’s distribution curves in two extreme cases, are illustrated by numerical simulations. Notice that the probabilistic packet preemption may occur, for example, in an energy harvest (EH) node of a wireless sensor network, where the packet in the buffer can be replaced only when the node collects enough energy. In particular, to exhibit the usefulness of our idea and methods and highlight the merits of considering discrete time systems, in this paper, we provide detailed discussions showing how the results about continuous AoI are derived by analyzing the corresponding discrete time system and how the discrete age analysis is generalized to the system with multiple sources. In terms of packet service process, we also propose an idea to analyze the AoI of a system when the service time distribution is arbitrary. 相似文献
109.
Phenothiazine-based covalent organic frameworks with low exciton binding energies for photocatalysis
Weitao Wang Haotian Wang Xiaohui Tang Jinlei Huo Yan Su Chuangye Lu Yujian Zhang Hong Xu Cheng Gu 《Chemical science》2022,13(29):8679
Designing delocalized excitons with low binding energy (Eb) in organic semiconductors is urgently required for efficient photochemistry because the excitons in most organic materials are localized with a high Eb of >300 meV. In this work, we report the achievement of a low Eb of ∼50 meV by constructing phenothiazine-based covalent organic frameworks (COFs) with inherent crystallinity, porosity, chemical robustness, and feasibility of bandgap engineering. The low Eb facilitates effective exciton dissociation and thus promotes photocatalysis by using these COFs. As a demonstration, we subject these COFs to photocatalytic polymerization to synthesize polymers with remarkably high molecular weight without any requirement of the metal catalyst. Our results can facilitate the rational design of porous materials with low Eb for efficient photocatalysis.We report the construction of phenothiazine-based covalent organic frameworks, which exhibited diverse structures, the feasibility of bandgap engineering, and unprecedented ultralow exciton binding energy of ∼50 meV for photocatalytic polymerization. 相似文献
110.
Shanru He Yuanyuan Chen Lulu Wang Xue Bai Tingting Bu Jie Zhang Ming Lu Nam-Chul Ha Chunshan Quan Ki Hyun Nam Yongbin Xu 《Molecules (Basel, Switzerland)》2022,27(15)
Pyridoxal 5′-phosphate (PLP) is the active form of vitamin B6, but it is highly reactive and poisonous in its free form. YggS is a PLP-binding protein found in bacteria and humans that mediates PLP homeostasis by delivering PLP to target enzymes or by performing a protective function. Several biochemical and structural studies of YggS have been reported, but the mechanism by which YggS recognizes PLP has not been fully elucidated. Here, we report a functional and structural analysis of YggS from Fusobacterium nucleatum (FnYggS). The PLP molecule could bind to native FnYggS, but no PLP binding was observed for selenomethionine (SeMet)-derivatized FnYggS. The crystal structure of FnYggS showed a type III TIM barrel fold, exhibiting structural homology with several other PLP-dependent enzymes. Although FnYggS exhibited low (<35%) amino acid sequence similarity with previously studied YggS proteins, its overall structure and PLP-binding site were highly conserved. In the PLP-binding site of FnYggS, the sulfate ion was coordinated by the conserved residues Ser201, Gly218, and Thr219, which were positioned to provide the binding moiety for the phosphate group of PLP. The mutagenesis study showed that the conserved Ser201 residue in FnYggS was the key residue for PLP binding. These results will expand the knowledge of the molecular properties and function of the YggS family. 相似文献