首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   2124篇
  免费   302篇
  国内免费   286篇
化学   1110篇
晶体学   23篇
力学   100篇
综合类   11篇
数学   637篇
物理学   831篇
  2024年   2篇
  2023年   40篇
  2022年   73篇
  2021年   114篇
  2020年   91篇
  2019年   58篇
  2018年   65篇
  2017年   78篇
  2016年   110篇
  2015年   92篇
  2014年   133篇
  2013年   205篇
  2012年   261篇
  2011年   228篇
  2010年   169篇
  2009年   165篇
  2008年   129篇
  2007年   140篇
  2006年   132篇
  2005年   95篇
  2004年   65篇
  2003年   44篇
  2002年   27篇
  2001年   43篇
  2000年   30篇
  1999年   37篇
  1998年   20篇
  1997年   18篇
  1996年   14篇
  1995年   10篇
  1994年   4篇
  1993年   4篇
  1992年   4篇
  1991年   3篇
  1990年   6篇
  1989年   3篇
排序方式: 共有2712条查询结果,搜索用时 31 毫秒
21.
The Analytic Hierarchy Process (AHP) is a measurement methodology based on pair-wise comparisons that relies on judgment to derive priority scales. During its implementation, one constructs hierarchies, then makes judgments or performs measurements on pairs of elements with respect to a criterion to derive preference scales, which are then synthesized throughout the structure to select the preferred alternative.One of the areas where the AHP finds application is in the subjective phases of risk assessment (RA), where it is used to structure and prioritize diverse risk factors, including the judgments of experts. Since fuzzy logic (FL) has been shown to be an effective tool for accommodating human experts and their communication of linguistic variables, there has been research aimed at modeling the fuzziness in the AHP (FAHP), and recently the focus of some of that modeling has been with respect to RA.The literature discusses more than one FAHP model, which raises the question as to which are the prominent models and what are their characteristics. In response to this question, we examine three of the most influential FAHP models. The article proceeds as follows. It begins with a brief overview of the AHP and its limitations when confronted with a fuzzy environment. This is followed by a discussion of FL modifications of the AHP. A RA-based likelihood score example is used throughout. The article ends with a commentary on the findings.  相似文献   
22.
23.
In this article, a time discretization decoupled scheme for two‐dimensional magnetohydrodynamics equations is proposed. The almost unconditional stability and convergence of this scheme are provided. The optimal error estimates for velocity and magnet are provided, and the optimal error estimate for pressure are deduced as well. Finite element spatial discretization and numerical implementation are considered in our article (Zhang and He, Comput Math Appl 69 (2015), 1390–1406). © 2017 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq 33: 956–973, 2017  相似文献   
24.
Assume that a quadratic matrix-valued function \(\psi (X) = Q - X^{\prime }PX\) is given and let \(\mathcal{S} = \left\{ X\in {\mathbb R}^{n \times m} \, | \, \mathrm{trace}[\,(AX - B)^{\prime }(AX - B)\,] = \min \right\} \) be the set of all least-squares solutions of the linear matrix equation \(AX = B\). In this paper, we first establish explicit formulas for calculating the maximum and minimum ranks and inertias of \(\psi (X)\) subject to \(X \in {\mathcal S}\), and then derive from the formulas the analytic solutions of the two optimization problems \(\psi (X) =\max \) and \(\psi (X)= \min \) subject to \(X \in \mathcal{S}\) in the Löwner partial ordering. As applications, we present a variety of results on equalities and inequalities of the ordinary least squares estimators of unknown parameter vectors in general linear models.  相似文献   
25.
《中国化学快报》2023,34(2):107512
Eight polycyclic furanobutenolide-containing norcembrane diterpenoids featuring C19 frameworks (18) were rapidly recognized and isolated from the Hainan soft coral Sinularia sp. by the HSQC-based small molecule accurate recognition technology. Yonarolide A (1a), featuring an unprecedented 5/6/4/4/7 pentacyclic ring skeleton, was surprisingly obtained as a transformed product by leaving compound 1 under indoor natural light, and was further proved to be a [2 + 2] cycloaddition product of 1 by photochemical reaction. The absolute stereochemistry of 1a and the three known norcembrane diterpenoids 1, 4, and 7 were determined by using X-ray diffraction (XRD) analyses. Further, with the aid of XRD analysis, the structure of scabrolide B (2), which was previously reported of possessing 5/6/7 tricyclic skeleton, was firmly revised as 2a with the rare inelegane skeleton featured by the highly oxygenated 5/7/6 tricyclic carbocycle.  相似文献   
26.
《中国化学快报》2023,34(4):107736
Chalcogenative sulfones (thiosulfonates and selenosulfonates), as reactants for organic transformations, are widely used and interesting because of their potential to react with nucleophiles, electrophiles, and free radicals. As stable radical reagents, the synthesis and applications of chalcogenative sulfones have opened up a novel pathway to synthesize many kinds of compounds containing sulfur or selenium motifs. However, despite the numerous recent works on the synthesis and applications of thiosulfonates and selenosulfonates as radical reagents, no review has yet provided a summary of the literature. In this paper, we aim to review the synthesis and applications strategies of chalcogenative sulfones as radical reagents reported over the past several decades. Different types of catalysis are discussed in this review: (i) metal catalysis; (ii) visible-light catalysis; (iii) synergistic catalysis; and (iiii) other types. Concurrently, in visible-light catalysis and metallaphotoredox catalysis sections, we highlight that developing relatively environmentally friendly synthetic methods in this area is always a great challenge, but also a persistent pursuit. Finally, the scopes, limitations, mechanisms, and existing problems of some reactions are described briefly.  相似文献   
27.
基于工程教育认证的核心理念,制定了面向产出的高分子化学课程教学大纲。与传统课程教学大纲不同,本大纲的课程目标是使学生具备推演、阐述、分析和研究高分子材料领域复杂工程问题的能力,体现以学生为中心、面向产出和持续改进的理念。课程教学内容既包含知识点又包含能力要求,强调课程知识点与学生能力达成的支撑关系。在课程考核部分,提出了分目标模块化的考核方法和评分标准,满足了工程认证可衡量、易操作的考核要求。  相似文献   
28.
张晗  丁家旺  秦伟 《化学进展》2021,33(10):1756-1765
多肽具有分子量小、易于合成、生物兼容性好、稳定性高及序列灵活多样等优点。因此,多肽作为新型生物识别元件,已被广泛应用于生物传感器的构建。电化学分析灵敏度高、准确度好、设备简单、检测范围广且易于操作。本文介绍了基于多肽识别的电化学生物传感器技术,包括多肽的修饰与固定化、多肽与待测物的识别及检测原理;综述了近五年多肽电化学生物传感器对重金属离子、小分子、蛋白质、细菌和病毒的检测;展望了肽基电化学生物传感器的发展趋势。  相似文献   
29.
周亚楠  朱宇冉  闫新彤  曹羽宁  李佳  董斌  杨敏  李庆忠  刘晨光  柴永明 《催化学报》2021,42(3):431-438,中插25-中插28
电催化析氢(HER)是清洁制氢的一种有效途径,对于氢经济和氢能产业的发展具有重要意义.金属掺杂是提高电催化剂本征活性的有效方法,导电基底的采用也有利于电荷传输和催化性能的整体提高.尽管已有关于硒化物作为HER催化剂的相关报道,但是合成条件有限、导电性、本征活性的影响,其电催化性能仍有提升的空间.此外,在酸性电解液中的腐蚀和氧化极大限制了催化剂性能的发挥.基于此,本文以氮掺杂碳球为载体,采用金属Nb掺杂、非金属硫硒化物协同以及表面碳包覆的三重策略,将掺杂元素Nb和活性位中心元素Co封装到氮掺杂碳纳米球内并进行连续的硫硒化反应,成功构筑多级纳米结构(Nb-CoSeS@NC)以提高其电催化析氢性能.碳球可为活性位的生长和分散提供足够的空间,同时有效防止活性金属的腐蚀和分解,并阻止金属纳米颗粒的团聚.硫化过程实现了非金属硫元素的掺杂,对于提高硒化物的催化活性和导电性都有重要作用.通过扫描电镜(SEM)、透射电镜(TEM)、X射线衍射(XRD)、拉曼光谱、X射线光电子能谱(XPS)及电催化性能测试,详细研究了Nb-CoSeS@NC独特的纳米结构和电催化制氢性能,并分析了构效关系.XRD结果发现,引入Nb后Co9Se8和CoSe的特征峰移向更高的角度,表明其晶格体积的减小,有助于电荷传输.同时,氮掺杂碳球(NC)在26°可以观察到无定型碳的峰,而石墨碳的D带和G带强度比约为1.05,均表明NC中缺陷的存在,这可以进一步提高碳材料的导电性.SEM和TEM表征显示,催化剂为直径120 nm的均匀的纳米核壳结构,壳层约为30 nm,无明显的团聚和破碎,这是催化剂具有高稳定性的重要原因.表面的褶皱保证了大的活性比表面积,可以大大增加活性位点的数量.同时,催化剂与NC之间的紧密结合可以降低电子传输的阻抗进而改善其稳定性和析氢性能.分析高分辨率的TEM结果发现,Nb掺杂后,Nb-CoSeS@NC中Co9Se8的(222)晶面由0.301 nm减小至0.184 nm,与XRD结果相符.XPS表征揭示了引入Nb之后的电子效应.与CoSeS@NC相比,Nb的掺杂使Co 2p向更低的结合能移动,而Se 3d则移向高结合能移动,这是由于Nb导致了更强的电子相互作用.在0.5 M的H2SO4中测试催化剂的析氢性能,Nb-CoSeS@NC仅需115 mV的过电位便可以实现10 mA cm-2的电流密度,Tafel斜率为43 mV dec-1,优于CoSeS@NC等其他对比样品,且优于大多数掺杂型硒化物电催化剂.经过12 h稳定性测试,电流密度未见明显降低,表明该多级结构催化剂的优异稳定性.Nb-CoSeS@NC提高活性可归因为Nb的掺杂增强了催化剂的电子相互作用,有助于提高的其本征导电性.Nb、Co正离子可以形成氢化物-受体中心,可能会削弱S-H键和Se-H键,并促进H-H键的形成,因此,多元掺杂产生的协同效应可以有效促进HER过程.此外,坚固的氮掺杂纳米碳壳为活性位点的分散提供了足够的空间和优异的电荷传输性能,同时降低了金属活性位腐蚀的可能性.  相似文献   
30.
为了使用单细胞电感耦合等离子体质谱(SC-ICP-MS)方法准确测定单个细胞中的铬(Cr)、锰(Mn)、铁(Fe)、铜(Cu)和锌(Zn)等多种内源性金属元素,该文基于动态反应池(DRC)模式对目标分析物的反应气流量和极杆抑制参数q(RPq)进行了优化,并研究了进样速度、细胞密度、驻留时间等因素对SC-ICP-MS检测的影响。分别采用细胞悬液直接进样、使用超声波探头使细胞悬液中的细胞破碎后进样和使用浓硝酸消解细胞后进样的ICP-MS测定结果对SC-ICP-MS定量结果的准确性进行验证分析。实验结果表明,可采用超声波破碎细胞的ICP-MS测定结果评估SC-ICP-MS测定的单细胞内Zn和Cu含量的准确性,采用酸消解细胞的ICP-MS检测结果验证单细胞内Fe和Cr的含量。缺少细胞标准物质时对SC-ICP-MS方法定量结果进行多角度验证是必要的。研究表明,使用SC-ICP-MS法可以较好地进行单细胞元素相关分析。  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号