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   4200篇
  免费   176篇
  国内免费   228篇
化学   1125篇
晶体学   9篇
力学   49篇
综合类   21篇
数学   2038篇
物理学   1362篇
  2023年   22篇
  2022年   90篇
  2021年   94篇
  2020年   64篇
  2019年   55篇
  2018年   72篇
  2017年   72篇
  2016年   59篇
  2015年   51篇
  2014年   77篇
  2013年   263篇
  2012年   150篇
  2011年   336篇
  2010年   243篇
  2009年   468篇
  2008年   439篇
  2007年   361篇
  2006年   377篇
  2005年   231篇
  2004年   116篇
  2003年   81篇
  2002年   190篇
  2001年   142篇
  2000年   118篇
  1999年   71篇
  1998年   76篇
  1997年   40篇
  1996年   63篇
  1995年   29篇
  1994年   35篇
  1993年   8篇
  1992年   12篇
  1991年   10篇
  1990年   4篇
  1989年   7篇
  1988年   5篇
  1987年   5篇
  1986年   3篇
  1985年   6篇
  1984年   5篇
  1983年   5篇
  1981年   7篇
  1980年   7篇
  1979年   8篇
  1978年   5篇
  1977年   3篇
  1975年   3篇
  1974年   2篇
  1973年   6篇
  1959年   2篇
排序方式: 共有4604条查询结果,搜索用时 15 毫秒
21.
《Electroanalysis》2017,29(5):1206-1213
Organophosphorus (OP) pesticides are primarily used as insecticides and chemical warfare agents worldwide. Due to their impact on the environment and health, it is important to develop prompt and accurate pesticide analysis method. This review addresses recent advances and new trends in nanotechnology‐based biosensors for biological monitoring of exposures to OP pesticides and nerve agents. In order to determine them, we have to find the corresponding biomarkers. In 1989, the national academy of sciences (NAS)divided biomarkers into the following three categories: biomarker of exposure, biomarker of effect and biomarker of susceptibility (Figure 1A). The unique chemical and physical properties of nanomaterial have paved the way to new and improved sensing devices, in general, and electrochemical/optical biosensors, in particular. In this paper, background information and a general overview of electrochemical/immunoassay detection techniques are provided. Various nanomaterial labels are discussed. Usually nanomaterials can be roughly divided into nanometer powder, nanometer fiber, nanometer film, nanometer block and so on four classes, such as colloidal gold, semiconductor nanoparticles and carbon nanomaterial (Figure 1B). In addition, we discuss some future considerations and opportunities for advancing the use of biosensors for environmental and health studies.  相似文献   
22.
聚甲氧基二烷基醚(RO(CH2O)nR)具有高的十六烷值(CN)和含氧量,能显著改善柴油的燃烧特性,有效提高热效率,大幅减少碳烟和NOx排放,被认为是一种优良的环保型燃油组分.随着–R基碳链的增长,CN值、热值和闪点逐渐增大,密度和冷凝点逐渐降低.同时,该类化合物具有优异的溶解及渗透性能,能与许多有机溶剂互溶,低毒,可以用作溶剂或颜料分散剂.近年来,聚甲氧基二甲基醚(CH3O(CH2O)nCH3,PODEn,DMMn)的制备及应用研究受到广泛关注,而对封端基团(–R)碳数大于1的多醚类化合物的研究鲜有文献报道.本文以Br?nsted酸性离子液体为催化剂,对甲醛和二乙氧基甲烷或脂肪醇(碳数 ≥2)缩醛化反应制备聚甲氧基二烷基醚的反应性能进行了研究,考察了离子液体结构和酸性对其催化性能的影响.结果表明,–SO3H功能化的离子液体[MIMBs]HSO4在催化三聚甲醛与二乙氧基甲烷的缩醛化反应中表现出最好的催化活性.考察了催化剂用量、原料配比、反应温度、反应压力和反应时间等因素对反应性能的影响,并得到了最佳反应条件,在n([MIMBs]HSO4):n(DEM1):n(HCHO)=1:80:80,140°C下反应4 h,甲醛转化率达到了92.6%,DEM2–8选择性为95.1%.考察了不同甲醛源(三聚甲醛和多聚甲醛)与提供封端基团化合物(二乙氧基甲烷、乙醇、丙醇和丁醇)的缩醛化反应.结果发现,在反应过程中不生成水或不引入水的条件下,具有更高的反应转化率和产物选择性.分别采用静置分层和萃取实现了催化剂的分离与重复使用.推测反应机理认为,三聚甲醛首先在氢键作用下分解生成甲醛单体,甲醛和二乙氧基甲烷通过碳正离子反应机理实现了DEMn的链增长.  相似文献   
23.
以亲缘关系较近的猪、牛和羊3个物种的肌肉组织为研究对象,采用超高效液相色谱-串联质谱(UPLC-MS),筛选并确认了猪物种肉特异性肽生物标志物.3种纯肉样品经蛋白质提取、胰蛋白酶消化和UPLC-TripleTOF-MS分离鉴定,得到的总离子流图谱(TIC)与Uniprot蛋白质数据库对比分析,筛选出3个物种肉的3种高丰度同源蛋白和8种潜在的肽生物标志物;潜在的肽生物标志物经QTRAP-MS质谱的多反应模式(MRM)分析,最终确认了猪物种肉的5种肽生物标志物,其中3种肽生物标志物未见文献报道.  相似文献   
24.
Two new hybrid compounds, [Cu(1)(phen)(H2O)][Cu(2)(phen)(H2O)]([Cu(3)]0.25(H2O)][P2Mo5O23]·3.75H2O (1) and [Cu(en)2]1.5[P2Mo5O23]2·(enH2)3·2H2O (2) (phen = 1,10-phenanthroline, en = ethylenediamine), have been hydrothermally synthesized and characterized by IR, UV–Vis spectroscopy, X-ray photoelectron spectroscopy (XPS), powder XRD analyses, TG analyses, cyclic voltammogram analyses, elemental analyses, and single crystal X-ray diffraction analyses. Single crystal X-ray diffraction analyses reveal that the two compounds have a 1-D chain structure formed by Strandberg-type POMs and TMCs with –A–B–C–B–A–B–C–B– linking mode, then further extend into a 2-D layer structure through π?π or hydrogen bond interactions.  相似文献   
25.
In this paper, we mainly discuss the class of charming spaces. First, we show that there exists a charming space such that the Tychonoff product is not a charming space. Then we discuss some properties of charming spaces and give some characterizations of some class of charming spaces. Finally, we show that the Suslin number of an arbitrary charming rectifiable space is countable.  相似文献   
26.
In this short note, we give a characterization of domains satisfying Serre’s condition (R1) in terms of their canonical modules. In the special case of toric rings, this generalizes a result of the second author [9 Yanagawa, K. (2015). Dualizing complexes of seminormal a?ne semigroup rings and toric face rings. J. Algebra 425:367391.[Crossref], [Web of Science ®] [Google Scholar]] where the normality is described in terms of the “shape” of the canonical module.  相似文献   
27.
In this article, a multiobjective problem with a feasible set defined by inequality, equality and set constraints is considered, where the objective and constraint functions are locally Lipschitz. Several constraint qualifications are given and the relations between them are analyzed. We establish Kuhn-Tucker and strong Kuhn-Tucker necessary optimality conditions for (weak) quasi e?ciency in terms of the Clarke subdifferential. By using two new classes of generalized convex functions, su?cient conditions for local (weak) quasi e?cient are also provided. Furthermore, we study the Mond-Weir type dual problem and establish weak, strong and converse duality results.  相似文献   
28.
The ?-grading determined by a long simple root of a rank n+1 a?ne Lie algebra over ? arises from a representation of a rank n semi-simple complex Lie algebra. Analysis of the relationship between the grading and the representation yields constructions that generalize the minuscule and adjoint algorithms as well as Kac’s construction of nontwisted a?ne Lie algebras.  相似文献   
29.
In this paper, we propose two proximal-gradient algorithms for fractional programming problems in real Hilbert spaces, where the numerator is a proper, convex and lower semicontinuous function and the denominator is a smooth function, either concave or convex. In the iterative schemes, we perform a proximal step with respect to the nonsmooth numerator and a gradient step with respect to the smooth denominator. The algorithm in case of a concave denominator has the particularity that it generates sequences which approach both the (global) optimal solutions set and the optimal objective value of the underlying fractional programming problem. In case of a convex denominator the numerical scheme approaches the set of critical points of the objective function, provided the latter satisfies the Kurdyka-?ojasiewicz property.  相似文献   
30.
Wine metabolomics constitutes a powerful discipline towards wine authenticity assessment through the simultaneous exploration of multiple classes of compounds in the wine matrix. Over the last decades, wines from autochthonous Greek grape varieties have become increasingly popular among wine connoisseurs, attracting great interest for their authentication and chemical characterization. In this work, 46 red wine samples from Agiorgitiko and Xinomavro grape varieties were collected from wineries in two important winemaking regions of Greece during two consecutive vintages and analyzed using ultra-high performance liquid chromatography-quadrupole time-of-flight mass spectrometry (UHPLC-QToF-MS). A targeted metabolomics methodology was developed, including the determination and quantification of 28 phenolic compounds from different classes (hydroxycinnamic acids, hydroxybenzoic acids, stilbenes and flavonoids). Moreover, 86 compounds were detected and tentatively identified via a robust suspect screening workflow using an in-house database of 420 wine related compounds. Supervised chemometric techniques were employed to build an accurate and robust model to discriminate between two varieties.  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