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   93089篇
  免费   12533篇
  国内免费   6888篇
化学   42028篇
晶体学   603篇
力学   9968篇
综合类   927篇
数学   26756篇
物理学   32228篇
  2023年   922篇
  2022年   1674篇
  2021年   2558篇
  2020年   3063篇
  2019年   2818篇
  2018年   2238篇
  2017年   2721篇
  2016年   3390篇
  2015年   3015篇
  2014年   4524篇
  2013年   7420篇
  2012年   5389篇
  2011年   5748篇
  2010年   4778篇
  2009年   5903篇
  2008年   5994篇
  2007年   6412篇
  2006年   5246篇
  2005年   4334篇
  2004年   3708篇
  2003年   3586篇
  2002年   3189篇
  2001年   2689篇
  2000年   2174篇
  1999年   1850篇
  1998年   1643篇
  1997年   1451篇
  1996年   1297篇
  1995年   1368篇
  1994年   1223篇
  1993年   1146篇
  1992年   961篇
  1991年   666篇
  1990年   567篇
  1989年   453篇
  1988年   455篇
  1987年   445篇
  1986年   438篇
  1985年   580篇
  1984年   458篇
  1983年   254篇
  1982年   464篇
  1981年   589篇
  1980年   493篇
  1979年   561篇
  1978年   446篇
  1977年   347篇
  1976年   286篇
  1974年   98篇
  1973年   184篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
1.
We consider parametric optimization problems from an algebraic viewpoint. The idea is to find all of the critical points of an objective function thereby determining a global optimum. For generic parameters (data) in the objective function the number of critical points remains constant. This number is known as the algebraic degree of an optimization problem. In this article, we go further by considering the inverse problem of finding parameters of the objective function so it gives rise to critical points exhibiting a special structure. For example if the critical point is in the singular locus, has some symmetry, or satisfies some other algebraic property. Our main result is a theorem describing such parameters.  相似文献   
2.
The effect of ultrasound on the kinetics of anti-solvent crystallization of sucrose was studied. The influence of temperature, stirring rate, supersaturation and ultrasonic power on the anti-solvent crystallization of sucrose was investigated. The relationship between infrared spectral characteristic band of sucrose and supersaturation was determined with an online reaction analyzer. The crystal size distribution of sucrose was detected by a laser particle-size analyzer. Ultrasound accelerated the crystallization process, and had no impact on the crystal shape. Abegg, Stevens and Larson model was fitted to the experimental data, and the results were the following: At 298.15 K, the average size of crystals was 133.8 μm and nucleation rate was 4.87 × 109 m−3·s−1 without ultrasound. In an ultrasonic field, the average size was 80.5 μm, and nucleation rate was 1.18 × 1011 m−3·s−1. Ultrasound significantly reduced the average size of crystals and improved the nucleation rate. It was observed that the crystal size decreased with the increase of stirring rate in silent environment. When the stirring rate increased from 250 to 400 rpm, the average size decreased from 173.0 to 132.9 μm. However, the stirring rate had no significant impact on the crystal size in the ultrasonic field. In addition, the activation energy of anti-solvent crystallization of sucrose was decreased, and the kinetic constant of nucleation rate was increased due to the effect of ultrasound. In the ultrasonic field, the activation energy was reduced from 20422.5 to 790.5 J·mol−1, and the kinetic constant was increased from 9.76 × 102 to 8.38 × 108.  相似文献   
3.
氮和磷是水环境生物生长和繁殖必须的营养成分,影响水体初级生产力的水平,且水体富营养化水平与氮磷形态密切相关,随着水体环境的改变,沉积物会向水体释放氮磷,造成二次污染。同时,对外源氮磷污染来源的贡献进行定量识别,可有效管理和控制水体氮磷污染负荷。毗河和石亭江是沱江的重要支流,影响着长江母亲河的水质。采用钼锑抗分光光度法和连续提取法研究在枯水期和丰水期毗河和石亭江水体和表层沉积物中总氮(TN)、总磷(TP)及各形态氮磷的分布特性,对比不同土地利用类型河流氮磷行为特性及释放风险,并采用Multiple Linear Regression of the Absolute Principal Component Scores(APCS-MLR)受体模型进行氮磷污染源的识别和量化。研究结果表明:① 研究区水体和表层沉积物中氮磷均处于不同程度的污染水平,水体枯水期TP的主要贡献者是颗粒态无机磷(PIP)和颗粒态有机磷(POP),而丰水期却是颗粒态无机磷(PIP)和溶解态无机磷(DIP),两水期水体中TN的主要贡献者是硝态氮(NO-3-N)和有机氮(ON)。而在表层沉积物中,TP的主要贡献者是钙结合态磷(HCl-P),TN的主要贡献者是酸解态氮(HN)。在枯水期和丰水期,毗河表层沉积物生物有效磷(BAP)占TP的平均值(19.7%和23.0%)比石亭江的平均值(11.0%和12.5%)占比更高,具有较高的磷释放风险。研究发现,枯水期氮磷污染程度高于丰水期,而且石亭江的氮磷污染程度高于毗河。②APCS-MLR模型在毗河提取了城镇生活污水、生活垃圾堆积产生的渗滤液、动植物残体分解和养殖业废水4个污染源因子,其中城镇生活污水对毗河氮磷污染的贡献最大(枯水期50.9%,丰水期54.8%),而在石亭江提取了工业生产中产生的废水等、动植物残体的降解、农业废弃物的风化、农田排水渠的农业废水和农药化肥的不合理施用5个污染源因子,其中工业生产中产生的废水等对石亭江氮磷污染的贡献最大(枯水期58.7%,丰水期55.8%)。因此,当地相关部门应加强对高贡献污染源的管控,从而降低流域氮磷污染负荷。  相似文献   
4.
Organic solar cells (OSCs) harvesting indoor light are highly promising for emerging technologies, such as internet of things. Herein, the photovoltaic performance of PTB7-Th:PC71BM solar cells constructed using “optimized (with 1,8-diiodooctane (DIO))” and “non-optimized (without DIO)” processing conditions are compared for indoor and outdoor applications. We find that in comparison to the “optimized” solar cell, the “non-optimized” solar cell is less efficient under simulated solar light illumination (100 mW cm−2, spectral range 350–1100 nm), owing to significant bimolecular charge carrier recombination losses. However, under simulated indoor illumination (3.28 mW cm−2, spectral range 400–700 nm), bimolecular recombination losses are effective suppressed, thus the power conversion efficiency of the solar cell without DIO was increased to 14.7 %, higher than that of the solar cell with DIO (14.2 %). These results suggest that the common strategy used to optimize the OSCs could be undesired for indoor OSCs. We demonstrate that the efforts for realizing the desired “morphology” of the active layer for the outdoor OSCs may be unnecessary for indoor OSCs, allowing us to realize high-efficiency indoor OSCs using a non-halogenated solvent.  相似文献   
5.
The reaction of N2 with trinuclear niobium and tungsten sulfide clusters Nb3Sn and W3Sn (n=0–3) was systematically studied by density functional theory calculations with TPSS functional and Def2-TZVP basis sets. Dissociations of N−N bonds on these clusters are all thermodynamically allowed but with different reactivity in kinetics. The reactivity of Nb3Sn is generally higher than that of W3Sn. In the favorite reaction pathways, the adsorbed N2 changes the adsorption sites from one metal atom to the bridge site of two metal atoms, then on the hollow site of three metal atoms, and at that place, the N−N bond dissociates. As the number of ligand S atoms increases, the reactivity of Nb3Sn decreases because of the hindering effect of S atoms, while W3S and W3S2 have the highest reactivity among four W3Sn clusters. The Mayer bond order, bond length, vibrational frequency, and electronic charges of the adsorbed N2 are analyzed along the reaction pathways to show the activation process of the N−N bond in reactions. The charge transfer from the clusters to the N2 antibonding orbitals plays an essential role in N−N bond activation, which is more significant in Nb3Sn than in W3Sn, leading to the higher reactivity of Nb3Sn. The reaction mechanisms found in this work may provide important theoretical guidance for the further rational design of related catalytic systems for nitrogen reduction reactions (NRR).  相似文献   
6.
A detailed study of the geometry, aromatic character, electronic and magnetic properties for a series of positively charged N-doped polycyclic aromatic hydrocarbons (PAHs) was performed. Magnetic properties of the examined molecules were analyzed by means of the magnetically induced current density calculated using the diamagnetic-zero version of the continuous transformation of origin of current density (CTOCD-DZ) method. The comparative study of the local aromaticity of the studied molecules was performed using several different indices: energy effect (ef), harmonic oscillator model of aromaticity (HOMA) index, six centre delocalization index (SCI) and nucleus independent chemical shifts (NICS). The presence of N-atoms in the inner rings was found to cause a planarity distortion in the studied N-doped systems. The geometric changes and charged nature of the studied N-doped systems do not significantly influence the current density and the local aromaticity distribution in comparison with the corresponding parent benzenoid hydrocarbons. The present study demonstrates how quantum chemical calculations can be used for rational design of novel PAHs and for fine tuning of their properties.  相似文献   
7.
New lanthanide dimethyl-N-benzoylamidophosphate (HL) based tetrakis-complexes NEt4[LnL4] (Ln3+=La, Nd, Sm, Eu, Gd, Tb, Dy) are reported. The complexes are characterized by means of NMR, IR, absorption, and luminescent spectroscopy as well as by elemental, X-Ray, and thermal gravimetric analyses. The phenyl groups of the four ligands of the complex anion are directed towards one side, while the methoxy groups are directed in the opposite side, which makes the complexes under consideration structurally similar to calixarenes. The effect of changing the alkali metal counterion to the organic cation NEt4+ on the structure and properties of the tetrakis-complex [LnL4]- is analyzed. The complexes exhibit bright characteristic for respective lanthanides luminescence. Rather high intensity of the band of 5D07F4 transition, observed in the luminescence spectrum of NEt4[EuL4], is discussed based on theoretical calculations.  相似文献   
8.
Dehydrogenation of an organic compound is the first and the most fundamental elementary reaction in many organic reactions. In ethanol oxidation reaction (EOR) to form CO2, there are a total of 46 pathways in C2HxO (x=1–6) species leading to the removal of all six hydrogen atoms in five C−H bonds and one O−H bond. To investigate the degree of dehydrogenation in EOR under operando conditions, we performed density function theory (DFT) calculations to study 28 dehydrogenation steps of C2HxO on Ir(100). An activation energy surface was then constructed and compared with that of the C−C bond cleavages to understand the importance of the degree of dehydrogenation in EOR. The results show that there are likely 28 dehydrogenations in EOR under fuel cell temperatures and the last two hydrogens in C2H2O are less likely cleaved. On the other hand, deep dehydrogenation including 45 dehydrogenations can occur under ethanol steam reforming conditions.  相似文献   
9.
One of the most common problems in wounds is delayed healing and complications such as infection. Therefore, the need for novel materials accelerates the healing of wounds especially abdominal wounds after surgery besides high efficiency and safety is mandatory. The rate of wound healing, anti-inflammatory and biocompatibility of Zn-Al LDH (Zn-Al layer double hydroxide) alone and loaded with Curcumin (Zn-Al LDH/Curcumin) was screened via in-vivo assays through intramuscular implantation in rat abdominal wall with intact peritoneum cavity. The implanted drugs were formed through Curcumin loaded into LDH of Zn-Al with drug release of 56.78 ± 1.51% within 24 h. The synthesized nanocomposite was characterized by (TGA/DTA) thermal analysis, (XRD) X-ray diffraction, (FESEM) Field emission scanning electron microscopy, (HRTEM) high resolution transmission electron microscope, energy dispersive X-ray (EDX) and low-temperature N2 adsorption, pore volume and average pore size distribution. The integrity of blood circulation, inflammatory signs, wound healing rate, capacity of tissue integration, antigenicity and composite biocompatibility, auto fluorescence ability of collagen bundles and the tensile strength of the muscle were assessed histopathologically after 7 and 30 days’ post-implantation. Excellent wound healing ability was achieved with shortest length between the wound gap edges and higher tensile strength of the muscle. Besides emit florescence very well followed by good healing and tensile muscles strength in Curcumin while very low strength with scar formation in Zn-Al LDH/Curcumin in both acute and chronic wound. No signs of inflammation in Curcumin & Zn-Al LDH. No vessels obstruction or bleeding observed in both Zn-Al LDH and Curcumin more than Zn-Al LDH/Curcumin and control which examined through candling. Good healing & infiltrated immune cells in same groups through histopathological examination. This work supports the anti-inflammatory, wound healing and biocompatibility of both LDH and Curcumin with living matter, increasing their biomedical applications in this era with safety and increasing efficacy with prolonged drug release.  相似文献   
10.
Supercapacitors (SCs) with high energy density and power density are a research hotspot. Herein, we report a flexible porous carbon membrane supercapacitor prepared by electrospinning polyacrylonitrile (PAN) with γ-cyclodextrin-MOF (γ-CD-MOF) and then carbonizing at 900 °C. BET results showed that the supercapacitor retained the skeleton of γ-CD, γ-CD-MOF and the pores formed by the spun-fibers, which were 0.73, 1.09 and 23–186 nm, respectively, showing a high specific surface area of 134.7 m2/g. The hierarchically porous structures ensure rapid charge transfer and ion diffusion, resulting in the PAN/γ-CD-MOF carbon electrode with a high capacity of 283.3 F/g. Moreover, the supercapacitor had a high energy density up to 17.5 Wh/kg and power density up to 6 kW/kg. Significantly, it showed excellent cycle stability with a capacitance retention of 97.5% after 6000 cycles. This work provides a supramolecular strategy to construct a flexible porous carbon membrane, which has potential for supercapacitor applications.  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