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   9599篇
  免费   1470篇
  国内免费   900篇
化学   6707篇
晶体学   94篇
力学   516篇
综合类   61篇
数学   1088篇
物理学   3503篇
  2024年   28篇
  2023年   168篇
  2022年   316篇
  2021年   324篇
  2020年   350篇
  2019年   340篇
  2018年   297篇
  2017年   273篇
  2016年   411篇
  2015年   435篇
  2014年   521篇
  2013年   715篇
  2012年   848篇
  2011年   833篇
  2010年   596篇
  2009年   561篇
  2008年   614篇
  2007年   502篇
  2006年   525篇
  2005年   420篇
  2004年   380篇
  2003年   290篇
  2002年   286篇
  2001年   218篇
  2000年   152篇
  1999年   178篇
  1998年   154篇
  1997年   175篇
  1996年   165篇
  1995年   121篇
  1994年   123篇
  1993年   96篇
  1992年   63篇
  1991年   56篇
  1990年   60篇
  1989年   41篇
  1988年   30篇
  1987年   22篇
  1986年   35篇
  1985年   29篇
  1984年   23篇
  1983年   20篇
  1982年   11篇
  1981年   13篇
  1980年   16篇
  1979年   10篇
  1978年   22篇
  1977年   10篇
  1976年   13篇
  1974年   12篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
Ti3C2TX MXene was synthesized by exfoliating pristine Ti3AlC2 phase with hydrofluoric acid. The simple methods of mechanical mixing and drop-casting of Ti3C2TX and MWCNTs were carried out to prepare sensing electrode of Ti3C2TX/MWCNTs/GCE. The composite and topography, especially the surface functional groups of Ti3C2TX/MWCNTs were analyzed by XRD, SEM, FTIR, XPS, and Raman spectrum. The results turned out that Ti3C2TX was characteristic by accordion-like 2D nanostructure with the surfaces terminated with −OH, −F, and =O. When combining with acid pretreated, the interaction between the functional groups of Ti3C2TX and MWCNTs facilitated the convenience and reproducibility of the robust modified electrodes and could make Ti3C2TX/MWCNTs/GCE possess good synergistic catalytic acceleration by increasing the electron transfer efficiency as well as adsorption and aggregation of MOP analyte onto the electrode surface. Versatile electrochemical measurements of CV, DPV and EIS were used to investigate the electrochemical performance of Ti3C2TX/MWCNTs/GCE sensing platform. The linear detection range is 0.01–100 μM with the limit of detection of 0.0092 μM (S/N=3). The sensor has good stability, repeatability, reproducibility and anti-interference. In the detection of serum and urine samples, it has a good recovery rate.  相似文献   
992.
Y chromosome kits are successfully applied in cases where human biological material exists. With the development of genotyping ability, more Y chromosomal markers are needed for finer identification of male individuals and lineages. In this study, a developmental validation of a newly emerged Y chromosome kit that combines two different kinds of markers: 38 Y-STRs and 3 Y-indels are conducted. The results show that this kit has high sensitivity when there is a small amount of DNA (125 pg), more than one male (minor:major = 1:7), or a mixture of males and females (male:female = 125pg:1875pg), inhibited substances (800 μM hematin and more than 1600 ng/μL humic acid). The kit exhibits high precision level with a standard deviation of allele size no more than 0.14 nt. Locus DYS481 shows the largest stutter rate, with three stutters per true allele. Population samples are well identified (MP of 0.001106), and mutations can be observed in father–son pairs (46 mutations in 70 pairs, 10 in locus DYS627). Out of all the population samples, 13.2% belong to haplogroup M117-O2a2b1a1, with their ethnic group being Han Chinese. The results show that this kit can improve the performance of identifying male individuals, obtaining more unique haplotypes (increasing from 894 to 918 of 1000 male samples) and higher discrimination capacity (increasing from 0.942 to 0.955) in this study compared to previous widely used Yfiler Plus kit. Besides, it gives information about their paternal lineages in forensic genetic casework and genealogical database construction.  相似文献   
993.
Kyrgyz ethnic group is one of the nomads in China, with the majority in Xinjiang and a small part of them living in Heilongjiang province. Historically, they have went through five migrations westward due to the wars. The name “Kyrgyz” means 40 tribes, originating from the primary groups of Kyrgyz. However, it is a largely understudied population, especially from the Y chromosome. In this study, we used a previously validated high-resolution Y-chromosome single nucleotide polymorphisms (Y-SNPs) and short tandem repeats (Y-STRs) system to study Kyrgyz ethnic group. A total of 314 male samples of Kyrgyz ethnic group were genotyped by 173 Y-SNPs and 27 Y-STRs. After data analysis, the results unveiled that Kyrgyz ethnic group was a population with high percentage of both haplogroup C2a1a3a1d∼-F10091 (91/134) and R1a1a1b2a2-Z2124 (109/134), which has never been reported. This implied that Kyrgyz ethnic group might have gone through bottleneck effects twice, with these two main lineages left. Mismatch analysis indicated that the biggest mismatch number in haplogroup C2a1a3a1d∼-F10091 was 10, while that of haplogroup R1a1a1b2a2-Z2124 was 20. This huge difference reflected the different substructure in two lineages, suggesting that haplogroup C2a1a3a1d∼-F10091 might have the least admixture compared to the other two lineages. After admixture modelling with other datasets, the conclusion could be drawn that Kyrgyz ethnic group had great genetic affinity with Punjabi from Lahore, Pakistan, which supported that Kyrgyz ethnic group in China was close to central Asian.  相似文献   
994.
Ren H. Luo  Huan J. Keh 《Electrophoresis》2021,42(21-22):2134-2142
The electrophoresis and electric conduction of a suspension of charged spherical particles in a salt-free solution are analyzed by using a unit cell model. The linearized Poisson-Boltzmann equation (valid for the cases of relatively low surface charge density or high volume fraction of the particles) and Laplace equation are solved for the equilibrium electric potential profile and its perturbation caused by the imposed electric field, respectively, in the fluid containing the counterions only around the particle, and the ionic continuity equation and modified Stokes equations are solved for the electrochemical potential energy and fluid flow fields, respectively. Explicit analytical formulas for the electrophoretic mobility of the particles and effective electric conductivity of the suspension are obtained, and the particle interaction effects on these transport properties are significant and interesting. The scaled zeta potential, electrophoretic mobility, and effective electric conductivity increase monotonically with an increase in the scaled surface charge density of the particles and in general decrease with an increase in the particle volume fraction, keeping each other parameter unchanged. Under the Debye-Hückel approximation, the dependence of the electrophoretic mobility normalized with the surface charge density on the ratio of the particle radius to the Debye screening length and particle volume fraction in a salt-free suspension is same as that in a salt-containing suspension, but the variation of the effective electric conductivity with the particle volume fraction in a salt-free suspension is found to be quite different from that in a suspension containing added electrolyte.  相似文献   
995.
The development of a new three-component chromatography-free reaction of isocyanides, amines and elemental sulfur allowed us the straightforward synthesis of thioureas in water. Considering a large pool of organic and inorganic bases, we first optimized the preparation of aqueous polysulfide solution from elemental sulfur. Using polysulfide solution, we were able to omit the otherwise mandatory chromatography, and to isolate the crystalline products directly from the reaction mixture by a simple filtration, retaining the sulfur in the solution phase. A wide range of thioureas synthesized in this way confirmed the reasonable substrate and functional group tolerance of our protocol.  相似文献   
996.
Fuel cells have attracted increasing attention due to their low cost, high energy density, low environmental pollution, and abundant raw materials. Oxygen reduction reaction (ORR) is a core technology of fuel cells, and the development of new electrocatalysts with high ORR performance is highly desirable. Herein, we synthesize a series of B, N co-doped hierarchical porous carbons using a soft template method with the integration of self-assembly, calcination and etching. The obtained materials exhibit hierarchical porous structures, controllable pore distribution, partial graphite structures, and B, N co-doping. They can function as the cost-effective and metal-free electrocatalysts, facilitating the diffusion of electrolyte ions and the improvement of ORR performance. Especially, the B, N co-doped porous carbon with the B-to-N molar ratio of 5 (BNC-5) displays a high ORR activity with a half-wave potential (E1/2) of 0.73 V, an onset potential (Eonset) of 0.94 V, and a high limiting current density (JL) of 5.98 mA cm−2, superior to the N-doped C (NC) and BNC-1 (the B-to-N molar ratio=1), BNC-3 (the B-to-N molar ratio=3) and BNC-7 (the B-to-N molar ratio=7) under the identical conditions. Moreover, the BNC-5 exhibits good cycling stability after 5000 cyclic voltammetry (CV) cycles and excellent tolerance toward even 3 M methanol. This research provides a new approach for the facile synthesis of dual element-doped carbon electrocatalysts with high ORR performance.  相似文献   
997.
Despite intensive scientific efforts on the development of organic batteries, their full potential is still not being realized. The individual components, such as electrode materials and electrolytes, are in most cases developed independently and are not adjusted to each other. In this context, we report on the performance optimization of a full-organic solid-state battery system by the mutual adaptation of the electrode materials and an ionic liquid (IL)-based gel polymer electrolyte (GPE). The formulation of the latter was designed for a one-step manufacturing approach and can be applied directly to the electrode surface, where it is UV-cured to yield the GPE without further post-treatment steps. Herein, a special focus was placed on the applicability in industrial processes. A first significant capacity increase was achieved by the incorporation of the IL into the electrode composite. Furthermore, the GPE composition was adapted applying acrylate- and methacrylate-based monomers and combinations thereof with the premise of a fast curing step. Furthermore, the amount of IL was varied, and all combinations were evaluated for their final performance in cells. The latter variation revealed that a high ionic conductivity is not the only determining factor for a good cell performance. Next to a sufficient conductivity, the interaction between electrode and electrolyte plays a key role for the cell performance as it enhances the accessibility of the counter ions to the redox-active sites.  相似文献   
998.
Although the production of near-infrared (NIR)-absorbing organic polymers with an excellent nonlinear optical (NLO) response is vital for various optoelectronic devices and photodynamic therapy, the molecular design and relevant photophysical investigation still remain challenging. In this work, large NLO activity is observed for an NIR-absorbing bithiophene-based polymer with a unique head-to-head linkage in the NIR region. The saturable absorption coefficient and modulation depth of the polymer are determined as ∼−3.5×105 cm GW−1 and ∼32.43%, respectively. Notably, the polymer exhibits an intrinsic nonlinear refraction index up to ∼−9.36 cm2 GW−1, which is six orders of magnitude larger than that of CS2. The maximum molar-mass normalized two-photon absorption cross-section (σ2/M) of this polymer can be up to ∼14 GM at 1200 nm. Femtosecond transient absorption measurements reveal significant spectral overlap between the 2PA and excited state absorption in the 1000–1400 nm wavelength range and an efficient triplet quantum yield of ∼36.7%. The results of this study imply that this NIR-absorbing polymer is promising for relevant applications.  相似文献   
999.
To investigate the effects of oxygen-containing functional groups on the adsorption of volatile organic compounds (VOCs) with different polarity, oxygen-rich porous carbon materials (OPCs) were synthesized by heat treatment of glucose/potassium oxalate material. The carbon material had a large specific surface area (1697 m2 g−1) and a high oxygen content (18.95 at.%). OPC exhibited high adsorption capacity of toluene (309 mg g−1) and methanol (447 mg g−1). The specific surface area and total pore volume determined the adsorption capacity of toluene and methanol at the high-pressure range, while the oxygen-containing groups became the main factor affecting the methanol adsorption at the low-pressure range due to the hydrogen bond interaction through the density functional theory (DFT) calculations. This study provides an important hint for developing a novel O-doped adsorbent for the VOCs adsorption applications and analyzing the role of oxygen-containing groups in the VOCs adsorption under the low-pressure range.  相似文献   
1000.
Nitrogen transfer from cyanide anion to an aldehyde is emerging as a promising method for the synthesis of aromatic nitriles. However, this method still suffers from a disadvantage that a use of stoichiometric Cu(II) or Cu(I) salts is required to enable the reaction. As we report herein, we overcame this drawback and developed a catalytic method for nitrogen transfer from cyanide anion to an alcohol via the complete cleavage of the C≡N triple bond using phen/Cu2O as the catalyst. The present condition allowed a series of benzyl alcohols to be smoothly converted into aromatic nitriles in moderate to high yields. In addition, the present method could be extended to the conversion of cinnamic alcohol to 3-phenylacrylonitrile.  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