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   13659篇
  免费   2269篇
  国内免费   1491篇
化学   9493篇
晶体学   124篇
力学   914篇
综合类   95篇
数学   1651篇
物理学   5142篇
  2024年   46篇
  2023年   306篇
  2022年   517篇
  2021年   557篇
  2020年   583篇
  2019年   511篇
  2018年   493篇
  2017年   429篇
  2016年   619篇
  2015年   666篇
  2014年   760篇
  2013年   1010篇
  2012年   1154篇
  2011年   1178篇
  2010年   810篇
  2009年   746篇
  2008年   833篇
  2007年   771篇
  2006年   693篇
  2005年   578篇
  2004年   420篇
  2003年   351篇
  2002年   325篇
  2001年   283篇
  2000年   237篇
  1999年   279篇
  1998年   267篇
  1997年   196篇
  1996年   221篇
  1995年   216篇
  1994年   184篇
  1993年   168篇
  1992年   132篇
  1991年   143篇
  1990年   144篇
  1989年   108篇
  1988年   93篇
  1987年   79篇
  1986年   61篇
  1985年   62篇
  1984年   29篇
  1983年   33篇
  1982年   26篇
  1981年   20篇
  1980年   13篇
  1979年   10篇
  1978年   8篇
  1977年   10篇
  1974年   6篇
  1973年   9篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
951.
本文设计开发了一种以2,6-二甲酰基对甲苯酚为母体的新型荧光探针HMI,可用于高效识别EtOH-H2O (8/2, v/v, HEPES 10 mM, pH =7.4)体系中的CO32-。HMI在660 nm处显示发射带,加入CO32-后,在600 nm的等吸收点激发时,原来在660 nm处的荧光淬灭,而以540 nm为中心的新发射带荧光显着增加,为比率型荧光探针。HMI对CO32-表现出高选择性且具有较强的抗干扰能力。此外,荧光探针HMI对CO32-荧光响应的检测限较低,可达到3.938×10-6 M。更具有意义的是,HMI探针对CO32-的检测能够在实际水样中起到很好的应用,而且细胞成像研究表明,HMI可用于活体MCF-7细胞中CO32-的成像。  相似文献   
952.
Catalytic transfer hydroge nation(CTH) of furfural(FF) to furfu ryl alcohol(FFA) has received great intere st in recent years.He rein,Cu-Cs bimetallic supported catalyst,CuCs(2)-MCM,was developed for the CTH of FF to FFA using formic as hydrogen donor.CuCs(2)-MCM achieved a 99.6% FFA yield at an optimized reaction conditions of 170℃,1 h.Cu species in CuCs(2)-MCM had dual functions in catalytically decomposing formic acid to generate hydrogen and hydrogenating FF to FFA.The doping of Cs made the size of Cu particles smaller and improved the dispersion of the Cu active sites.Impo rtantly,the Cs species played a favorable role in enhancing the hydrogenation activity as a promoter by adjusting the surface acidity of Cu species to an appropriate level.Correlation analysis showed that surface acidity is the primary factor to affect the catalytic activity of CuCs(2)-MCM.  相似文献   
953.
Aromatic organoboron compounds are highly valuable building blocks in organic chemistry. They were mainly synthesized through aromatic C−H and C−Het borylation, in which transition metal-catalysis dominate. In the past decade, with increasing attention to sustainable chemistry, numerous transition metal-free C−H and C−Het borylation transformations have been developed and emerged as efficient methods towards the synthesis of aromatic organoboron compounds. This account mainly focuses on recent advances in transition metal-free aromatic C−H, C−N, C−S, and C−O borylation transformations and provides insights to where further developments are required.  相似文献   
954.
It is still challenging to design and develop the state-of-the-art photocatalysts toward CO2 photoreduction. Enormous researchers have focused on the halide perovskites in the photocatalytic field for CO2 photoreduction, due to their excellent optical and physical properties. The toxicity of lead-based halide perovskites prevents their large-scale applications in photocatalytic fields. In consequence, lead-free halide perovskites (LFHPs) without the toxicity become the promising alternatives in the photocatalytic application for CO2 photoreduction. In recent years, the rapid advances of LFHPs have offer new chances for the photocatalytic CO2 reduction of LFHPs. In this review, we summarize not only the structures and properties of A2BX6, A2B(I)B(III)X6, and A3B2X9-type LFHPs but also their recent progresses on the photocatalytic CO2 reduction. Furthermore, we also point out the opportunities and perspectives to research LFHPs photocatalysts for CO2 photoreduction in the future.  相似文献   
955.
细胞内溶酶体的pH值对细胞自噬、吞噬、酶加工等各项生命活动有着重要影响.细胞核是真核细胞中最大的细胞器,控制着生物体内的遗传和代谢过程,参与代谢过程的酶对pH值的变化很敏感.因此,研究细胞体内的pH值变化至关重要.我们设计并以简单的两步反应合成了一种新型荧光探针NpH-1.该探针以萘酰亚胺作为荧光团,以吗啉基团作为对p...  相似文献   
956.
In this study, ultrasonic-assisted cellulase extraction (UCE) was applied to extract flavonoids and polyphenols from the Nymphaea hybrid flower. The extraction conditions were optimized using the response surface method (RSM) coupled with a Box-Behnken design. The crude extract of Nymphaea hybrid (NHE) was further purified using AB-8 macroporous resins, and the purified extract (NHEP) was characterized by FTIR and HPLC. In vitro activity determination by chemical method showed that NHEP displayed strong free radical scavenging abilities against the DPPH and ABTS radicals, good reduction power, and hyaluronidase inhibition. The cell viability by CCK-8 assays showed that NHEP had no significant cytotoxicity for B16 and HaCaT cells when the concentration was below 100 μg/mL and 120 μg/mL, respectively. NHEP with a concentration of 20–160 μg/mL can more effectively reduce the ROS level in H2O2 damaged HaCaT cells compared with 10 μg/mL of VC. The 40 μg/mL of NHEP had similar activity against intracellular melanin production in the B16 melanoma cells compared with 20 μg/mL Kojic acid. Good activities of antioxidation, whitening and protective effect against H2O2-induced oxidative damage promote the potential for NHEP as a functional raw material in the field of cosmetics and medicine.  相似文献   
957.
Protein arginine methyltransferases 5 (PRMT5) is a clinically promising epigenetic target that is upregulated in a variety of tumors. Currently, there are several PRMT5 inhibitors under preclinical or clinical development, however the established clinical inhibitors show favorable toxicity. Thus, it remains an unmet need to discover novel and structurally diverse PRMT5 inhibitors with characterized therapeutic utility. Herein, a series of tetrahydroisoquinoline (THIQ) derivatives were designed and synthesized as PRMT5 inhibitors using GSK-3326595 as the lead compound. Among them, compound 20 (IC50: 4.2 nM) exhibits more potent PRMT5 inhibitory activity than GSK-3326595 (IC50: 9.2 nM). In addition, compound 20 shows high anti-proliferative effects on MV-4-11 and MDA-MB-468 tumor cells and low cytotoxicity on AML-12 hepatocytes. Furthermore, compound 20 possesses acceptable pharmacokinetic profiles and displays considerable in vivo antitumor efficacy in a MV-4-11 xenograft model. Taken together, compound 20 is an antitumor compound worthy of further study.  相似文献   
958.
A new liquid crystalline polyacetylene containing a phenyl benzoate mesogen (5) is synthesized,whose mesomorphic properties are found to be easily "tunab1e" by simple mechanical perturbation. Thepolymerization of 10- [ 4 - (4' -methoxyphenoxycarbonyl )phenoxycarbonyl] - 1 -decyne (4 ) in itiated by theWCl_6-Ph_4Sn/dioxane complex yields polymer 5 with a M_w of 28400. The molecular structure of 5 ischaracterized by NMR, IR, and UV spectroscopy and its liquid crystalline behavior is investigated by DSC,POM, and XRD analysis. Upon mechanical perturbation, 5 exhibits unusual agitation-induced high-strengthdisclinations, shear-induced inversion walls, and solidification-induced banded textures. Such phenomenahave been observed in the main-chain liquid crystalline polymers with rigid backbones, but have seldom beenreported for the side-chain liquid crystalline polymers with flexible backbones, suggesting that the rigidpolyacetylene backbone of 5 plays a constructive role in inducing the novel molecular alignments.  相似文献   
959.
Calixarenesareregardedasthethirdgenerationofh0stmoleculesbecauseoftheirinclusionabilitytocati0ns,anionsandneutralmoleculesI'2.Duringthepastdecademosteff0rtshavebeentakenonthefunctionalizati0n0fcalixareness0thattheycanbeappliedn0tonlyastheionoph0resintheextractionprocess','andassensitivematerialsforionelectrodes"',butalsoastheenZymemimicscatalyzingthecleavageofphosphatediesters"'.Inordertoenablethemtoincludeandrecognizelargerchemicalspecies,manyappr0acheshavebeenusedtoc0nstructoIigo-calixarene…  相似文献   
960.
MoO3在Al2O3薄膜表面扩散的研究   总被引:3,自引:0,他引:3  
氧化物和盐类在高比表面载体上的单层分散现象已被大量实验所证实[1].MoO_3在γ-Al_2O_3等高比表面载体上的分散已经研究很多,近来的研究证实MoO3等在α-Al2O3等小比表面载体上也能自发单层分散[2],但是分散的过程仍然缺乏直接的观察研究.本工作通过多种表面分析方法首次研究了MoO3在平整无定形的Al2O3薄膜上的扩散过程以及影响因素.发现除温度升高外、水汽的存在对该扩散过程也有促进作用.1实验部分1.1样品的制备采用SS-3200真空磁控溅射镀膜机,通入Ar-O2作为反应气,直流磁控…  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