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   14186篇
  免费   2235篇
  国内免费   1317篇
化学   10269篇
晶体学   175篇
力学   813篇
综合类   70篇
数学   1762篇
物理学   4649篇
  2024年   14篇
  2023年   308篇
  2022年   321篇
  2021年   470篇
  2020年   667篇
  2019年   570篇
  2018年   505篇
  2017年   426篇
  2016年   692篇
  2015年   715篇
  2014年   748篇
  2013年   1094篇
  2012年   1250篇
  2011年   1260篇
  2010年   828篇
  2009年   831篇
  2008年   974篇
  2007年   830篇
  2006年   743篇
  2005年   704篇
  2004年   518篇
  2003年   415篇
  2002年   359篇
  2001年   310篇
  2000年   260篇
  1999年   271篇
  1998年   184篇
  1997年   140篇
  1996年   188篇
  1995年   165篇
  1994年   137篇
  1993年   123篇
  1992年   104篇
  1991年   89篇
  1990年   90篇
  1989年   67篇
  1988年   63篇
  1987年   48篇
  1986年   40篇
  1985年   42篇
  1984年   37篇
  1983年   17篇
  1982年   16篇
  1981年   19篇
  1980年   11篇
  1979年   8篇
  1976年   10篇
  1975年   11篇
  1971年   7篇
  1969年   5篇
排序方式: 共有10000条查询结果,搜索用时 22 毫秒
21.

This paper presents the stabilization effects of inorganic filler, cerium-doped lead zirconate titanate on high-density polyethylene. The filler was loaded in two concentrations (1 and 3 wt%). The dopant contents in PbZrO3 were 0, 0.05, 0.075, 0.1 and 0.125 mol%. The degradation of hybrid samples was accomplished by γ-irradiation at various doses up to 200 kGy. The isothermal and nonisothermal chemiluminescence (CL) and thermal analysis (TG-DSC) were applied for the thermal stability characterization of modified HDPE samples. The mechanistic considerations and radiochemical consequences caused by the variation of filler concentration and doping level are discussed. The results demonstrate that the filler acts efficiently as stabilizer at low concentration of additive when the lower filler amount is present. The start of degradation precedes melting by four processes through which the chain scission and radical oxidation represent the essential degradation stage. The filler concentration influences the degradation due to the intimate interaction between solid-state defects and free radicals. The polymer protection against oxidation is based on the scavenging of radicals by the doping elements, that is, they trap and block radicals delaying material aging. The present results open a new perspective in the quality amelioration of organic products toward high durability.

  相似文献   
22.
Tetrathiatriarylmethyl (TAM, trityl) radicals have found wide applications as spin probes/labels for EPR spectroscopy and imaging, and as polarizing agents for dynamic nuclear polarization. The high hydrophilicity of TAM radicals is essential for their biomedical applications. However, the synthesis of hydrophilic TAM radicals (e.g., OX063) is extremely challenging and has only been reported in the patent literature, to date. Herein, an efficient synthesis of a highly water-soluble TAM radical bis(8-carboxyl-2,2,6,6-tetramethylbenzo[1,2-d:4,5-d′]bis([1,3]dithiol-4-yl)-mono-(8-carboxyl-2,2,6,6-tetrakis(2-hydroxyethyl)benzo[1,2-d:4,5-d′]bis([1,3]dithiol-4-yl)methyl (TFO), which contains four additional hydroxylethyl groups, relative to the Finland trityl radical CT-03, is reported. Similar to OX063, TFO exhibits excellent properties, including high water solubility in phosphate buffer, low log P, low pKa, long relaxation times, and negligible binding with bovine serum albumin. On the other hand, TFO has a sharper EPR line and higher O2 sensitivity than those of OX063. Therefore, in combination with its facile synthesis, TFO should find wide applications in magnetic resonance related fields and this synthetic approach would shed new light on the synthesis of other hydrophilic TAM radicals.  相似文献   
23.
Han  Peigeng  Zhang  Xue  Mao  Xin  Yang  Bin  Yang  Songqiu  Feng  Zhaochi  Wei  Donghui  Deng  Weiqiao  Pullerits  Tõnu  Han  Keli 《中国科学:化学(英文版)》2019,62(10):1405-1413
Lead-free halide double perovskites have gathered wide scientific interest since they are environmentally friendly and stable.However,compared to the lead perovskites,their optoelectronic properties are compromised.Herein we report a series of bulk lead-free mixed Bi-In halide double perovskites:Cs_2AgBi_(1-x)In_xCl_6(0x1).The Cs_2AgBi_(0.125)In_(0.875)Cl_6breaks the parity-forbidden transition and retains direct band gap structure,having warm-white light emission,with photoluminescence quantum efficiency(PLQE)of 70.3%,much higher than the PLQE of reported lead perovskite materials.Its exciton self-trapping dynamics is investigated.Meanwhile,the Cs_2AgBi_(0.125)In_(0.875)Cl_6nanocrystals and Cs_2AgBi_(0.125)In_(0.875)Cl_6microcrystals can be synthesized by modified hot injection and rapid cooling crystallization,respectively.The size effect of Cs_2AgBi_(0.125)In_(0.875)Cl_6is studied on the photoluminescence(PL)property.Additionally,the bulk material exhibits excellent stability on exposure to light,humidity and air for more than 3 months.It is a promising candidate as highly efficient warm white-light emitting material for road lighting.  相似文献   
24.
A challenging deoxygenation of alkoxyl radicals from readily accessible alcohol derivatives was developed, affording facile synthesis of functionalized alkenes with good functional group tolerance under mild reaction conditions. Because alkoxyl radicals can easily undergo β-fragmentations or hydrogen abstractions, this new strategy for deoxygenation of alkoxyl radicals is highly valuable. Moreover, mechanistic studies revealed that the electron-neutral phosphine acts as the deoxygenation reagent.  相似文献   
25.
Tricaine methanesulfonate is one of most commonly used anesthetics in fish during blood sampling, artificial propagation and long‐distance transportation. In this study, an accurate method for the quantitative determination of tricaine in fish samples by a stable isotope dilution assay coupled with high‐performance liquid chromatography–triple quadrupole mass spectrometry was developed. Tricaine‐D5 was synthesized and used as an isotopically labeled internal standard for the determination of tricaine. The analytical performance of the method was validated for tricaine determination in marine fish and freshwater fish. The determination of tricaine was linear in the range of 2.0–200.0 μg L?1. The limit of detection and limit of quantitation for fish muscle tissues were 1.0 and 4.0 μg kg?1, respectively. Good recoveries were obtained in the range of 92.08–97.50%. The inter‐ and intra‐assay relative standard deviations (RSD values) were investigated, and the values were 0.39–3.01 and 0.85–2.77%, respectively. The values of CCα and CCβ were 10.21–10.43 and 10.42–10.87 μg kg?1, respectively. The clearance of MS‐222 from grass carp was further studied using our method. The results demonstrate that MS‐222 could be well absorbed and rapidly eliminated after bath administration.  相似文献   
26.
Investigating the dilatancy, acoustic emission and failure characteristics of fissured rock are significant to ensure their geotechnical stability. In this paper, the uniaxial and triaxial compression experiments with AE monitoring under different loading rates were carried out on fissured rock specimens with the same geometrical distribution of two pre-existing flaws. The dilatancy and AE activity of these specimens were discussed, and the effects of the confining pressure and loading rate on the mechanical parameters and failure characteristics were analyzed. The results show that the exponential strength criterion is more suitable than the Mohr–Coulomb strength criterion to characterize the strength characteristics of fissured rock. The crack evolution and failure characteristics of fissured rock specimens are more complicated than those of intact rock specimens. The failure characteristics of the fissured rock follow the tensile shear coalescence model, crack branching occurs with increasing the loading rate, and the multi-section coalescence model is verified with increasing the confining pressure. The phenomena of stress drop and yield platform usually occur after the dilatancy onset, the specimen does not fail instantaneously, and the propagation and coalescence of cracks cause a sharp increase in the AE signals, circumferential strain, and volumetric strain.  相似文献   
27.
为了提高难溶性药物的溶出速率,采用水热合成法制备了MCM-41和SBA-15两种介孔二氧化硅载体材料,利用浸渍法将模型药茴拉西坦负载于两种载体上.利用扫描电子显微镜(SEM)、高分辨透射电子显微镜(HRTEM)、小角X射线衍射(XRD)、N2吸附-脱附、红外光谱(IR)、差热-热重(DTA-TG)对载药前后载体材料的表面形貌、粒径、孔径、孔容、比表面积、晶胞参数、骨架结构等进行测试,结果表明MCM-41和SBA-15具有相同的二维六方孔道结构,孔径及孔容分别为3.49 nm和6.67 nm,载药后的载药量分别为17;和22;,药物以非晶态装载于介孔孔道中没有影响介孔二氧化硅的骨架结构,但使介孔孔容及比表面积都有所降低.通过在不同pH溶出介质中负载于载体上的茴拉西坦与原料药晶体的溶出比较发现,两种载体均能够显著提高茴拉西坦的溶出速率.结合材料表征、载药量及溶出度综合比较,SBA-15载体的载药及释药性能均优于MCM-41载体.  相似文献   
28.
29.
Chen  Wei  Han  Qi  Liu  Jingbo 《Aequationes Mathematicae》2019,93(2):425-432
Aequationes mathematicae - We discuss equivalence conditions for the non-existence of non-trivial meromorphic solutions to the Fermat Diophantine equation $$f^m(z)+g^n(z)=1$$ with integers $$m,n\ge...  相似文献   
30.
Accurate diagnosis of tumor characteristics, including its location and boundary, is of immense value to subsequent therapy. Activatable magnetic resonance imaging (MRI) contrast agents that respond to tumor-specific microenvironments, such as the redox state, pH, and enzyme activity, enable better mapping of tumor tissue. However, the practical application of most reported activatable agents is hampered by problems including potential toxicity, inefficient elimination, and slow activation. In this study, we developed a zwitterionic iron complex (Fe-ZDS) as a positive MRI contrast agent for tumor-specific imaging. Fe-ZDS could dissociate in weakly acidic solution rapidly, accompanied by clear longitudinal relaxivity (r1) enhancement, which enabled the complex to act as a pH-sensitive contrast agent for tumor-specific MR imaging. In vivo experiments showed that Fe-ZDS rapidly enhanced the tumor-to-normal contrast ratio by >40 %, which assisted in distinguishing the tumor boundary. Furthermore, Fe-ZDS circulated freely in the bloodstream and was excreted relatively safely via kidneys owing to its zwitterionic nature. Therefore, Fe-ZDS is an ideal candidate for a tumor-specific MRI contrast agent and holds considerable potential for clinical translation.  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