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   396篇
  免费   9篇
  国内免费   83篇
化学   396篇
晶体学   8篇
物理学   84篇
  2023年   2篇
  2022年   5篇
  2021年   2篇
  2020年   3篇
  2019年   8篇
  2018年   5篇
  2017年   5篇
  2016年   10篇
  2015年   6篇
  2014年   8篇
  2013年   12篇
  2012年   35篇
  2011年   26篇
  2010年   16篇
  2009年   16篇
  2008年   24篇
  2007年   24篇
  2006年   32篇
  2005年   25篇
  2004年   29篇
  2003年   18篇
  2002年   19篇
  2001年   6篇
  2000年   16篇
  1999年   22篇
  1998年   21篇
  1997年   15篇
  1996年   13篇
  1995年   7篇
  1994年   7篇
  1993年   17篇
  1992年   8篇
  1991年   10篇
  1990年   7篇
  1989年   7篇
  1987年   2篇
排序方式: 共有488条查询结果,搜索用时 187 毫秒
11.
《Analytical letters》2012,45(12):2237-2250
Abstract

An ultrasensitive electrochemical immunoassay based on biocatalytic deposition has been proposed for the detection of Schistosoma japonicum antibody (SjAb) in infected rabbit serum. Schistosoma japonicum antigen (SjAg) was immobilized on the gold electrode surface via glutaraldehyde crosslink and then incubated with infected rabbit serum containing SjAb; finally, the goat anti-rabbit IgG labeled with alkaline phosphatase was sandwiched to form the immunocomplex on the gold electrode surface. The alkaline phosphatase converted nonelectroactive substrate into the reducing agent and the latter, in turn, reduced metal ions to form electroactive metallic product on the electrode surface. Linear sweep voltammetry (LSV) was used to quantify the amount of the deposited silver and give the analytical signal for SjAb. Assay conditions such as the antigen concentration and enzymatic silver deposition time were optimized. The electrochemical immunosensor was able to realize a reliable determination of SjAb in the dilution range from 1:5000 to 1:100 with a detection limit of 1:6457 of dilution ratio. The feasibility of the proposed immunosensor for possible clinical applications was also investigated by analyzing real serum samples.  相似文献   
12.
The synthesis and crystal structure of γ‐aminobutyric acid naphthalene diimides derivative with the LaIII coordination complex, [La(L)(DMF)Cl]n, was reported, which is a twofold interpenetrating metal‐organic framework architecture. The coordination polymer was characterized by elemental analysis, infrared spectroscopy, thermal gravimetric analysis, and single‐crystal X‐ray diffraction. The optical properties of the crystallized complex were investigated both in solution and the solid state.  相似文献   
13.
A convenient one‐pot synthetic protocol towards THF and DME solvates of lanthanum and other early lanthanide tribromides was developed using the water‐catalyzed reaction of lanthanide(III) oxides with highly reactive Me3SiBr in situ formed from commercially available disilane Si2Me6 and Br2. This practical route allows to obtain the target lanthanum tribromide solvates [LaBr3(thf)4] ( 1a ) and [LaBr3(dme)2]2 ( 1b ) as well as analogous early lanthanide molecular tribromide solvates [NdBr3(thf)4] ( 2a ), [NdBr3(dme)2] ( 2b ), [SmBr3(thf)2] ( 3a ), and [SmBr3(dme)2] ( 3b ) difficult to prepare by other solution‐based procedures. The molecular structure of 1b· 2CH2Cl2 was determined by an XRD study.  相似文献   
14.
Despite the strong technological importance of lanthanide complexes, their formation processes are rarely investigated. This work is dedicated to determining the influence of synthesis parameters on the formation of [Ce(bipy)2(NO3)3] as well as Ce3+‐ and Tb3+‐substituted [La(bipy)2(NO3)3] (bipy = 2,2′‐bipyridine) complexes. To this end, we performed in situ luminescence measurements, synchrotron‐based X‐ray diffraction (XRD) analysis, infrared spectroscopy (IR), and measured pH value and/or ion conductivity during their synthesis process under real reaction conditions. For the [Ce(bipy)2(NO3)3] complex, the in situ luminescence measurements initially presented a broad emission band at 490 nm, assigned to the 5d→4f Ce3+ ions within the ethanolic solvation shell. Upon the addition of bipy, a red shift to 700 nm was observed. This shift was attributed to the changes in the environment of the Ce3+ ions, indicating their desolvation and incorporation into the [Ce(bipy)2(NO3)3] complex. The induction time was reduced from 8 to 3.5 min, by increasing the reactant concentration by threefold. In contrast, [La(bipy)2(NO3)3] crystallized within days instead of minutes, unless influenced by high Ce3+ and Tb3+ concentrations. Monitoring and controlling the influence of the reaction parameters on the structure of emissive complexes is important for the development of rational synthesis approaches and optimization of their structure‐related properties like luminescence.  相似文献   
15.
High pressure synthesis of solid material tends to increase the density,coordination number,symmetry of material and shorten bond length.The solid synthesized at a high pressure and decompressed to ambient pressure often exhibits a metastable "stretched" state,within the high pressure stability field.The crystal grown at a high pressure is of great importance with the development of high pressure technology.Crystal growth is an important factor in the material synthesis.And many methods including gas,solid and solution methods have been used to obtain various single crystals[1].Especially,flux method is an important method for crystal growth,where the components of the desired substance dissolved in a solvent(flux) grow in the process of deposit.Its advantage is that the crystal growth displays natural facets and the disadvantage is that the crystals are relatively small.Up to date,some solid materials have been successfully synthesized by high pressure flux method[2-7].  相似文献   
16.
Single-crystalline LaF3 flakes was synthesized through a facile solution-phase approach in aqueous ammonia and ethylenediamine. Applying the thermal treatment at 100 ℃ for 20 h, the LaF3 recrystallized, grew epitaxially and precipitated into flakes in aqueous ammonia or ethylenediamine. The formation of flakes could be attributed to the coordination effect of the solvent.  相似文献   
17.
氧化铝是高温催化反应中常用的载体材料. 高于1 000 ℃时, Al2O3通过表面活性原子的迁移和表面羟基脱水发生烧结, 并向α相转变[1,2], 同时随着比表面积剧烈下降, 导致催化剂活性组分聚集, 催化剂活性下降等. 大量研究表明, 稀土元素, 硅及碱土元素可明显改善氧化铝的热稳定性[3~8]. 本文以溶胶-凝胶法单独引入Ba元素, 考察了Ba添加量对Al2O3热稳定性的影响. 还采用溶胶-凝胶与表面浸渍相结合的方式共同引入La和Ba, 考察了两元素协同作用对Al2O3热稳定性的影响.  相似文献   
18.
19.
TiO2-coated sericite powders were prepared by the chemical deposition method starting from lamellar sericite and TiCl4 in the presence or absence of La3+ cations. After calcination at 900 °C for 1 h, the resultant TiO2 nanoparticles on the sericite surfaces existed in anatase phase. The light scattering indexes of the TiO2-coated lamellar sericite powders were dozens of times higher than that of the naked lamellar sericite powders. The presence of La3+ in the deposition solution was beneficial to the formation of the small-sized anatase TiO2 nanoparticles, resulting in the formation of the dense and uniform island-like TiO2 coating layers in a large range of the weight ratios of TiO2 to sericite from 5% to 20%. The TiO2-coated lamellar sericite powders prepared in the presence of La3+ had higher light scattering index than that prepared in the absence of La3+. XPS analysis shows that when La3+ cations were absent in the reaction solution, TiO2 coating layers anchored at the sericite surface via the Ti-O-Si and Ti-O-Al bonds. The presence of La3+ cations caused the formation of Si-O-La and Al-O-La bonds at the sericite surface and Ti-O-La bond at the surface of TiO2 coating layers. After coating TiO2 on the sericite surface, the yellowness of the TiO2-coated sericite powders obviously increased and the brightness slightly decreased.  相似文献   
20.
The yet unknown intermetallic phase La5Al3Ni2 was obtained by partially crystallizing amorphous La50Al25Ni25 at 550 K (further heating above 600 K leads to irreversible disappearance of this phase), and its crystal structure was determined from X‐ray powder diffraction data. The crystal structure of the La5Al3Ni2 phase constitutes a new structure type (Cmcm, a = 14.231Å, b = 6.914Å, c = 10.460Å, oC40) and is built from [Al3Ni2] chains surrounded by La atoms. In the ternary system La‐Al‐Ni La5Al3Ni2 is located on the section La50Al50−nNin (0 ≤ n ≤ 50) with the binary compounds LaAl and LaNi as end members. Strikingly, also the crystal structures of the end members can be conceived as chain structures with Al and Ni chains surrounded by La, respectively.  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