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   1087篇
  免费   146篇
  国内免费   165篇
化学   956篇
晶体学   21篇
力学   26篇
综合类   38篇
数学   24篇
物理学   333篇
  2024年   3篇
  2023年   18篇
  2022年   60篇
  2021年   51篇
  2020年   51篇
  2019年   30篇
  2018年   39篇
  2017年   45篇
  2016年   52篇
  2015年   43篇
  2014年   63篇
  2013年   67篇
  2012年   81篇
  2011年   59篇
  2010年   58篇
  2009年   59篇
  2008年   62篇
  2007年   77篇
  2006年   63篇
  2005年   67篇
  2004年   49篇
  2003年   51篇
  2002年   38篇
  2001年   41篇
  2000年   33篇
  1999年   20篇
  1998年   17篇
  1997年   10篇
  1996年   12篇
  1995年   11篇
  1994年   7篇
  1993年   14篇
  1992年   7篇
  1991年   8篇
  1990年   8篇
  1989年   10篇
  1988年   5篇
  1987年   1篇
  1985年   1篇
  1984年   2篇
  1983年   1篇
  1982年   1篇
  1981年   2篇
  1959年   1篇
排序方式: 共有1398条查询结果,搜索用时 15 毫秒
71.
Sol–gel glasses with Fe3O4 nanoparticles having particle sizes laying in the range 10–20 nm were encapsulated in the porous network of silica resulting in nanocomposites having both optical and magnetic properties. Spectroscopic and photoluminescence studies indicated that Fe3O4 nanocrystals are embedded in the silica matrix with no strong Si–O–Fe bonding. The composites exhibited a blue luminescence. The optical absorption edge of the composites red shifted with increasing concentration of Fe3O4 in the silica matrix. There is no obvious shift in the position of the luminescence peak with the concentration of Fe3O4 except that the intensity of the peak is decreased. The unique combinations of magnetic and optical properties are appealing for magneto–optical applications.  相似文献   
72.
The detection of Allura red (AR) by electrochemical reduction using a different electrode from the conventional mercury electrode is presented. A carbon paste with cobalt (II, III) oxide composite electrode (CoOx/CPE) is reported for the first time for the detection of AR. Moreover, others dyes such as tartrazine (TZ), sunset yellow (SY), amaranth (AM), Ponceaut 4‐R (P‐4R), and Sudan (SD) as well as pharmaceutical agents such as paracetamol (PMC) that are present in samples that contained AR did not show a reduced signal between 0.0 and ?0.3 V, which is the potential range where AR reduction was observed. The surface electroactivity was studied using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM). The presence of CoOX increased the cathodic peak current for AR by more than 50 % and 65 % via CV and square wave voltammetry (SWV), respectively, compared with an unmodified carbon paste electrode. Under the optimal parameters, (pH=3.0, accumulation time (tACC)=60 s and accumulation potential (EACC)=0.50 V), the detection limit for AR was 0.05 μmol L?1. The new sensor was sensitive and stable for the detection of AR. Moreover, it was easily manufactured and very convenient for food samples such as soft and isotonic drinks as well as chili sauce.  相似文献   
73.
Endophytic fungi were isolated from red alga Asparagopsis taxiformis - Falkenbergia stage, collected from the Brazilian coast, and were identified as Annulohypoxylon stygium (AT-03) and A. yungensis (AT-06) based on their macro/micromorphological and molecular features. Bioassay-guided fractionation of the EtOAc extract from laboratory cultures of both strains yielded known compounds pyrogallol from A. stygium, (3R)-scytalone and (3R,4R)-4-hydroxy-scytalone from A. yungensis. Pyrogallol was active against methicillin-resistant Staphylococcus aureus (MRSA) and Escherichia coli strains. An inactive fraction from A. stygium afforded two additional compounds, (3R,4R)-3,4,5-trihydroxy-1-tetralone and tyrosol. Optically active compounds had their stereochemistry determined by circular dichroism (CD) spectroscopy.  相似文献   
74.
In this study, the electronic structures and optical properties of a cyclometalated Pt(II) complex (M1) and a series of derivatives (M1–F, M1–CF3, and M1–CN) with electron-withdrawing substituents (–F, –CF3, and –CN) at the carbazole moiety were theoretically investigated by density functional theory and time-dependent density functional theory. The calculation results reveal that these Pt complexes display deep red phosphorescence emission above Λ = 640 nm. When the 3MLCT/π → π* to triplet metal-centered 3MC/d–d state decay mechanism is taken into consideration, the nonradiative decay rate constant (knr) decreased in the order M1 > M1–CF3 > M1–F > M1–CN. The <T1|HSOC|Sm> and kr values of M1-F are similar with those of M1, however the Knr rate ofM1-F is larger than that of M1. M1–F is expected to have improved quantum yields. Moreover, through the analyses of the HOMO/LUMO level and triplet energy, it is found that the introduction of –F and –CN substituents in M1 results in efficient energy transfer from the host material 4,4′-N,N′-dicarbazole-biphenyl to these complexes. In view of the electroluminescent applications in organic light-emitting diodes, M1–F can serve as efficient deep-red guest materials with improved electron injection and transport ability.  相似文献   
75.
ABO hemolytic disease of the newborn (ABO-HDN), which may cause neonatal jaundice and polycythemia, or even stillbirth or neonatal death, is widespread in China. Prenatal testing for the fetal ABO blood group can reduce unnecessary concerns or ensure prompt treatment. Herein, we presented a method to employ high-density silica microbeads (SiO2 MBs) for capturing fetal nucleated red blood cells (fnRBCs) in maternal peripheral blood, and we detected the ABO genotype of the fetus using these captured cells. We evaluated 52 patients using the SiO2 MBs. Among 26 pregnant women with type O blood, 8 (30.8%) of the fetuses had type A blood, 5 (19.2%) had type B blood, and 13 (50%) had type O blood. SRY genes were detected in all 27 male fetuses. This study represents a simple and effective method for noninvasive prenatal detection of the fetal ABO genotype. We believe that this method has great potential for noninvasive prenatal testing of the fetal Rh blood group and other fetal diseases as well.  相似文献   
76.
77.
茜素红S荧光猝灭法测定壳聚糖含量   总被引:8,自引:0,他引:8  
在pH 5.0的NaAc-HAc缓冲液中壳聚糖对茜素红S的荧光强度具有明显的猝灭作用,且猝灭程度F0/F与加入的壳聚糖浓度成线性关系,据此建立一种测定壳聚糖含量的荧光猝灭法。确定了最佳测定条件,线性回归方程为F0/F=-0.438 37 0.436 27c(mg·L-1),线性范围为0-16.667 mg·L-1,r=0.996,检测限为0.473 mg·L-1;平均回收率为100.60%,测定了样品中壳聚糖的含量,并考察了干扰因素对测定的影响。采用该方法可测定复杂样品中微量壳聚糖含量。  相似文献   
78.
本文测量了全反式β胡萝卜素在二甲基亚砜中81–25 ℃ 范围的紫外–可见吸收和拉曼光谱. 结果表明, 随温度降低, 紫外–可见吸收光谱、拉曼光谱都发生红移, 拉曼光谱线型变窄, 散射截面增加这些现象的发生是由于随温度降低, β胡萝卜素分子的热无序降低、分子结构有序性增加、π电子离域扩展, 有效共轭长度增加, 分子的电子能隙变窄. 另外, 随着温度的降低, 溶剂密度增加, 由Lorentz-Lorenz 关系得知相伴的折射率增加, 从而引起吸收光谱的红移. CC键键长增加, 使CC 键拉曼光谱红移; 振动弛豫时间变长, 各CC 键之间的键长差减小, 线宽变窄; 但由于声子, π电子耦合加强使CC键拉曼线型不对称程度增加, 低频端"肩"扩展, CC键的弱阻尼相干振动增加, 使拉曼散射截面增加. 关键词: β胡萝卜素 分子结构有序 红移 拉曼散射截面  相似文献   
79.
有机染料掺杂玻璃的制备及荧光性能   总被引:3,自引:0,他引:3       下载免费PDF全文
雷宁  叶辉 《发光学报》1996,17(2):156-163
铅-锡-氟磷酸盐玻璃是各种激光染料及非线性染料的理想基质,本文报道了荧光素及吖啶红掺杂铅-锡-氟磷酸盐玻璃的荧光性能,并且将吖啶红掺入有机改性的钛凝胶(TiO2-Ormosil),对两者的荧光性能进行了比较。  相似文献   
80.
Nile red bound to human serum albumin (HSA) shows an order of magnitude increase in the probe's fluorescence intensity. Here, we report on the fluorescence characteristics of the probe-protein complex in Trizma buffer (pH 7.1), urea, guanidine hydrochloride, and AOT/isooctane/buffer reverse micelles using both steady—state and time-resolved fluorescence techniques. With a view to illustrating the use of extrinsic probe fluorescence spectroscopy in protein research, we demonstrate that protein unfolding can be observed through measurements of the probe's time-resolved anisotropy and steady-state fluorescence spectrum. Moreover, this shows that thermal unfolding is fundamentally different from using denaturant, with respect to changes in both the nanosecond diffusional rotation of the probe at intermediate stages and in the denatured protein's structure. Also, the large Stokes shift of Nile red allows the changes in the environment of the probe-protein complex in reverse micelles of varying waterpool size to be easily identified in the steady-state fluorescence. This was not seen in earlier work exploiting the intrinsic tryptophan fluorescence of HSA and further demonstrates the complementary information that extrinsic fluorescence probe studies can offer protein science. We discuss the complex acrylamide quenching characteristics of Nile red bound to HSA in terms of the possibility of at least two binding sites for the probe and the effect of acrylamide on the probe-protein structure at very high quencher concentrations.  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