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   35429篇
  免费   4173篇
  国内免费   2890篇
化学   17974篇
晶体学   311篇
力学   1542篇
综合类   111篇
数学   2919篇
物理学   9347篇
综合类   10288篇
  2024年   153篇
  2023年   643篇
  2022年   1126篇
  2021年   1190篇
  2020年   1097篇
  2019年   1029篇
  2018年   903篇
  2017年   824篇
  2016年   1302篇
  2015年   1339篇
  2014年   1683篇
  2013年   2068篇
  2012年   2681篇
  2011年   2738篇
  2010年   1870篇
  2009年   1810篇
  2008年   2019篇
  2007年   1871篇
  2006年   1691篇
  2005年   1492篇
  2004年   1135篇
  2003年   857篇
  2002年   854篇
  2001年   708篇
  2000年   716篇
  1999年   1051篇
  1998年   974篇
  1997年   970篇
  1996年   948篇
  1995年   791篇
  1994年   686篇
  1993年   531篇
  1992年   531篇
  1991年   481篇
  1990年   376篇
  1989年   372篇
  1988年   277篇
  1987年   231篇
  1986年   152篇
  1985年   99篇
  1984年   53篇
  1983年   43篇
  1982年   35篇
  1981年   18篇
  1980年   11篇
  1979年   10篇
  1978年   6篇
  1976年   9篇
  1975年   11篇
  1957年   6篇
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
951.
952.
A novel hybrid PKS–NRPS alkaloid, xylarialoid A (1), containing a 13-membered macrocyclic moiety and [5,5,6] fused tricarbocyclic rings, together with ten known cytochalasins (2–11), was isolated from a plant-derived endophytic fungus, Xylaria arbuscula. The chemical structures of all compounds were elucidated using 1D and 2D NMR, HR ESIMS spectroscopic analyses, and electronic circular dichroism (ECD) calculation. Compounds 1–3 and 10 exhibited significant antitumor activities against A549 and Hep G2 cell lines, with IC50 values of 3.6–19.6 μM. In addition, compound 1 showed potent anti-inflammatory activity against LPS-induced nitric oxide (NO) production in macrophage RAW 264.7 cells (IC50, 6.6 μM).  相似文献   
953.
Summary Two high-performance liquid chromatography (HPLC) techniques were developed for the determination of binding constants in the interaction of serum albumin with L-tryptophan: internal calibration and external calibration. The results obtained were compared with those obtained by the classical method of equilibrium dialysis and by gel filtration. While all the methods are equally reliable, the internal and external calibration techniques seem to be superior in their simplicity, speed and convenience.  相似文献   
954.
用粉状白钨酸作原针,在一般条件下制备K3W2Cl9,产率达53%,证明白钨酸是比黄钨酸优越的钨化学试剂。研究了K3W2Cl9经离子又换转化为酸的形态后与Ndz2(C03)3的反应。得到了新的化合物NdW2Cl9,提出了一条新的制备溶解度大的各种金属离子与W2Cl93-的化合物的途径。 对K3W2Cl9和NdW2Cl9进行了紫外可见尤谱和X针线粉末衍射的测定。  相似文献   
955.
A gold film electrode formed in situ on glassy carbon is used as the working electrode for the determination of tin over the range 0.1–10 μg ml?1. Gold(III) added to the solution provides the film and serves as the oxidant for stripping. Two stripping curves corresponding to Sn(Au) → Sn(II) and Sn(II) → Sn(IV) were observed; either can be used for determinations of tin. The equations for the transition time (i.e., stripping signal) and stripping curve derived were verified experimentally.  相似文献   
956.
Fossil fuels are expected to be the major source of energy for the next few decades. However, combustion of nonrenewable resources leads to the release of large quantities of CO2, the primary greenhouse gas. Notably, the concentration of CO2 in the atmosphere is increasing annually at an astounding rate. Electrochemical CO2 reduction (ECR) to value-added fuels and chemicals using electricity from intermittent renewable energy sources is a carbon-neutral method to alleviate anthropogenic CO2 emissions. Despite the steady progress in the selective generation of C1 products (CO and formic acid), the production of multi-carbon species still suffers from low selectivity and efficiency. As an ECR product, ethylene (C2H4) has a higher energy density than do C1 species and is an important industrial feedstock in high demand. However, the conversion of CO2 to C2H4 is plagued by low productivity and large overpotential, in addition to the severe competing hydrogen evolution reaction (HER) during the ECR. To address these issues, the design and development of advanced electrocatalysts are critical. Here, we demonstrate fine-tuning of ECR to C2H4 by taking advantage of the prominent interaction of Cu with shape-controlled CeO2 nanocrystals, that is, cubes, rods, and octahedra predominantly covered with (100), (110), and (111) surfaces, respectively. We found that the selectivity and activity of the ECR depended strongly on the exposed crystal facets of CeO2. The overall ECR Faradaic efficiency (FE) over Cu/CeO2(110) (FE ≈ 56.7%) surpassed that of both Cu/CeO2(100) (FE ≈ 51.5%) and Cu/CeO2(111) (FE ≈ 48.4%) in 0.1 mol·L-1 KHCO3 solutions with an H-type cell. This was in stark contrast to the exclusive occurrence of the HER over pure carbon paper, CeO2(100), CeO2(110), and CeO2(111). In particular, the FE toward C2H4 formation and the partial current density increased in the sequence Cu/CeO2(111) < Cu/CeO2(100) < Cu/CeO2(110) within applied bias potentials from -1.00 to -1.15 V (vs. the reversible hydrogen electrode), reaching 39.1% over Cu/CeO2(110) at a mild overpotential (1.13 V). The corresponding values for Cu/CeO2(100) and Cu/CeO2(111) were FEC2H4 ≈ 31.8% and FEC2H4 ≈ 29.6%, respectively. The C2H4 selectivity was comparable to that of many reported Cu-based electrocatalysts at similar overpotentials. Furthermore, the FE for C2H4 remained stable even after 6 h of continuous electrolysis. The superior ECR activity of Cu/CeO2(110) to yield C2H4 was attributed to the metastable (110) surface, which not only promoted the effective adsorption of CO2 but also remarkably stabilized Cu+, thereby boosting the ECR to produce C2H4. This work offers an alternative strategy to enhance the ECR efficiency by crystal facet engineering.  相似文献   
957.
In the present work, radiation crosslinking of different branched poly (vinyl acetate) have beemstudied and the validity of the relationship between sol fraction and radiation dose: R(S+S~(1/2)=1/U_(1qo)+p′_o/q_oR~βto branched poly(vinyl acetate) have been assured.  相似文献   
958.
孙放  于德泉 《有机化学》1985,5(5):395-398
C_(20)-二萜生物碱结构复杂,环上大多有含氧的基团。利用NMR、MS等确定羟基、羰基在分子中的位置往往不够有力。特別是对于C_1~3或C_(11)位上羰基,没有可靠而简便的光谱鉴別方法。我们通过对几个Atisine型含羰基化合物的圆二色谱研究发现,由CD谱确定羰基在C_6位、C_(11)位及C_(13)位是一种简便有效的方法。  相似文献   
959.
Developing non-noble-metal oxygen evolution reaction(OER) electrocatalysts with high performance is critical to electrocatalytic water splitting. In this work, we fabricated Co Fe-layered double hydroxide(LDH) nanowire arrays on graphite felt(Co Fe-LDH/GF) via a hydrothermal method. The Co Fe-LDH/GF, as a robust integrated 3 D OER anode, exhibits excellent catalytic activity with the need of low overpotential of 252 and 285 m V to drive current densities of 10 and 100 m A/cm2 in 1.0 mol/L KOH, r...  相似文献   
960.
燃料电池是一种将化学能直接转化为电能的能量转换装置,具有能量密度高、利用率高、清洁安静等优点。在不同类型的燃料电池中,质子交换膜燃料电池(PEMFC)不仅能量密度高,而且具有在近常温条件下工作的特点,因此受到广泛关注。目前,商业化PEMFC仍采用铂基纳米材料作为催化剂,其中缺乏低成本、高效的阴极催化剂是限制PEMFC性能提升和成本降低的关键因素之一。本文综述PEMFC催化剂的结构可控制备及其对阴极氧还原反应和膜电极性能的影响,阐述调控催化剂结构提高PEMFC性能的方法,特别是提高贵金属催化剂的利用率,降低膜电极中贵金属用量的研究进展。  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