全文获取类型
收费全文 | 18009篇 |
免费 | 2417篇 |
国内免费 | 2874篇 |
专业分类
化学 | 14214篇 |
晶体学 | 282篇 |
力学 | 755篇 |
综合类 | 264篇 |
数学 | 1968篇 |
物理学 | 5817篇 |
出版年
2024年 | 32篇 |
2023年 | 171篇 |
2022年 | 414篇 |
2021年 | 454篇 |
2020年 | 483篇 |
2019年 | 543篇 |
2018年 | 454篇 |
2017年 | 416篇 |
2016年 | 708篇 |
2015年 | 773篇 |
2014年 | 928篇 |
2013年 | 1311篇 |
2012年 | 1468篇 |
2011年 | 1512篇 |
2010年 | 1163篇 |
2009年 | 1125篇 |
2008年 | 1384篇 |
2007年 | 1273篇 |
2006年 | 1160篇 |
2005年 | 971篇 |
2004年 | 914篇 |
2003年 | 826篇 |
2002年 | 925篇 |
2001年 | 740篇 |
2000年 | 570篇 |
1999年 | 441篇 |
1998年 | 277篇 |
1997年 | 284篇 |
1996年 | 235篇 |
1995年 | 209篇 |
1994年 | 185篇 |
1993年 | 174篇 |
1992年 | 158篇 |
1991年 | 113篇 |
1990年 | 104篇 |
1989年 | 87篇 |
1988年 | 50篇 |
1987年 | 52篇 |
1986年 | 41篇 |
1985年 | 36篇 |
1984年 | 26篇 |
1983年 | 18篇 |
1982年 | 12篇 |
1981年 | 14篇 |
1980年 | 10篇 |
1978年 | 11篇 |
1977年 | 7篇 |
1976年 | 8篇 |
1974年 | 5篇 |
1973年 | 7篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
991.
Uniform-sized fluorescent molecularly imprinted polymers were prepared by one-step swelling and suspension polymerization, while chlorpyrifos, methacrylic acid, ethylene glycol dimethacrylate, and oil-soluble CdSe/ZnS quantum dots were used as the carrier, template molecule, functional monomer, cross-linker, and fluorophor, respectively. The morphology, adsorption dynamics, binding ability, and selectivity of quantum dot-labeled molecularly imprinted polymers were evaluated. The dosage of quantum dots for labeling the molecularly imprinted polymers was optimized. The results showed that the optimized dose of quantum dots was 200?µL using a concentration of 8.0?µM. The microsphere size was approximately 10?µm with a honeycombed surface. The quantum dot-labeled molecularly imprinted polymers had an even brightness and a high selectivity. In the presence of different concentrations of chlorpyrifos, a decrease in the fluorescence intensity of the quantum dot-labeled molecularly imprinted polymer was clearly identified by flow cytometry. The whole detection process was accomplished within 2?h including pretreatment. This method was used for the determination of chlorpyrifos in tap water samples. 相似文献
992.
超高效液相色谱-四极杆-飞行时间质谱法定性筛查保健食品中西地那非及其相关功效类非法添加化合物 总被引:1,自引:0,他引:1
建立了超高效液相色谱-四极杆-飞行时间质谱(UPLC-Q-TOF-MS)定性筛查102种西地那非及其相关功效化合物的方法。甲醇超声提取样品;采用Agilent Poroshell 120 SB-C18色谱柱(75 mm×3.0 mm,2.7 μm),以0.1%(v/v)甲酸水溶液-乙腈为流动相梯度洗脱,流速0.4 mL/min;采用电喷雾离子(ESI)源,Q-TOF-MS作检测器,正离子模式检测;与对照品保留时间、母离子及碎片离子精确相对分子质量、元素组成比对,准确定性。西地那非等100种化合物在10种基质中的检出限为0.1~50 mg/kg或0.1~50 mg/L。并分类归纳了文中涉及的98种磷酸二酯酶5抑制剂质谱碎片裂解规律,为可疑物的识别和鉴定提供参考。该方法已应用于实际样品的测定,检出19种化合物,有效打击了非法添加行为。 相似文献
993.
酶对天然底物的高度专一性是酶的特点之一. 然而关于酶是如何对底物具有高度专一性以及识别能力, 我们的理解仍然缺乏. 本文以植物体系中发现的一组甲酯酶(MESs)对一些底物[包括水杨酸甲酯(MeSA), 茉莉酮酸甲酯(MeJA)和吲哚-3-乙酸甲酯(MeIAA)]的催化反应为例, 报道了同源建模和理论计算对茉莉酮酸甲酯酶(AtMES10)和水杨酸结合蛋白2(SABP2)的研究结果. 基于简单的锁-钥匙理论(底物与酶结合时不发生基团的碰撞或严重排斥), 以底物对接到酶的活性部位(即底物中—COO的一部分占据可被催化丝氨酸亲核进攻的位置) 为原则, 可以在空间上为酶对底物的专一性提供解释. 模拟结果表明, SABP2可对MeSA有高活性, 对MeJA和MeIAA有低或无活性; AtMES10可对MeJA有高活性, 而对MeSA和MeIAA有低或无活性, 这与实验结果相一致. 因此, 相关酶的结构预测与计算机模拟对了解酶的底物专一性具有重要的意义. 相似文献
994.
Chloroacetate‐Promoted Selective Oxidation of Heterobenzylic Methylenes under Copper Catalysis 下载免费PDF全文
Dr. Jianming Liu Xin Zhang Hong Yi Dr. Chao Liu Ren Liu Dr. Heng Zhang Prof. Dr. Kelei Zhuo Prof. Dr. Aiwen Lei 《Angewandte Chemie (International ed. in English)》2015,54(4):1261-1265
The efficient selective oxidation and functionalization of C? H bonds with molecular oxygen and a copper catalyst to prepare the corresponding ketones was achieved with ethyl chloroacetate as a promoter. In this transformation, various substituted N‐heterocyclic compounds were well tolerated. Preliminary mechanistic investigations indicated that organic radical species were involved in the overall process. The N‐heterocyclic compounds and ethyl chloroacetate work synergistically to activate C? H bonds in the methylene group, which results in the easy generation of free radical intermediates, thus leading to the corresponding ketones in good yields. 相似文献
995.
One‐pot Synthesis of CdS Nanocrystals Hybridized with Single‐Layer Transition‐Metal Dichalcogenide Nanosheets for Efficient Photocatalytic Hydrogen Evolution 下载免费PDF全文
Junze Chen Dr. Xue‐Jun Wu Lisha Yin Dr. Bing Li Dr. Xun Hong Zhanxi Fan Bo Chen Prof. Can Xue Prof. Hua Zhang 《Angewandte Chemie (International ed. in English)》2015,54(4):1210-1214
Exploration of low‐cost and earth‐abundant photocatalysts for highly efficient solar photocatalytic water splitting is of great importance. Although transition‐metal dichalcogenides (TMDs) showed outstanding performance as co‐catalysts for the hydrogen evolution reaction (HER), designing TMD‐hybridized photocatalysts with abundant active sites for the HER still remains challenge. Here, a facile one‐pot wet‐chemical method is developed to prepare MS2–CdS (M=W or Mo) nanohybrids. Surprisedly, in the obtained nanohybrids, single‐layer MS2 nanosheets with lateral size of 4–10 nm selectively grow on the Cd‐rich (0001) surface of wurtzite CdS nanocrystals. These MS2–CdS nanohybrids possess a large number of edge sites in the MS2 layers, which are active sites for the HER. The photocatalytic performances of WS2–CdS and MoS2–CdS nanohybrids towards the HER under visible light irradiation (>420 nm) are about 16 and 12 times that of pure CdS, respectively. Importantly, the MS2–CdS nanohybrids showed enhanced stability after a long‐time test (16 h), and 70 % of catalytic activity still remained. 相似文献
996.
Sainan Ma Huiyu Yuan Lejuan Cai Xinyu Wang Hui Long Yang Chai Yuen Hong Tsang 《Materials Today Chemistry》2018
The development of cost-effective, durable and high-efficient oxygen evolution reaction (OER) electrocatalysts is an extremely critical technology for the large-scale industrial water electrolysis. Here, a new strategy is proposed to significantly enhance the electrocatalytic activity by forming a hybrid electrode of NiSe and Fe4.4Ni17.6Se16 through direct selenization of porous iron-nickel (FeNi) alloy foam via thermal selenization process. The obtained self-supported Fe4.4Ni17.6Se16/NiSe hybrid (FNS/NiSe) foam displays outstanding durability and remarkable catalytic activity in 1.0 M KOH with low overpotentials of 242 and 282 mV to achieve the current densities of 100 and 500 mA cm?2, respectively. To the best of our knowledge, it exceeds most of the reported OER electrocatalysts in alkaline electrolytes. 相似文献
997.
998.
气相色谱-负化学源质谱法测定禽蛋及蛋制品中氟虫腈及其代谢物 总被引:2,自引:0,他引:2
建立了气相色谱-负化学源质谱联用技术(GC-NCI-MS)测定禽蛋及蛋制品中氟虫腈及其3种代谢物残留量的方法。样品经乙腈提取,分散固相萃取技术QuEChERS净化,采用基质校正曲线外标法定量。在0.005~0.10mg/L范围内氟虫腈及其3种代谢物均呈现良好的线性关系,所有目标物的定量限均在0.025~0.10μg/kg范围内,均能满足国内外的限量要求。在0.1、2.0、4.0、20.0μg/kg 4个添加水平下,氟虫腈及其3种代谢物的平均回收率均处于87.0%~99.3%,RSD均≤12.7%,说明该法有较高的准确度和较好的稳定性。综上所述,该法灵敏度、准确度较高,精密度较好,可用于禽蛋及蛋制品中氟虫腈及其代谢物残留量的测定。 相似文献
999.
1000.
具有热活化延迟荧光(thermally activated delayed fluorescence, TADF)特性的配合物可以同时利用单重态和三重态激子,因此发光量子效率较高,近年来受到广大科研工作者的关注。特别是铜金属有机配合物,最低单重态和最低三重态的能量差较小,又可以通过不同配体或取代基进行调节,所以具有较好TADF性能。本文根据配位原子的类型,汇总和分析了近5年具有TADF性质的铜配合物的结构特点和发光性能,并简要讨论了其在有机发光二极管(organic light-emitting diodes,OLEDs)中的潜在应用。 相似文献