全文获取类型
收费全文 | 1769篇 |
免费 | 133篇 |
国内免费 | 395篇 |
专业分类
化学 | 1889篇 |
晶体学 | 69篇 |
力学 | 18篇 |
综合类 | 12篇 |
数学 | 4篇 |
物理学 | 305篇 |
出版年
2024年 | 1篇 |
2023年 | 18篇 |
2022年 | 28篇 |
2021年 | 49篇 |
2020年 | 55篇 |
2019年 | 55篇 |
2018年 | 48篇 |
2017年 | 63篇 |
2016年 | 73篇 |
2015年 | 88篇 |
2014年 | 104篇 |
2013年 | 193篇 |
2012年 | 128篇 |
2011年 | 108篇 |
2010年 | 98篇 |
2009年 | 102篇 |
2008年 | 109篇 |
2007年 | 102篇 |
2006年 | 105篇 |
2005年 | 103篇 |
2004年 | 96篇 |
2003年 | 88篇 |
2002年 | 68篇 |
2001年 | 49篇 |
2000年 | 47篇 |
1999年 | 53篇 |
1998年 | 39篇 |
1997年 | 23篇 |
1996年 | 32篇 |
1995年 | 35篇 |
1994年 | 29篇 |
1993年 | 11篇 |
1992年 | 18篇 |
1991年 | 16篇 |
1990年 | 11篇 |
1989年 | 8篇 |
1988年 | 7篇 |
1987年 | 4篇 |
1986年 | 9篇 |
1985年 | 6篇 |
1984年 | 3篇 |
1983年 | 2篇 |
1982年 | 1篇 |
1981年 | 3篇 |
1980年 | 4篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1975年 | 1篇 |
1959年 | 1篇 |
排序方式: 共有2297条查询结果,搜索用时 17 毫秒
1.
Dr. Liangqi Gui Xiaoyun Miao Chengjun Lei Kailin Wang Dr. Wei Zhou Dr. Beibei He Prof. Qing Wang Dr. Ling Zhao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(47):11007-11014
Implementing sustainable energy conversion and storage technologies is highly reliant on crucial oxygen electrocatalysis, such as the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). However, the pursuit of low cost, energetic efficient and robust bifunctional catalysts for OER and ORR remains a great challenge. Herein, the novel Na-ion-deficient Na2−xCoP2O7 catalysts are proposed to efficiently electrocatalyze OER and ORR in alkaline solution. The engineering of Na-ion deficiency can tune the electronic structure of Co, and thus tailor the intrinsically electrocatalytic performance. Among the sodium cobalt phosphate catalysts, the Na1.95CoP2O7 (NCPO5) catalyst exhibits the lowest ΔE (EJ10,OER−EJ−1,ORR) of only 0.86 V, which favorably outperforms most of the reported non-noble metal catalysts. Moreover, the Na-ion deficiency can stabilize the phase structure and morphology of NCPO5 during the OER and ORR processes. This study highlights the Na-ion deficient Na2−xCoP2O7 as a promising class of low-cost, highly active and robust bifunctional catalysts for OER and ORR. 相似文献
2.
《Acta Crystallographica. Section C, Structural Chemistry》2018,74(9):1045-1052
A new tantalum phosphate, tridecasodium distrontium ditantalum nonaphosphate, Na13Sr2Ta2(PO4)9, was prepared using the high‐temperature flux method. The structure can be described as a three‐dimensional open framework containing isolated [TaV2(PO4)9]17− units that are interlocked by Na and Sr ions. Band structure studies by the first‐principles method revealed that Na13Sr2Ta2(PO4)9 is an insulator with an indirect band gap of 4.78 eV, which makes it suitable as a luminescent host matrix. A series of solid solutions, i.e. Na13Sr2–xTa2(PO4)9:xDy3+ (x = 0.01, 0.02, 0.04, 0.06, 0.08, 0.1, 0.12 and 0.14), were prepared and their photoluminescence properties studied. Under 350 nm light excitation, these emit two typical emissions of the Dy3+ ion, i.e. the 4F9/2→6H15/2 transition centred at 476 nm and the 4F9/2→6H13/2 transition centred at 570 nm. 相似文献
3.
Yolk‐Shell Porous Microspheres of Calcium Phosphate Prepared by Using Calcium L‐Lactate and Adenosine 5′‐Triphosphate Disodium Salt: Application in Protein/Drug Delivery 下载免费PDF全文
Guan‐Jun Ding Prof. Dr. Ying‐Jie Zhu Chao Qi Tuan‐Wei Sun Dr. Jin Wu Dr. Feng Chen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(27):9868-9876
A facile and environmentally friendly approach has been developed to prepare yolk‐shell porous microspheres of calcium phosphate by using calcium L ‐lactate pentahydrate (CL) as the calcium source and adenosine 5′‐triphosphate disodium salt (ATP) as the phosphate source through the microwave‐assisted hydrothermal method. The effects of the concentration of CL, the microwave hydrothermal temperature, and the time on the morphology and crystal phase of the product are investigated. The possible formation mechanism of yolk‐shell porous microspheres of calcium phosphate is proposed. Hemoglobin from bovine red cells (Hb) and ibuprofen (IBU) are used to explore the application potential of yolk‐shell porous microspheres of calcium phosphate in protein/drug loading and delivery. The experimental results indicate that the as‐prepared yolk‐shell porous microspheres of calcium phosphate have relatively high protein/drug loading capacity, sustained protein/drug release, favorable pH‐responsive release behavior, and a high biocompatibility in the cytotoxicity test. Therefore, the yolk‐shell porous microspheres of calcium phosphate have promising applications in various biomedical fields such as protein/drug delivery. 相似文献
4.
Dr. Jian Yang Dr. Ke Li Prof. Chunzhong Li Prof. Jinlou Gu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(51):23152-23156
Apyrase is an important family of extracellular enzymes that catalyse the hydrolysis of high-energy phosphate bonds (HEPBs) in ATP and ADP, thereby modulating many physiological processes and driving life activities. Herein, we report an unexpected discovery that cerium-based metal–organic frameworks (Ce-MOFs) of UiO-66(Ce) have intrinsic apyrase-like activity for ATP/ADP-related physiological processes. The abundant CeIII/CeIV couple sites of Ce-MOFs endow them with the ability to selectively catalyse the hydrolysis of HEPBs of ATP and ADP under physiological conditions. Compared to natural enzymes, they could resist extreme pH and temperature, and present a broad range of working conditions. Based on this finding, a significant inhibitory effect on ADP-induced platelet aggregation was observed upon exposing the platelet-rich plasma (PRP) to the biomimetic UiO-66(Ce) films, prefiguring their wide application potentials in medicine and biotechnology. 相似文献
5.
In this contribution we report on fluorotrimethyl[(Z)-pentafluoropropen-1-yl]phosphorane as a phosphorus based fluorinating reagent. Its solid state structure can be described as a trigonal bipyramid featuring elongated axial bonds due to the formation of a 3-center 4-electron bond. Abstraction of the fluoride ion leads to a shortening of the axial P–C bond. Thus the title compound can be utilized for substitution of bromine with fluorine and for the transfer of fluoride ions onto electrophilic compounds. Reaction with Sn(C2F5)2Br2 afforded salt [P(CH3)3(C3F5)]2[Sn(C2F5)2F4]. When fluorotrimethyl[(Z)-pentafluoropropen-1-yl]phosphorane was treated with P(C2F5)2F the primarily produced anion is sufficiently nucleophilic to attack the propenyl group of the cation in β-position to the phosphorus atom to yield zwitterionic [Me3PCF=C(CF3)–PF3(C2F5)2]. 相似文献
6.
Luis Eduardo Serrano-Mora María L. Zambrano-Zaragoza Nstor Mendoza-Muoz Gerardo Leyva-Gmez Zaida Urbn-Morln David Quintanar-Guerrero 《Molecules (Basel, Switzerland)》2021,26(7)
The purpose of the study was to develop a novel, directly compressible, co-processed excipient capable of providing a controlled-release drug system for the pharmaceutical industry. A co-processed powder was formed by adsorption of solid lipid nanoparticles (SLN) as a controlled-release film onto a functional excipient, in this case, dicalcium phosphate dihydrate (DPD), for direct compression (Di-Tab®). The co-processed excipient has advantages: easy to implement; solvent-free; industrial scaling-up; good rheological and compressibility properties; and the capability to form an inert platform. Six different batches of Di-Tab®:SLN weight ratios were prepared (4:0.6, 3:0.6, 2:0.6, 1:0.6, 0.5:0.6, and 0.25:0.6). BCS class III ranitidine hydrochloride was selected as a drug model to evaluate the mixture’s controlled-release capabilities. The co-processed excipients were characterized in terms of powder rheology and dissolution rate. The best Di-Tab®:SLN ratio proved to be 2:0.6, as it showed high functionality with good flow and compressibility properties (Carr Index = 16 ± 1, Hausner Index = 1.19 ± 0.04). This ratio could control release for up to 8 h, so it fits the ideal profile calculated based on biopharmaceutical data. The compressed systems obtained using this powder mixture behave as a matrix platform in which Fickian diffusion governs the release. The Higuchi model can explain their behavior. 相似文献
7.
Herein, we report an addition to the toolbox for the monitoring and quantification of the hydrolytic decay of pentose-1-phosphates, which are known to be elusive and difficult to quantify. This communication describes how apparent equilibrium shifts of a nucleoside phosphorolysis reaction can be employed to calculate hydrolytic loss of pentose-1-phosphates based on the measurement of post-hydrolysis equilibrium concentrations of a nucleoside and a nucleobase. To demonstrate this approach, we assessed the stability of the relatively stable ribose-1-phosphate at 98 °C and found half-lives of 1.8–11.7 h depending on the medium pH. This approach can be extended to other sugar phosphates and related reaction systems to quantify the stability of UV-inactive and hard-to-detect reaction products and intermediates. 相似文献
8.
Qiuyu He Lirong Cao Yiran Wei Prof. Gregory R. Dake 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(42):e202201328
The utility of 2-diphenylphosphoryloxy-1,3-dienes for the construction of substituted six-membered nitrogen heterocycles is presented. These dienes undergo boron trifluoride-promoted aza-Diels–Alder reactions when reacted with imines or related species formed in situ using aldehydes and amine derivatives. The stability of the dienes allows this three-component reaction to be carried out with no special precautions to eliminate water or air. Thirty-one examples of this process are presented. The usefulness of the enol phosphate functional group is highlighted in further reactions after the cycloaddition step to generate functionalized piperidenes or pyridines. 相似文献
9.
“氮及其化合物”复习教学中,通过社会性科学议题“是否应该停止使用氮肥”,在真实复杂的两难问题情境中,使学生基于物质类别和元素价态视角分析、设计氮肥的制备、使用以及减少其对环境影响中涉及的含氮物质的转化,提高学生自主应用氮元素“价-类”二维图综合分析、解决真实问题的能力,促进证据推理与模型认知、科学探究与创新意识、科学态度与社会责任等多维度化学学科核心素养的融合发展。经过多轮教学改进,结合教学效果抽提出以下教学策略:课上课下统筹安排,合理设置任务,提高学生参与议题的兴趣,促使学生全身心投入对议题的探讨;聚焦真实问题解决,将议题的探讨过程与关键能力持续进阶紧密结合并相互促进;让学生经历“做真事、真做事、真反思、真发展”的完整过程。 相似文献
10.
流动注射法同时测定海水中氨氮和磷酸盐 总被引:1,自引:0,他引:1
采用流动注射法同时测定海水中氨氮和磷酸盐的含量。在优化的试验条件下,氨氮和磷酸盐的线性范围分别为0.25 mg·L-1和0.30 mg·L-1以内,检出限(3S/N)分别为0.42μg·L-1和0.56μg·L-1。氨氮和磷酸盐加标回收率分别在85.0%~103%和86.7%~103%之间,测定值的相对标准偏差(n=6)分别在0.43%~5.3%和0~4.1%之间。方法用于分析标准物质,测定结果与分光光度法的结果一致。 相似文献