全文获取类型
收费全文 | 622篇 |
免费 | 21篇 |
国内免费 | 73篇 |
专业分类
化学 | 687篇 |
力学 | 1篇 |
物理学 | 28篇 |
出版年
2023年 | 4篇 |
2022年 | 7篇 |
2021年 | 10篇 |
2020年 | 7篇 |
2019年 | 16篇 |
2018年 | 8篇 |
2017年 | 9篇 |
2016年 | 26篇 |
2015年 | 11篇 |
2014年 | 13篇 |
2013年 | 54篇 |
2012年 | 24篇 |
2011年 | 24篇 |
2010年 | 26篇 |
2009年 | 34篇 |
2008年 | 36篇 |
2007年 | 79篇 |
2006年 | 46篇 |
2005年 | 34篇 |
2004年 | 31篇 |
2003年 | 23篇 |
2002年 | 19篇 |
2001年 | 18篇 |
2000年 | 15篇 |
1999年 | 11篇 |
1998年 | 15篇 |
1997年 | 13篇 |
1996年 | 12篇 |
1995年 | 8篇 |
1994年 | 13篇 |
1993年 | 13篇 |
1992年 | 8篇 |
1991年 | 17篇 |
1990年 | 9篇 |
1989年 | 10篇 |
1988年 | 6篇 |
1987年 | 2篇 |
1986年 | 3篇 |
1984年 | 1篇 |
1983年 | 1篇 |
排序方式: 共有716条查询结果,搜索用时 203 毫秒
1.
Yang Su Xinlu Wang Minghang Zhang Huimin Guo Prof. Haizhu Sun Gang Huang Prof. Dongtao Liu Prof. Guangshan Zhu 《Angewandte Chemie (International ed. in English)》2023,62(45):e202308182
Zn-I2 batteries have attracted attention due to their low cost, safety, and environmental friendliness. However, their performance is still limited by the irreversible growth of Zn dendrites, hydrogen evolution reactions, corrosion, and shuttle effect of polyiodide. In this work, we have prepared a new porous polymer (CD-Si) by nucleophilic reaction of β-cyclodextrin with SiCl4, and CD-Si is applied to the solid polymer electrolyte (denoted PEO/PVDF/CD-Si) to solve above-mentioned problems. Through the anchoring of the CD-Si, a conductive network with dual transmission channels was successfully constructed. Due to the non-covalent anchoring effect, the ionic conductivity of the solid polymer electrolytes (SPE) can reach 1.64×10−3 S cm−1 at 25 °C. The assembled symmetrical batteries can achieve highly reversible dendrite-free galvanizing/stripping (stable cycling for 7500 h at 5 mA cm−2 and 1200 h at 20 mA cm−2). The solid-state Zn-I2 battery shows an ultra-long life of over 35,000 cycles at 2 A g−1. Molecular dynamics simulations are performed to elucidate the working mechanism of CD-Si in the polymer matrix. This work provides a novel strategy towards solid electrolytes for Zn-I2 batteries. 相似文献
2.
利用α-环糊精(α-CD)与含有聚乙二醇(PEG)链段的聚合物Pluronic F127的超分子作用制备水凝胶.该物理交联水凝胶的交联点包括α-CD与PEG链包合物堆积形成的微晶区和聚合物疏水链段聚集区.优化水凝胶组分,得到具有较低固含量和较短凝胶化时间的体系用于胰岛素的负载和释放研究.通过X射线衍射(XRD),扫描显微镜(SEM)对水凝胶结构进行表征.通过紫外分光光度计监测胰岛素的释放过程,结果表明,水凝胶释药时间约为65 h,且释放曲线较为平缓.细胞毒性实验结果表明该水凝胶材料对细胞生长无明显抑制作用.小鼠体内释药实验结果表明该水凝胶载体对延长胰岛素的释药时间有一定效果,可作为多肽类药物的缓释体系. 相似文献
3.
4.
成功构筑了β-环糊精修饰的三维还原氧化石墨烯复合材料(3D-rGO/β-CD),并对该复合材料进行扫描电子显微镜、傅里叶红外光谱、热重分析和拉曼光谱分析等一系列的表征,分析了其形貌和结构的特征。进一步将其修饰到玻碳电极(GCE)表面,构建了一种新型电化学传感器(3D-rGO/β-CD/GCE)。利用3D-rGO/β-CD/GCE电化学传感器,通过微分脉冲伏安法(DPV)对左氧氟沙星(LEV)进行了检测。其中,具有多孔结构的三维还原氧化石墨烯具有优异的导电性能、比表面积大、化学稳定性好等优良的性质,而修饰的β-环糊精能在其环形腔内与客体分子结合形成超分子包合物,进而可以对LEV进行有效识别。研究结果显示,在最优实验条件下,3D-rGO/β-CD/GCE对左氧氟沙星的检测具有较宽的线性范围(1~150μmol/L),且检测限可达0.33μmol/L,同时该修饰电极还表现出良好的选择性和稳定性。此外,成功将其应用于实际水样中LEV的检测,表明该传感器具有一定的应用潜力。 相似文献
5.
M. Narender M. Somi Reddy N. Srilakshmi Krishnaveni K. Surendra Y. V. D. Nageswar 《合成通讯》2013,43(10):1463-1470
A mild and efficient method for the regeneration of carbonyl compounds from oximes at room temperature in impressive yields has been developed using iodosobenzene/KBr in the presence of β‐cyclodextrin in water. 相似文献
6.
The main objective of this study is to provide an insight into the interactions involved during adsorption of the alcohols on β-CD composite nanostructured membrane. Interactions between β-cyclodextrin (β-CD) and alcohols (methanol, ethanol and butanol) are studied using the QM/MM method. Magnitude of interaction energies show that the alcohols are adsorbed on the membrane. In addition, the thermochemical analysis suggests that the formation of these host-guest complexes is enthalpy driven. 相似文献
7.
Konkala Karnakar Katla Ramesh Sabbavarapu Narayana Murthy Yadavalli Venkata Durga Nageswar 《Helvetica chimica acta》2013,96(12):2276-2281
The first example of the stereoselective synthesis of (Z)‐ and (E)‐allyl aryl sulfides and selenides from Baylis? Hillman acetates under neutral conditions in H2O by supramolecular catalysis involving β‐cyclodextrin is reported. β‐Cyclodextrin can be recovered and reused. The reaction is very efficient in providing allyl aryl sulfides and selenides in good‐to‐excellent yields with clean reaction profiles under mild reaction conditions. 相似文献
8.
The detection of phthalates in human biologic fluids remains an important research objective because it provides an important measure of an individual’s exposure to this class of compounds, which have known deleterious health effects. Moreover, the ability to accomplish such detection in fluids that are easy to collect, such as saliva and urine, provides additional practical advantages. Reported herein is the application of cyclodextrin-promoted fluorescence energy transfer and fluorescence modulation to accomplish precisely such detection: the development of sensitive and selective florescence-based detection methods for phthalates in saliva, an easily collectable human biologic fluid. Such saliva-based detection methods occur with high levels of selectivity (100% differentiation) and sensitivity (limits of detection as low as 0.089?µM), and provide significant potential in the development of practical phthalate detection devices. 相似文献
9.
In this paper, the interactions of meso-Tetrakis (4-sulfonatophenyl) porphyrin (TPPS 4 ) and six cyclodextrins have been studied, respectively, by fluorescence spectroscopy, polarography and thin-layer chromatography. The inclusion constants of different methods are determined and the comparison of inclusion capacity of various cyclodextrins indicates that for the ionic cyclodextrins the charge interaction plays an important role in the inclusion procedure. The thermodynamic parameters of interaction imply that the inclusion process shows the enthalpy-entropy compensation effect. Cyclodextrin, being regarded as an artificial analogue of proteinoid of heme, provides a protective sheath for porphyrin. However, the TPPS 4 , encapsulated within this saccharid-coated barrier, its solubility is enhanced prominently, which exhibits that this interaction may modify the biological properties of TPPS 4 that owned the similar properties as hematoporphyrin. 相似文献
10.
环糊精包结作用下水溶液共聚合制备疏水改性阳离子聚丙烯酰胺及其絮凝效果研究 总被引:1,自引:0,他引:1
在水溶液中制备了甲基环糊精(Me-β-CD)/疏水单体2-苯氧乙基丙烯酸酯(POEA)的包结物(1a)。利用紫外-可见光谱及核磁共振波谱等检测手段研究了Me-β-CD与POEA的包合作用,并对包合物的结构、性能进行了表征和分析。同时在水溶液中引发丙烯酰胺(AM)、阳离子单体丙烯酰氧乙基三甲基氯化铵(DAC)以及1a的均相共聚合得到疏水修饰的阳离子聚丙烯酰胺P(AM-DAC-POEA),实现了用绿色方法合成高效高分子絮凝剂的目的,并对该高分子对高岭土模拟污水的絮凝效果进行了考察。 相似文献