全文获取类型
收费全文 | 236篇 |
免费 | 13篇 |
国内免费 | 37篇 |
专业分类
化学 | 235篇 |
力学 | 3篇 |
综合类 | 1篇 |
数学 | 23篇 |
物理学 | 24篇 |
出版年
2023年 | 5篇 |
2022年 | 6篇 |
2021年 | 14篇 |
2020年 | 8篇 |
2019年 | 11篇 |
2018年 | 3篇 |
2017年 | 10篇 |
2016年 | 5篇 |
2015年 | 19篇 |
2014年 | 13篇 |
2013年 | 21篇 |
2012年 | 21篇 |
2011年 | 15篇 |
2010年 | 10篇 |
2009年 | 8篇 |
2008年 | 12篇 |
2007年 | 14篇 |
2006年 | 15篇 |
2005年 | 8篇 |
2004年 | 8篇 |
2003年 | 3篇 |
2002年 | 6篇 |
2001年 | 5篇 |
2000年 | 6篇 |
1999年 | 15篇 |
1998年 | 9篇 |
1997年 | 3篇 |
1996年 | 5篇 |
1995年 | 5篇 |
1993年 | 1篇 |
1990年 | 2篇 |
排序方式: 共有286条查询结果,搜索用时 484 毫秒
1.
Cui X Delgado R Carapuça HM Drew MG Félix V 《Dalton transactions (Cambridge, England : 2003)》2005,(20):3297-3306
A tetraazamacrocycle containing ferrocene moieties has been synthesized and characterized. The tetraprotonated form of this compound was evaluated as a receptor (R) for anion recognition of several substrates (S), Cl(-), PF(6)(-), HSO(4)(-), H(2)PO(4)(-) and carboxylates, such as p-nitrobenzoate (p-nbz(-)), phthalate (ph(2-)), isophthalate (iph(2-)) and dipicolinate (dipic(2-)). (1)H NMR titrations in CD(3)OD indicated that this receptor is not suitable for recognizing HSO(4)(-) and H(2)PO(4)(-), but weakly binds p-nbz(-), and strongly interacts with ph(2-), dipic(2-), and iph(2-) anions forming 1 : 2 assembled species. The largest beta(2) binding constant was determined for ph(2-), followed by dipic(2-) and finally iph(2-). The effect of the anionic substrates on the electron-transfer process of the ferrocene units of R was evaluated using cyclic voltammetry (CV) and square wave voltammetry (SWV) in methanol solution and 0.1 mol dm(-3)(CH(3))(4)NCl as the supporting electrolyte. Titrations of the receptor were undertaken by addition of anion solutions in their tetrabutylammonium or tetramethylammonium forms. The protonated ligand exhibits a reversible voltammogram, which shifts cathodically in the presence of the substrates. The data revealed kinetic constraints in the formation of the receptor/substrate entity for dipic(2-), ph(2-) and iph(2-) anions, but not for p-nbz(-). In spite of the slow kinetics of assembled species formation with the ph(2-) substrate, this anion provides the largest redox-response when the supramolecular entity is formed, followed by dipic(2-), iph(2-) and finally p-nbz(-) anions. This trend is in agreement with the (1)H NMR results and the values of the binding constants. Single crystal X-ray structures of the receptor with PF(6)(-), ph(2-), iph(2-) and p-nbz(-) were carried out and showed that supermolecules with a RS(2) stoichiometry are formed with the first three anions, but RS(4) with p-nbz(-). In all cases the binding occurs outside the macrocyclic cavity via N-H...O=C hydrogen bonds for carboxylate anions and N-H...F hydrogen bonds for the PF(6)(-) anion, which is in agreement with the solution results. The macrocyclic framework adopts different conformations in order to interact with each substrate having Fe...Fe intramolecular distances ranging from 10.125(14) to 12.783(15)A. 相似文献
2.
锡—邻菲咯啉络合物吸附极谱波的研究及应用 总被引:3,自引:0,他引:3
研究了锡-邻菲咯啉体系的极谱行为,在pH=2.50的0.10mol/L氯乙酸-氯乙酸钠介质中,在单扫描极谱上,Sn-邻菲咯啉络合物于-0.41V电位处产生一良好的吸附还原波。波高与Sn的浓度在2.0×10^-8-4.0×10^-6mol/L范围内呈线性关系;检出限为1.0×10^-8mol/L Sn,对合金标样中的锡进行测定,取得了满意的结果。 相似文献
3.
Nanostructured LiCoO2 fibers were prepared by the sol-gel related electrospinning technique using metal acetate and citric acid as starting materials. The transformation from the xerogel fibers to the LiCoO2 fibers and the nanostructure of LiCoO2 fibers have been investigated in detail. The LiCoO2 fibers with 500 nm to 2 mum in diameter were composed of polycrystalline nanoparticles in sizes of 20-35 nm. Cyclic voltammetry and charge-discharge experiments were applied to characterize the electrochemical properties of the fibers as cathode materials for lithium-ion batteries. The cyclic voltammogram curves indicated faster diffusion and migration of Li+ cations in the nanostructured LiCoO2 fiber electrode. In the first charge-discharge process, the LiCoO2 fibers showed the initial charge and discharge capacities of 216 and 182 (mA.h)/g, respectively. After the 20th cycle, the discharge capacity decreased to 123 (mA.h)/g. The X-ray diffraction and high-resolution transmission electron microscopy analyses indicated that the large loss of capacity of fiber electrode during the charge-discharge process might mainly result from the dissolution of cobalt and lithium cations escaping from LiCoO2 to form the crystalline Li2CO3 and CoF2 impurities. 相似文献
4.
5.
6.
Raana Kashfi‐Sadabad Laura Gonzalez‐Fajardo Derek Hargrove Bahar Ahmadi Daniel Munteanu Sina Shahbazmohamadi Michael Jay Xiuling Lu 《Particle & Particle Systems Characterization》2019,36(4)
Nonspecific high‐energy radiation for treatment of metastatic ovarian cancer is limited by damage to healthy organs, which can be mitigated by the use of radiosensitizers and image‐guided radiotherapy. Gold (Au) and tantalum oxide (TaOx) nanoparticles (NPs), by virtue of their high atomic numbers, find utility in the design of bimetallic NP systems capable of high‐contrast computed tomography (CT) imaging as well as a potential radiosensitizing effect. These two radio‐dense metals are integrated into dendritic mesoporous silica NPs (dMSNs) with radial porous channels for high surface‐area loading of therapeutic agents. This approach results in stable, monodispersed dMSNs with a uniform distribution of Au on the surface and TaOx in the core that exhibits CT attenuation up to seven times greater than iodine or monometallic dMSNs without either TaOx or Au. Tumor targeting is assessed in a metastatic ovarian cancer mouse model. Ex vivo micro‐CT imaging of collected tumors shows that these NPs not only accumulate at tumor sites but also penetrate inside tumor tissues. This study demonstrates that after intraperitoneal administration, rationally designed bimetallic NPs can simultaneously serve as targeted contrast agents for imaging tumors and to enhance radiation therapy in metastatic ovarian cancer. 相似文献
7.
A palladium(II)-catalyzed highly regioselective tandem reactions of o-alkynylbenzoates with methyl vinyl ketone for the synthesis of isocoumarins was developed. It is a convenient, mild and environmentally benign reaction with moderate to high yield. The reaction is initiated by the Pd(II) species and regenerate the Pd(II) species to complete the catalytic cycle without the necessity of a redox system. 相似文献
8.
Rhodium(III)-catalyzed [4 + 1] cyclization of azobenzenes with α-Cl ketones has been developed. 3-Acyl-2H-indazoles could be easily afforded in up to 97% yields for more than 30 examples. The obtained products are potentially valuable in organic synthesis and drug discovery. This protocol featured with high efficiency, extensive functional group tolerance and mild reaction conditions. The one-step efficient construction of an anti-inflammatory agent confirms the practicability of this procedure. 相似文献
9.
A ferrocene-initiated radical reaction of benzoquinone with amines has been successfully developed for the direct access to diaminobenzoquinone imines in high yields,in which the comme rcially available and cheap ferrocene was employed as a radical initiator and TBHP was used as an oxidant.Moreover,this reaction could be achieved with low loading of ferrocene(0.5 mol%).This protocol is highly efficient with good substrate tolera nce and provides a new approach for the construction of benzoquinone imines with potential pharmaceutical interest. 相似文献
10.
利用标量化方法建立对称向量拟均衡问题有效解的存在性定理.作为标量化方法的应用,利用这一方法得到向量变分不等式和拟向量变分不等式有效解的存在性定理. 相似文献