全文获取类型
收费全文 | 257篇 |
免费 | 16篇 |
专业分类
化学 | 223篇 |
晶体学 | 2篇 |
数学 | 24篇 |
物理学 | 24篇 |
出版年
2023年 | 5篇 |
2022年 | 8篇 |
2021年 | 4篇 |
2020年 | 16篇 |
2019年 | 11篇 |
2018年 | 5篇 |
2017年 | 5篇 |
2016年 | 6篇 |
2015年 | 9篇 |
2014年 | 9篇 |
2013年 | 19篇 |
2012年 | 40篇 |
2011年 | 33篇 |
2010年 | 13篇 |
2009年 | 18篇 |
2008年 | 26篇 |
2007年 | 18篇 |
2006年 | 6篇 |
2005年 | 5篇 |
2004年 | 4篇 |
2003年 | 4篇 |
2002年 | 1篇 |
2001年 | 1篇 |
1998年 | 2篇 |
1997年 | 2篇 |
1996年 | 1篇 |
1995年 | 1篇 |
1977年 | 1篇 |
排序方式: 共有273条查询结果,搜索用时 15 毫秒
1.
Cover Picture: Coordination Chemistry of N‐Heterocyclic Nitrenium‐Based Ligands (Chem. Eur. J. 19/2015)
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
2.
Catherine Weetman Amelie Porzelt Prasenjit Bag Franziska Hanusch Shigeyoshi Inoue 《Chemical science》2020,11(18):4817
Main group multiple bonds have proven their ability to act as transition metal mimics in the last few decades. However, catalytic application of these species is still in its infancy. Herein we report the second neutral NHC-stabilised dialumene species by use of a supporting aryl ligand (3). Different to the trans-planar silyl-substituted dialumene (3Si), compound 3 features a trans-bent and twisted geometry. The differences between the two dialumenes are explored computationally (using B3LYP-D3/6-311G(d)) as well as experimentally. A high influence of the ligand''s steric demand on the structural motif is revealed, giving rise to enhanced reactivity of 3 enabled by a higher flexibility in addition to different polarisation of the aluminium centres. As such, facile activation of dihydrogen is now achievable. The influence of ligand choice is further implicated in two different catalytic reactions; not only is the aryl-stabilised dialumene more catalytically active but the resulting product distributions also differ, thus indicating the likelihood of alternate mechanisms simply through a change of supporting ligand.Ligand controlled reactivity: a trans-bent and twisted geometry enables dihydrogen activation and enhanced catalytic activity for NHC-stabilised dialumenes. 相似文献
3.
Abstract A green and efficient methodology has been developed for the direct conversion of aryl aldehydes to the corresponding tert-butyl peresters. The reaction has been carried out in absence of any solvent and the sunlight is used as the green source of energy. In this reaction tetrabutylammonium iodide (TBAI) acts as the mild organo catalyst and tert-butyl hydroperoxide (TBHP) serve as the source of tert-butyl group. 相似文献
4.
Prasenjit Maity Susmit Basu Sumit Bhaduri Goutam Kumar Lahiri 《Journal of molecular catalysis. A, Chemical》2007,270(1-2):117-122
High nuclearity platinum carbonyl cluster anions (Chini's clusters) have been used as precursors to prepare a platinum nanocatalyst. The ionic polyelectrolyte poly(diallyldimethylammonium chloride) has been used as the support material for anchoring [Pt30(CO)60]2− via ion-pairing and subsequent stabilization of the nanoparticles. The polymer-supported material has been studied by spectroscopy (NIR, 13C NMR, and IR) and TEM before and after its use as a water soluble hydrogenation catalyst. The nanocatalyst is found to be effective for the chemoselective hydrogenation of olefinic, aldehydic and ketonic double bonds. For most of the substrates isolation of the product and reuse of the catalyst are extremely easy due to the automatic phase separation of the products from the catalyst. The spectral features of the fresh catalyst show retention of the carbonyl ligands and molecular identity of the parent cluster, but after use the carbonyl ligands appear to be lost. TEM of the supported material before and after use as a catalyst shows the presence of platinum nanoparticles with majority (≥70%) of the particles in the range of 2–6 nm. Smaller particles are dominant in the used catalyst and this observation is rationalized on the basis of the known reactivity of Chini's clusters with dihydrogen. 相似文献
5.
Moorthy JN Venkatakrishnan P Mal P Venugopalan P 《The Journal of organic chemistry》2003,68(2):327-330
The supramolecular nonbonded C-H...X interactions between formyl hydrogens and ortho-halogen atoms (Br/Cl) have been exploited to achieve conformational control in the solid state of dimethyl-substituted iso- and terephthaladehydes (1-3) for unprecedented diphotocyclization. It is shown that the dihalogen substitution also contributes to the stability of the benzocyclobutenols relative to their precursor photoenols, so that the solid-state photolysis of dialdehydes 2b, 2c, and 3b leads to diphotocyclization to afford respectable yields of bis-benzocyclobutenols. 相似文献
6.
Subhajit Bhunia Pranay Saha Parikshit Moitra Matthew A. Addicoat Santanu Bhattacharya 《Chemical science》2022,13(26):7920
Solid porous and crystalline covalent organic frameworks (COFs) are characterized by their higher specific BET surface areas and functional pore walls, which allow the adsorption of various bioactive molecules inside the porous lattices. We have introduced a perylene-based COF, PER@PDA-COF-1, which acts as an effective porous volumetric reservoir for an anticancer drug, mitoxantrone (MXT). The drug-loaded COF (MXT–PER@PDA-COF-1) exhibited zero cellular release of MXT towards cancer cells, which can be attributed to the strong intercalation between the anthracene-dione motif of the drug and the perylene-based COF backbone. Here, we have introduced a strategy involving the serum-albumin-triggered intracellular release of mitoxantrone from MXT–PER@PDA-COF-1. The serum albumin acts as an exfoliating agent and as a colloidal stabilizer in PBS medium (pH = 7.4), rapidly forming a protein corona around the exfoliated COF crystallites and inducing the sustained release of MXT from the COF into tumorigenic cells.Solid porous and crystalline covalent organic frameworks (COFs) are characterized by their higher specific BET surface areas and functional pore walls, which allow the adsorption of various bioactive molecules inside the porous lattices. 相似文献
7.
4,4′-bipyridine bridged two Cu (II) complexes, [Cu2L12(4,4′-bipy)(H2O)2](ClO4)2 ( 1 ) and [Cu2L22(4,4′-bipy)]n·(2H2O)n ( 2 ) (where, HL1 = 2-[(3-methylamino-propylimino)-methyl]-phenol, H2L2 = 3-[(2-hydroxy-3-methoxy-benzylidene)-amino]-propionic acid, and 4,4′-bipy = 4,4′-bipyridine) have been synthesized and characterized by single crystal structure determination, mass spectrometry, FT-IR, electronic absorption, and emission spectroscopy. Complex 1 is dinuclear cationic compound and counter balanced by perchlorate anion, whereas complex 2 possesses 1D poly-nuclear structure. Both the complexes crystallize in monoclinic system with P21/c space group and the copper centers possess square pyramidal geometry. H-bonding, C-H···π, π···π interactions results the formation of two dimentional supramolecular structure for both the complexes. Interactions of complexes with bovine serum albumins (BSA) and human serum albumins (HSA) have been studied by using electronic absorption and emission spectroscopic technique. The calculated values of binding constants (Kb) are (9.22 ± 0.26) × 105 L mol−1 ( 1 -BSA), (7.19 ± 0.16) × 105 L mol−1 ( 1 -HSA), (5.05 ± 0.20) × 105 L mol−1 ( 2 -BSA) and (3.56 ± 0.25) × 105 L mol−1 ( 2 -HSA). The mechanism of serum albumins-complex interactions have been investigated by fluorescence lifetime measurement. Fluorescence spectroscopic studies indicate that both the complexes interact with calf thymas-DNA. Catecholase activity of the complexes has been studied in methanol using 3,5-di-tert-butylcatechol (3,5-DTBC) as substrate and the result show that both the complexes are active for catalytic oxidation of 3,5-DTBC to 3,5-di-tert-butylquinone (3,5-DTBQ) in presence of molecular oxygen. Calculated values of turnover numbers are 71.81 ± 1.04 h−1 and 69.45 ± 0.74 h−1 for 1 and 2 , respectively. 相似文献
8.
9.
10.
Pradep Mathur Anjan K. Bhunia Ch. Srinivasu Shaikh Md. Mobin 《Phosphorus, sulfur, and silicon and the related elements》2013,188(4-5):899-901
Group 16 elements serve as useful bridging and stabilising single atom ligands in mixed-metal carbonyl complexes and impart unusual reactivity on coordinated acetylenic moieties. Reactions of [Fe 3 (CO) 9 (μ 3 -E) 2 ] (E = S, or Se) with mononuclear acetylide complexes, [CpM(CO)_3-x(CCR)] (M = Mo or W, x = 0, R = Ph; M = Fe, x = 1, R = Ph or ferrocenyl) under facile conditions yield complexes featuring acetylide coupling, acetylide-flip and formation of oxo and acetylide-bridged complexes. In presence of free acetylenes, unusual ligand systems arising from C─S bond formation are observed and under certain conditions, formation of quinones by coupling of acetylenes with carbon monoxide is facilitated. 相似文献