全文获取类型
收费全文 | 2672篇 |
免费 | 255篇 |
国内免费 | 431篇 |
专业分类
化学 | 3112篇 |
晶体学 | 44篇 |
力学 | 7篇 |
综合类 | 18篇 |
数学 | 10篇 |
物理学 | 167篇 |
出版年
2023年 | 36篇 |
2022年 | 34篇 |
2021年 | 74篇 |
2020年 | 111篇 |
2019年 | 104篇 |
2018年 | 76篇 |
2017年 | 84篇 |
2016年 | 114篇 |
2015年 | 114篇 |
2014年 | 137篇 |
2013年 | 265篇 |
2012年 | 165篇 |
2011年 | 136篇 |
2010年 | 121篇 |
2009年 | 151篇 |
2008年 | 142篇 |
2007年 | 163篇 |
2006年 | 156篇 |
2005年 | 161篇 |
2004年 | 160篇 |
2003年 | 142篇 |
2002年 | 103篇 |
2001年 | 80篇 |
2000年 | 55篇 |
1999年 | 64篇 |
1998年 | 45篇 |
1997年 | 51篇 |
1996年 | 38篇 |
1995年 | 37篇 |
1994年 | 37篇 |
1993年 | 48篇 |
1992年 | 36篇 |
1991年 | 11篇 |
1990年 | 20篇 |
1989年 | 8篇 |
1988年 | 18篇 |
1987年 | 5篇 |
1986年 | 8篇 |
1985年 | 7篇 |
1984年 | 3篇 |
1983年 | 2篇 |
1982年 | 4篇 |
1980年 | 5篇 |
1979年 | 9篇 |
1978年 | 2篇 |
1977年 | 6篇 |
1976年 | 4篇 |
1973年 | 1篇 |
1972年 | 1篇 |
1969年 | 1篇 |
排序方式: 共有3358条查询结果,搜索用时 15 毫秒
1.
《Mendeleev Communications》2022,32(2):180-182
New amino phospha betaines were obtained by quaternization of potassium salt of amino phosphonate and higher alkyl bromides. The structure of isopropyl (N-dodecyl-N,N- dimethylammoniomethyl)phosphonate was confirmed by single crystal X-ray diffraction. All synthesized compounds demonstrate high antibacterial and antifungal activities. 相似文献
2.
The dissolution behavior of carbon steel in ammonium chloride (NH4Cl) solution containing sodium thiosulfate (Na2S2O3) of various concentrations (0.01 and 0.1 M) was investigated using electrochemical impedance spectroscopy (EIS) and other nonelectrochemical techniques. The weight loss and polarization measurements indicate a significant increase in the NH4Cl corrosion rate of carbon steel on addition of Na2S2O3. The EIS measurements exhibited two capacitive loops at multiple direct current (dc) potentials for both the concentrations. Electrical equivalent circuit (EEC) and reaction mechanism analysis (RMA) were employed to analyze the impedance data. A four-step mechanism with two intermediate adsorbate species of same charge was proposed to explain the dissolution behavior of carbon steel in the given system. The surface coverage values enumerated that the surface was entirely covered with adsorbed species unlike in the pure NH4Cl system. Charge transfer resistance and polarization resistance values estimated from RMA parameters indicate the increase in a dissolution rate with dc potential. The surface morphology was inspected via field emission scanning electron microscopy, and the corrosion products including surface state of carbon steel electrode were analyzed using energy dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy. 相似文献
3.
Timm Bergholz Dr. Benjamin Oelkers Dr. Benedikt Huber Prof. Bernhard Roling Prof. Dr. Jörg Sundermeyer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2613-2620
New salts based on imidazolium, pyrrolidinium, phosphonium, guanidinium, and ammonium cations together with the 5‐cyanotetrazolide anion [C2N5]? are reported. Depending on the nature of cation–anion interactions, characterized by XRD, the ionic liquids (ILs) have a low viscosity and are liquid at room temperature or have higher melting temperatures. Thermogravimetric analysis, cyclic voltammetry, viscosimetry, and impedance spectroscopy display a thermal stability up to 230 °C, an electrochemical window of 4.5 V, a viscosity of 25 mPa s at 20 °C, and an ionic conductivity of 5.4 mS cm?1 at 20 °C for the IL 1‐butyl‐1‐methylpyrrolidinium 5‐cyanotetrazolide [BMPyr][C2N5]. On the basis of these results, the synthesized compounds are promising electrolytes for lithium‐ion batteries. 相似文献
4.
Fine‐Tuning of Lewis Acidity: The Case of Borenium Hydride Complexes Derived from Bis(phosphinimino)amide Boron Precursors 下载免费PDF全文
Dr. Kuldeep Jaiswal Dr. Billa Prashanth Dr. Sanjay Singh 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(31):11035-11041
Reactions of bis(phosphinimino)amines LH and L′H with Me2S ? BH2Cl afforded chloroborane complexes LBHCl ( 1 ) and L′BHCl ( 2 ), and the reaction of L′H with BH3 ? Me2S gave a dihydridoborane complex L′BH2 ( 3 ) (LH=[{(2,4,6‐Me3C6H2N)P(Ph2)}2N]H and L′H=[{(2,6‐iPr2C6H3N)P(Ph2)}2N]H). Furthermore, abstraction of a hydride ion from L′BH2 ( 3 ) and LBH2 ( 4 ) mediated by Lewis acid B(C6F5)3 or the weakly coordinating ion pair [Ph3C][B(C6F5)4] smoothly yielded a series of borenium hydride cations: [L′BH]+[HB(C6F5)3]? ( 5 ), [L′BH]+[B(C6F5)4]? ( 6 ), [LBH]+[HB(C6F5)3]? ( 7 ), and [LBH]+[B(C6F5)4]? ( 8 ). Synthesis of a chloroborenium species [LBCl]+[BCl4]? ( 9 ) without involvement of a weakly coordinating anion was also demonstrated from a reaction of LBH2 ( 4 ) with three equivalents of BCl3. It is clear from this study that the sterically bulky strong donor bis(phosphinimino)amide ligand plays a crucial role in facilitating the synthesis and stabilization of these three‐coordinated cationic species of boron. Therefore, the present synthetic approach is not dependent on the requirement of weakly coordinating anions; even simple BCl4? can act as a counteranion with borenium cations. The high Lewis acidity of the boron atom in complex 8 enables the formation of an adduct with 4‐dimethylaminopyridine (DMAP), [LBH ? (DMAP)]+[B(C6F5)4]? ( 10 ). The solid‐state structures of complexes 1 , 5 , and 9 were investigated by means of single‐crystal X‐ray structural analysis. 相似文献
5.
Clément Falaise Dr. May Nyman 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(41):14678-14687
For 11 years now, the structural diversity and aesthetic beauty of uranyl–peroxide capsules have fascinated researchers from the diverse fields of mineralogy, polyoxometalate chemistry, and nuclear fuel technologies. There is still much to be learned about the mechanisms of the self‐assembly process, and the role of solution parameters including pH, alkali template, temperature, time, and others. Here we have exploited the high solubility of the UO22+/H2O2/LiOH aqueous system to address the effect of the hydroxide concentration. Important techniques of this study are single‐crystal X‐ray diffraction, small‐angle X‐ray scattering, and Raman spectroscopy. Three key phases dominate the solution speciation as a function of time and the LiOH/UO22+ ratio: the uranyl–triperoxide monomer [UO2(O2)3]4?and the two capsules [(UO2)(O2)(OH)]2424?(U24) and [(UO2)(O2)1.5]2828?(U28). When the LiOH/U ratio is around three, U28 forms rapidly and this cluster can be isolated in high yield and purity. This result was most surprising and challenges the hypothesis that alkali templating is the most important determinant in the cluster geometry. Moreover, analogous experiments with KOH, NH4OH, and TEAOH (TEA=tetraethylammonium) also rapidly yield U28, which suggests that U28 is the kinetically favored species. Complete mapping of the pH–time phase space reveals only a narrow window of the U28 dominance, which is why it was previously overlooked as an important kinetic species in this chemical system, as well as others with different counterions. 相似文献
6.
Cross‐Coupling of Organolithium with Ethers or Aryl Ammonium Salts by C−O or C−N Bond Cleavage 下载免费PDF全文
Ze‐Kun Yang Dong‐Yu Wang Hiroki Minami Hiroyuki Ogawa Takashi Ozaki Dr. Tatsuo Saito Dr. Kazunori Miyamoto Dr. Chao Wang Prof. Dr. Masanobu Uchiyama 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(44):15693-15699
Various aryl‐, alkenyl‐, and/or alkyllithium species reacted smoothly with aryl and/or benzyl ethers with cleavage of the inert C?O bond to afford cross‐coupled products, catalyzed by commercially available [Ni(cod)2] (cod=1,5‐cyclooctadiene) catalysts with N‐heterocyclic carbene (NHC) ligands. Furthermore, the coupling reaction between the aryllithium compounds and aryl ammonium salts proceeded under mild conditions with C?N bond cleavage in the presence of a [Pd(PPh3)2Cl2] catalyst. These methods enable selective sequential functionalizations of arenes having both C?N and C?O bonds in one pot. 相似文献
7.
Dr. Christian Hering‐Junghans Max Thomas Dr. Alexander Villinger Prof. Dr. Axel Schulz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(18):6713-6717
This work describes the synthesis and full characterization of elusive chloropnictenium ion salts of the type [RAr*N(SiMe)ECl][A] (RAr*=2,6‐(CHPh2)‐4‐R‐C6H2, R=Me, tBu; E=Sb, Bi; A?=GaCl4, Al(OCH(CF3)2)4). In these species the cation is significantly stabilized by weak arene interactions to flanking phenyl groups of the RAr* moiety. In this context the bonding situation has been studied by computational means and the reactivity towards the Lewis base 4‐dimethylaminopyridine (dmap) was investigated. 相似文献
8.
Silver(I)‐Catalyzed Enantioselective [3+2]‐Cycloaddition Reaction of α‐Silylimines: A Facile Route to Quaternary‐Carbon‐Rich Scaffolds 下载免费PDF全文
Dr. Naredla Kesava‐Reddy Christopher Golz Prof. Dr. Carsten Strohmann Dr. Kamal Kumar 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(51):18373-18377
A silver‐catalyzed highly enantioselective 1,3‐dipolar cycloaddition reaction of α‐silylimines with pyrone‐based trisubstituted olefins was developed affording bi‐ and tricyclic α‐quaternary‐carbon‐rich pyrano‐pyrrolidines in excellent yields. The tricyclic benzopyrone adducts thus obtained were efficiently transformed into highly complex tetracyclic scaffolds supporting four consecutive stereogenic centers with three quaternary carbons. 相似文献
9.
《Mendeleev Communications》2022,32(5):629-631
The Michael–Mannich cascade cyclization of cyano olefins, ethyl 4,4,4-trifluoro-3-oxobutanoate, aromatic aldehydes and ammonium acetate provides convenient stereoselective formation of ethyl 5,5-dicyano-4,6-diaryl-2-hydroxy-2-(trifluoromethyl)piperidine-3-carboxylates with fourstereogenic centers and dialkyl 4,6-diaryl-5-cyano-2-hydroxy-2-(trifluoromethyl)piperidine-3,5-dicarboxylates with five stereogenic centers. Ammonium acetate plays dual role, acting as a base and as a nitrogen source. 相似文献
10.
Doris Chen Elizabeth V. Jones Corey W. Williams Tan-Khang N. Huynh Tristan C. McPhail Prof. Dr. Stefan France 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(52):e202201368
Herein, a SnCl4-catalyzed intramolecular, interrupted homo-Nazarov cascade biscyclization to access angular (hetero)aryl-fused polycycles is reported. Subsequent decarboxylation of the readily enolizable products afforded the angular products in up to 71 % yield over two steps, with the trans-diastereomers as the major products. The cyclopropyl homo-Nazarov cyclization precursors were formed using a scalable and modular synthetic route that, ultimately, offers access to 6,6,6-, 6,6,5-, 6,5,6-, 6,6,5,6-, and 6,6,6,5-fused angular polycyclic products. To showcase the rigor and utility of the method, an 8-step total synthesis of (±)-1-oxoferruginol, an antibacterial aromatic abietane diterpenoid, was disclosed. 相似文献