全文获取类型
收费全文 | 480031篇 |
免费 | 21129篇 |
国内免费 | 1355篇 |
专业分类
化学 | 286511篇 |
晶体学 | 6552篇 |
力学 | 20734篇 |
综合类 | 13篇 |
数学 | 53595篇 |
物理学 | 135110篇 |
出版年
2023年 | 4494篇 |
2021年 | 5995篇 |
2020年 | 8233篇 |
2019年 | 6597篇 |
2018年 | 7886篇 |
2017年 | 6305篇 |
2016年 | 13740篇 |
2015年 | 10360篇 |
2014年 | 12902篇 |
2013年 | 24967篇 |
2012年 | 18847篇 |
2011年 | 20655篇 |
2010年 | 16665篇 |
2009年 | 16395篇 |
2008年 | 18923篇 |
2007年 | 18643篇 |
2006年 | 16819篇 |
2005年 | 15009篇 |
2004年 | 13910篇 |
2003年 | 12225篇 |
2002年 | 12061篇 |
2001年 | 13581篇 |
2000年 | 10178篇 |
1999年 | 8014篇 |
1998年 | 6657篇 |
1997年 | 6474篇 |
1996年 | 6243篇 |
1995年 | 5656篇 |
1994年 | 5518篇 |
1993年 | 5442篇 |
1992年 | 5956篇 |
1991年 | 6024篇 |
1990年 | 5781篇 |
1989年 | 5576篇 |
1988年 | 5638篇 |
1987年 | 5514篇 |
1986年 | 5222篇 |
1985年 | 6729篇 |
1984年 | 6873篇 |
1983年 | 5452篇 |
1982年 | 5565篇 |
1981年 | 5576篇 |
1980年 | 5217篇 |
1979年 | 5570篇 |
1978年 | 5738篇 |
1977年 | 5715篇 |
1976年 | 5701篇 |
1975年 | 5388篇 |
1974年 | 5337篇 |
1973年 | 5193篇 |
排序方式: 共有10000条查询结果,搜索用时 26 毫秒
11.
Dominik Vítek Prof. Aleš Růžička Lise Vermeersch Dr. Libor Dostál Dr. Jan Turek Prof. Roman Jambor 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(70):e202202639
Reactivity studies of the GeII→B complex L(Cl)Ge⋅BH3 ( 1 ; L=2-Et2NCH2-4,6-tBu2-C6H2) were performed to determine the effect on the GeII→B donation. N-coordinated compounds L(OtBu)Ge⋅BH3 ( 2 ) and [LGe⋅BH3]2 ( 3 ) were prepared. The possible tuning of the GeII→B interaction was proved experimentally, yielding compounds 1-PPh2-8-(LGe)-C10H6 ( 4 ) and L(Cl)Ge⋅GaCl3 ( 5 ) without a GeII→B interaction. In 5 , an unprecedented GeII→Ga coordination was revealed. The experimental results were complemented by a theoretical study focusing on the bonding in 1 − 5 . The different strength of the GeII→E (E=B, Ga) donation was evaluated by using energy decomposition analysis. The basicity of different L(X)Ge groups through proton affinity is also assessed. 相似文献
12.
Dr. Kyung-Seok Kang Dr. Krishnan A. Iyer Prof. Dr. Jeffrey Pyun 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(35):e202200115
In this concept review, the fundamental and polymerization chemistry of inverse vulcanization for the preparation of statistical and segmented sulfur copolymers, which have been actively developed and advanced in various applications over the past decade is discussed. This concept review delves into a discussion of step-growth polymerization constructs to describe the inverse vulcanization process and discuss prepolymer approaches for the synthesis of segmented sulfur polyurethanes. Furthermore, this concept review discusses the advantages of inverse vulcanization in conjunction with dynamic covalent polymerization and post-polymerization modifications to prepare segmented block copolymers with enhanced thermomechanical and flame retardant properties of these materials. 相似文献
13.
Giang Truong Nguyen Prof. Dr. Liviu Ungur 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(30):e202200227
Employing radical bridges between anisotropic metal ions has been a viable route to achieve high-performance single-molecule magnets (SMMs). While the bridges have been mainly considered for their ability to promote exchange interactions, the crystal-field effect arising from them has not been taken into account explicitly. This lack of consideration may distort the understanding and limit the development of the entire family. To shed light on this aspect, herein we report a theoretical investigation of a series of N -radical-bridged diterbium complexes. It is found that while promoting strong exchange coupling between the terbium ions, the N -radical induces a crystal field that interferes destructively with that of the outer ligands, and thus reduces the overall SMM behavior. Based on the theoretical results, we conclude that the SMM behavior in this series could be further maximized if the crystal field of the outer ligands is designed to be collinear with that of the radical bridge. This conclusion can be generalized to all exchange-coupled SMMs. 相似文献
14.
Dr. Jordan Donat Mr. Patrick Dubourdeaux Dr. Martin Clémancey Dr. Julia Rendon Clara Gervasoni Mr. Morgan Barbier Jessica Barilone Dr. Jacques Pécaut Prof. Dr. Serge Gambarelli Prof. Dr. Pascale Maldivi Prof. Dr. Jean-Marc Latour 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(70):e202201875
Nitrene transfer reactions have emerged as one of the most powerful and versatile ways to insert an amine function to various kinds of hydrocarbon substrates. However, the mechanisms of nitrene generation have not been studied in depth albeit their formation is taken for granted in most cases without definitive evidence of their occurrence. In the present work, we compare the generation of tosylimido iron species and NTs transfer from FeII and FeIII precursors where the metal is embedded in a tetracarbene macrocycle. Catalytic nitrene transfer to reference substrates (thioanisole, styrene, ethylbenzene and cyclohexane) revealed that the same active species was at play, irrespective of the ferrous versus ferric nature of the precursor. Through combination of spectroscopic (UV-visible, Mössbauer), ESI-MS and DFT studies, an FeIV tosylimido species was identified as the catalytically active species and was characterized spectroscopically and computationally. Whereas its formation from the FeII precursor was expected by a two-electron oxidative addition, its formation from an FeIII precursor was unprecedented. Thanks to a combination of spectroscopic (UV-visible, EPR, Hyscore and Mössbauer), ESI-MS and DFT studies, we found that, when starting from the FeIII precursor, an FeIII tosyliodinane adduct was formed and decomposed into an FeV tosylimido species which generated the catalytically active FeIV tosylimide through a comproportionation process with the FeIII precursor. 相似文献
15.
Dr. Yolimar Gil Dr. Alejandro Castro-Alvarez Dr. Pablo Fuentealba Prof. Evgenia Spodine Dr. Daniel Aravena 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(48):e202200336
Enhancement of axial magnetic anisotropy is the central objective to push forward the performance of Single-Molecule Magnet (SMM) complexes. In the case of mononuclear lanthanide complexes, the chemical environment around the paramagnetic ion must be tuned to place strongly interacting ligands along either the axial positions or the equatorial plane, depending on the oblate or prolate preference of the selected lanthanide. One classical strategy to achieve a precise chemical environment for a metal centre is using highly structured, chelating ligands. A natural approach for axial-equatorial control is the employment of macrocycles acting in a belt conformation, providing the equatorial coordination environment, and leaving room for axial ligands. In this review, we present a survey of SMMs based on the macrocycle belt motif. Literature systems are divided in three families (crown ether, Schiff-base and metallacrown) and their general properties in terms of structural stability and SMM performance are briefly discussed. 相似文献
16.
Herraiz A. Gutierrez M. Ortega-Mier M. 《Central European Journal of Operations Research》2022,30(4):1427-1450
Central European Journal of Operations Research - We define a geometric transformation of Euclidean Travelling Salesman Problem (TSP) tours that leads to a new formulation of the TSP. For every... 相似文献
17.
Aequationes mathematicae - In this paper, we establish a new class of dynamic inequalities of Hardy’s type which generalize and improve some recent results given in the literature. More... 相似文献
18.
Yuki Shintani Taku Ohtomi Dr. Aya Shibata Dr. Yoshiaki Kitamura Koichiro M. Hirosawa Prof. Kenichi G. N. Suzuki Prof. Masato Ikeda 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(8):e202104421
Aqueous self-assembly of short peptides has attracted growing attention for the construction of supramolecular materials for various bioapplications. Herein, we describe how the thermolysin-assisted biocatalytic construction of a dipeptide hydrazide from an N-protected amino acid and an amino acid hydrazide leads to the formation of thermally stable supramolecular hydrogels. In addition, we demonstrate the post-assembly modification of the supramolecular architectures constructed in situ tethering hydrazide groups as a chemical handle by means of fluorescence imaging. 相似文献
19.
Journal of Structural Chemistry - Atomic and electronic structures of cyclic organosilicon compound 9,9,10,10-tetraethynyl-9,10-dihydrodisilaanthracene are studied by the density functional theory.... 相似文献
20.
Filatova S. M. Guseva M. K. Bodrova T. G. Parshina D. V. Budanova U. A. Sebyakin Yu. L. 《Russian Journal of General Chemistry》2022,91(1):S13-S23
Russian Journal of General Chemistry - The review article traces the main trends of the synthetic approach to the solution of the problem of overcoming the resistance of pathogenic bacterial... 相似文献