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61.
《Angewandte Chemie (International ed. in English)》2017,56(51):16126-16134
The chemistry of gold strongly focuses on the ubiquitous oxidation states +I and +III. The intermediate oxidation state +II is generally avoided in mononuclear gold species. In recent years, gold(II) has been increasingly suggested as a key intermediate in artificial photosynthesis systems, with gold(III) moieties acting as electron acceptors, as well as in gold‐catalyzed photoredox catalysis and radical chemistry. This Minireview provides a concise summary of confirmed and characterized mononuclear open‐shell gold(II) complexes. Recent findings on structural motifs and reactivity patterns will be discussed. Exciting developments in the fields of photosynthesis, photocatalysis, and potential roles in medicinal chemistry will be outlined. 相似文献
62.
《Angewandte Chemie (International ed. in English)》2017,56(15):4356-4360
The stabilization of high oxidation state nanoparticles by N‐heterocyclic carbenes is reported. Such nanoparticles represent an important subset in the field of nanoparticles, with different and more challenging requirements for suitable ligands compared to elemental metal nanoparticles. N‐Heterocyclic carbene coated NaYF4:Yb,Tm upconversion nanoparticles were synthesized by a ligand‐exchange reaction from a well‐defined precursor. This new photoactive material was characterized in detail and employed in the activation of photoresponsive molecules by low‐intensity near‐infrared light (λ =980 nm). 相似文献
63.
《Angewandte Chemie (International ed. in English)》2017,56(20):5598-5602
Owing to the difficulty in comprehensively characterizing nanocrystal (NC) surfaces, clear guidance for ligand design is lacking. In this work, a series of bidentate bis(pyridine) anthracene isomers (2,3‐PyAn, 3,3‐PyAn, 2,2‐PyAn) that differ in their binding geometries were designed to find the best complementary fit to the NC surface. The efficiency of triplet energy transfer (TET) from the CdSe NC donor to a diphenylanthracene (DPA) acceptor mediated by these isomers was used as a proxy for the efficacy of orbital overlap and therefore ligand binding. 2,3‐PyAn, with an intramolecular N–N distance of 8.2 Å, provided the best match to the surface of CdSe NCs. When serving as a transmitter for photon upconversion, 2,3‐PyAn yielded the highest upconversion quantum yield (QY) of 12.1±1.3 %, followed by 3,3‐PyAn and 2,2‐PyAn. The TET quantum efficiencies determined by ultrafast transient absorption measurements showed the same trend. 相似文献
64.
65.
Dr. Linda Iffland-Mühlhaus Dr. Beatrice Battistella Dr. Daniel Siegmund Prof. Dr. Kallol Ray Prof. Dr. Ulf-Peter Apfel 《欧洲无机化学杂志》2023,26(30):e202300418
Cobalt complexes are extensively studied as bioinspired models for non-heme oxygenases as they facilitate both the stabilization and characterization of metal-oxygen intermediates. As an analog to the well-known Co(cyclam) complex Co{N4} (cyclam=1,4,8,11-tetraazacyclotetradecane), the CoII complex Co{i-N4} with the isomeric isocyclam ligand (isocyclam=1,4,7,11-tetraazacyclotetradecane) was synthesized and characterized. Despite the identical N4 donor set of both complexes, Co{i-N4} enables the 2e−/2H+ reduction of O2 with a lower overpotential (ηeff of 385 mV vs. 540 mV for Co{N4} ), albeit with a diminished turnover frequency. Characterization of the intermediates formed upon O2 activation of Co{i-N4} reveals a structurally identified stable μ-peroxo CoIII dimer as the main product. A superoxo CoIII species is also formed as a minor product, as indicated by EPR spectroscopy. In further reactivity studies, the electrophilicity of these in situ generated Co−O2 species was demonstrated by the oxidation of the O−H bond of TEMPO−H (2,2,6,6-tetramethylpiperidin-1-ol) via a H atom abstraction process. Unlike the known Co(cyclam), Co{i-N4} can be employed in oxygen atom transfer reactions oxidizing triphenylphosphine to the corresponding phosphine oxide highlighting the impact of geometrical modifications of the ligand while preserving the ring size and donor atom set on the reactivity of biomimetic oxygen activating complexes. 相似文献
66.
Since the discovery of left-handed G-quadruplex (L-G4) structure formed by natural DNA, there has been a growing interest in its potential functions. This study utilised it to catalyse enantioselective Diels-Alder reactions, considering its different optical rotation compared to an ordinary G4. It was determined that when L-G4 was used with a combination of copper(II) ions, there was a good enantioselectivity (?52% ee) without further addition of ligands. When further consideration was given by adding G4 ligands, G4 was further stabilised, even obtaining a better enantioselectivity (up to ?80% ee). Moreover, when using ligands that have regulatory effects on G4, the ee value can be adjusted. In this work, a minimal left-handed G4 was reported. A follow-up study was also conducted, which recovers that the minimal left-handed G4 remains its catalytic effect and enantioselectivity, but is not so effective as the former case. This indicates that a complete G4 structure is relatively conducive to chiral catalysis. 相似文献
67.
针对大学本科一年级基础化学如“化学概论”等课程教学中,学生对于不断出现的专业名词及物理化学含义的理解问题,以“焓”“熵”等外来词汇以及角动量l、能级分裂单位“Dq”等缩写为例,从专业名词来源开始讲解,使学生在学习过程中既知其然又知其所以然,更好地理解化学专业词汇,尤其是外来词汇的内涵与物理化学意义。 相似文献
68.
Dong-Yang Liu Xiao-Xia Ren Xiao-Min Ning Mei-Hua Lin Yuan-Di Wu Jing Qian 《无机化学与普通化学杂志》2021,647(1):8-14
To investigate the coordination chemistry of modbc (2-methyl-6-oxygen-1,6-dihydro-3,4'-bipyridine-5-carbonitrile) with ZnII and CdII salts under the solvothermal conditions, six new MOFs with the formulas [Zn(modbc)2(mpa)]n ( 1 ), [Zn(modbc)(mpa)(H2O)]n ( 2 ), [Zn(modbc)(pa)0.5(H2O)]n ( 3 ), [Cd(modbc)(pa)0.5(H2O)]n ( 4 ), [Zn(modbc)2(tpa)]n ( 5 ), and [Cd(modbc)2(pda)(H2O)]n ( 6 ) (mpa = m-phthalic acid; pa = pyromellitic acid; tpa = terephthalic acid; pda = pentane diacid) were successfully synthesized by solvothermal reaction and fully characterized by elemental analysis, IR spectroscopy, single crystal, powder X-ray diffraction, thermal and photoluminescence properties. Though MOFs 3 and 4 have the same structure, we have obtained three different kinds of coordination configurations by the X-ray diffration analysis. Compared with 1 and 2 , coordination water has no effect on the solid fluorescence emission of MOFs. It is worth noting that the fluorescence intensity of 3 containing central ZnII atoms is very strong, whereas that of isomorphism 4 containing central CdII atoms has almost no fluorescence emission, showing that metal ions have very important influence on the fluorescence emission. Further, we found that solvents had an important effect on the fluorescence emission in liquid fluorescence of MOFs 1 – 6 . 相似文献
69.
Metalation of CH2OH-substituted triazolium salts with CoCl2 under basic conditions affords C,O-bidentate chelating carbene Co(III) complexes ( 3a , 3b ), while analogous phenyl-substituted triazolium salts produce monodentate carbene Co(II) complexes ( 3c , 3d ). The distinct substituent-induced properties of the metal centers were demonstrated by electrochemical measurements and catalytic activities in two specific processes. The complexes showed appreciable activity in the reduction of C=O bonds through hydrosilylation, with methoxybenzene-functionalized triazolylidene Co(III) complex 3a achieving a high selectivity towards aldehydes vs. ketones with turnover frequencies (TOFs) up to 200 h−1. The C,O-chelate systems were also active catalysts in the Biginelli process, a one-step three-component reaction for efficient dihydropyrimidinone synthesis. Optimization of reaction conditions provides high activity with complex 3a , reaching TOFs of 800 h−1, the highest activity known for cobalt NHC complexes to date. 相似文献
70.
Jordan De Jesus Silva Niccolò Bartalucci Benson Jelier Samantha Grosslight Tobias Gensch Claas Schünemann Bernd Müller Paul C. J. Kamer Christophe Copéret Matthew S. Sigman Antonio Togni 《Helvetica chimica acta》2021,104(12):e2100200
A synthetic method for the palladium-catalyzed cyanation of aryl boronic acids using bench stable and non-toxic N-cyanosuccinimide has been developed. High-throughput experimentation facilitated the screen of 90 different ligands and the resultant statistical data analysis identified that ligand σ-donation, π-acidity and sterics are key drivers that govern yield. Categorization into three ligand groups – monophosphines, bisphosphines and miscellaneous – was performed before the analysis. For the monophosphines, the yield of the reaction increases for strong σ-donating, weak π-accepting ligands, with flexible pendant substituents. For the bisphosphines, the yield predominantly correlates with ligand lability. The applicability of the designed reaction to a wider substrate scope was investigated, showing good functional group tolerance in particular with boronic acids bearing electron-withdrawing substituents. This work outlines the development of a novel reaction, coupled with a fast and efficient workflow to gain understanding of the optimal ligand properties for the design of improved palladium cross-coupling catalysts. 相似文献