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891.
Markus Suta Flavie Lavoie‐Cardinal Claudia Wickleder 《Angewandte Chemie (International ed. in English)》2020,59(27):10949-10954
Inorganic hosts, such as SrB4O7 or certain nitrides, intrinsically stabilize Eu2+ even when the dopant is an Eu3+‐based precursor and reducing conditions are not employed in the synthesis. Although this concept is well known in the synthesis of phosphorescent materials, the mechanistic details are scarcely understood. Herein, we demonstrate that trapped charge carriers, such as color centers, can also act as redox partners to stabilize certain oxidation states of activators. Eu‐activated CsMgCl3 and CsMgBr3 are used as examples. Upon doping with EuCl3 and in the absence of reducing conditions during the synthesis, dominant cyan or green luminescence from Eu2+ ions was observed. Photoluminescence spectroscopy at 10 K revealed that the reduction is correlated to color centers localized at defects. Although defects are typically undesired in phosphors, we have shown that their role may be underestimated and they could be used on purpose in the preparation of selected inorganic phosphors. 相似文献
892.
Yiyuan Han Zhixing Lin Jiajing Zhou Gyeongwon Yun Rui Guo Joseph J. Richardson Frank Caruso 《Angewandte Chemie (International ed. in English)》2020,59(36):15618-15625
Functional materials composed of proteins have attracted much interest owing to the inherent and diverse functionality of proteins. However, establishing general techniques for assembling proteins into nanomaterials is challenging owing to the complex physicochemical nature and potential denaturation of proteins. Here, a simple, versatile strategy is introduced to fabricate functional protein assemblies through the interfacial assembly of proteins and polyphenols (e.g., tannic acid) on various substrates (organic, inorganic, and biological). The dominant interactions (hydrogen‐bonding, hydrophobic, and ionic) between the proteins and tannic acid were elucidated; most proteins undergo multiple noncovalent stabilizing interactions with polyphenols, which can be used to engineer responsiveness into the assemblies. The proteins retain their structure and function within the assemblies, thereby enabling their use in various applications (e.g., catalysis, fluorescence imaging, and cell targeting). 相似文献
893.
Juan M. Venegas Zisheng Zhang Theodore O. Agbi William P. McDermott Anastassia Alexandrova Ive Hermans 《Angewandte Chemie (International ed. in English)》2020,59(38):16527-16535
Boron‐containing materials, and in particular boron nitride, have recently been identified as highly selective catalysts for the oxidative dehydrogenation of alkanes such as propane. To date, no mechanism exists that can explain both the unprecedented selectivity, the observed surface oxyfunctionalization, and the peculiar kinetic features of this reaction. We combine catalytic activity measurements with quantum chemical calculations to put forward a bold new hypothesis. We argue that the remarkable product distribution can be rationalized by a combination of surface‐mediated formation of radicals over metastable sites, and their sequential propagation in the gas phase. Based on known radical propagation steps, we quantitatively describe the oxygen pressure‐dependent relative formation of the main product propylene and by‐product ethylene. Free radical intermediates most likely differentiate this catalytic system from less selective vanadium‐based catalysts. 相似文献
894.
Florian A. Mann Niklas Herrmann Felipe Opazo Sebastian Kruss 《Angewandte Chemie (International ed. in English)》2020,59(40):17732-17738
Single‐walled carbon nanotubes (SWCNTs) are a 1D nanomaterial that shows fluorescence in the near‐infrared (NIR, >800 nm). In the past, covalent chemistry was less explored to functionalize SWCNTs as it impairs NIR emission. However, certain sp3 defects (quantum defects) in the carbon lattice have emerged that preserve NIR fluorescence and even introduce a new, red‐shifted emission peak. Here, we report on quantum defects, introduced using light‐driven diazonium chemistry, that serve as anchor points for peptides and proteins. We show that maleimide anchors allow conjugation of cysteine‐containing proteins such as a GFP‐binding nanobody. In addition, an Fmoc‐protected phenylalanine defect serves as a starting point for conjugation of visible fluorophores to create multicolor SWCNTs and in situ peptide synthesis directly on the nanotube. Therefore, these quantum defects are a versatile platform to tailor both the nanotube's photophysical properties as well as their surface chemistry. 相似文献
895.
AbstractEffective extraction of phyto-biomolecules insures retaining maximum functionality along with higher recovery. In this study, ultrasound-solvent assisted extraction (USAE) was employed for optimal extraction of phyto-biomolecules from Sesamum indicum (sesame) leaves using the approach of Response Surface Methodology (RSM). The optimized condition of 200?W power, 59% methanol concentration with 1:14?g/mL solid–liquid ratio and 15?min of extraction time yielded 367.39?±?1.85?mg GAE/100?g of total phenolic content, 96.72?±?3.27% of free radical scavenging activity and 81.20?±?2.87% of iron chelating activity respectively. The extract consist of essential phytocomponents like gallic acid, chlorogenic acid, and quercetin with lipid peroxidation activities of >50% over incubation time of 48?h. Also, showed antimicrobial activity against various Gram’s negative and positive food borne pathogens. The results of this study implied the importance of USAE for effective and optimum recovery of phyto-biomolecules from Sesame leaves with retained functional properties. 相似文献
896.
Siyuan Li Weidong Zhang Qiang Wu Lei Fan Xinyang Wang Xiao Wang Zeyu Shen Yi He Yingying Lu 《Angewandte Chemie (International ed. in English)》2020,59(35):14935-14941
A rechargeable Li metal anode coupled with a high‐voltage cathode is a promising approach to high‐energy‐density batteries exceeding 300 Wh kg?1. Reported here is an advanced dual‐additive electrolyte containing a unique solvation structure and it comprises a tris(pentafluorophenyl)borane additive and LiNO3 in a carbonate‐based electrolyte. This system generates a robust outer Li2O solid electrolyte interface and F‐ and B‐containing conformal cathode electrolyte interphase. The resulting stable ion transport kinetics enables excellent cycling of Li/LiNi0.8Mn0.1Co0.1O2 for 140 cycles with 80 % capacity retention under highly challenging conditions (≈295.1 Wh kg?1 at cell‐level). The electrolyte also exhibits high cycling stability for a 4.6 V LiCoO2 (160 cycles with 89.8 % capacity retention) cathode and 4.95 V LiNi0.5Mn1.5O4 cathode. 相似文献
897.
Samuel Stolz Marco Di Giovannantonio Jos I. Urgel Qiang Sun Amogh Kinikar Gabriela Borin Barin Max Bommert Roman Fasel Roland Widmer 《Angewandte Chemie (International ed. in English)》2020,59(33):14106-14110
In the emerging field of on‐surface synthesis, dehalogenative aryl–aryl coupling is unarguably the most prominent tool for the fabrication of covalently bonded carbon‐based nanomaterials. Despite its importance, the reaction kinetics are still poorly understood. Here we present a comprehensive temperature‐programmed x‐ray photoelectron spectroscopy investigation of reaction kinetics and energetics in the prototypical on‐surface dehalogenative polymerization of 4,4′′‐dibromo‐p‐terphenyl into poly(para‐phenylene) on two coinage metal surfaces, Cu(111) and Au(111). We find clear evidence for reversible dehalogenation on Au(111), which is inhibited on Cu(111) owing to the formation of organometallic intermediates. The incorporation of reversible dehalogenation in the reaction rate equations leads to excellent agreement with experimental data and allows extracting the relevant energy barriers. Our findings deepen the mechanistic understanding and call for its reassessment for surface‐confined aryl–aryl coupling on the most frequently used metal substrates. 相似文献
898.
Dr. Ryohei Yasukuni Prof. Nordin Félidj Dr. Leïla Boubekeur-Lecaque Stéphanie Lau-Truong Prof. Jean Aubard 《Chemphyschem》2020,21(22):2614-2619
Localized surface plasmon resonance (LSPR) excitation on the photochromic reaction of a diarylethene derivative (DE) was studied by surface enhanced Raman scattering (SERS). UV and visible light irradiations transform reversibly DE between open-form (OF) and closed-form (CF) isomers, respectively. A mixture of PMMA and DE (either OF or CF isomer) was spin-coated onto gold nanorods (GNRs) arrays, designed by electron beam lithography, with two localized surface plasmon resonances (LSPR) at distinct wavelengths, due to their anisotropy. The photochromic reaction rates from CF to OF isomers, under LSPR excitation, were monitored from SERS spectral changes under different polarizations, on the same GNR substrate to compare the effect of LSPR field strength. It appears that the photoisomerization rate was faster when LSPR was excited with the polarization parallel to the GNR long axis. The present results highlight a potential genuine mechanism, from near field LSPR excitation, involved in the photochromic enhancement of diarylethene photochromes. 相似文献
899.
Dr. Juliana Arriel Torres Dr. Gelson T. S. T. Da Silva Dr. Fernando Barbosa de Freitas Silva Dr. Caue Ribeiro 《Chemphyschem》2020,21(21):2392-2396
Tin dioxide (SnO2) has intrinsic characteristics that do not favor its photocatalytic activity. However, we evidenced that surface modification can positively influence its performance for CO2 photoreduction in the gas phase. The hydroxylation of the SnO2 surface played a role in the CO2 affinity decreasing its reduction potential. The results showed that a certain selectivity for methane (CH4), carbon monoxide (CO), and ethylene (C2H4) is related to different SnO2 hydrothermal annealing. The best performance was seen for SnO2 annealed at 150 °C, with a production of 20.4 μmol g−1 for CH4 and 16.45 μmol g−1 for CO, while for SnO2 at 200 °C the system produced more C2H4, probably due to a decrease of surface −OH groups. 相似文献
900.
Laurence Muhr Steve Pontvianne Katalin Selmeczi Cdric Paris Sandrine Boschi‐Muller Laetitia Canabady‐Rochelle 《Journal of separation science》2020,43(11):2031-2041
Some metal‐chelating peptides have antioxidant properties, with potential nutrition, health, and cosmetics applications. This study aimed to simulate their separation on immobilized metal ion affinity chromatography from their affinity constant for immobilized metal ion determined in surface plasmon resonance, both technics are based on peptide‐metal ion interactions. In our approach, first, the affinity constant of synthetic peptides was determined by surface plasmon resonance and used as input data to numerically simulate the chromatographic separation with a transport‐dispersive model based on Langmuir adsorption isotherm. Then, chromatographic separation was applied on the same peptides to determine their retention time and compare this experimental tR with the simulated tR obtained from simulation from surface plasmon resonance data. For the investigated peptides, the relative values of tR were comparable. Hence, our study demonstrated the pertinence of such numerical simulation correlating immobilized metal ion affinity chromatography and surface plasmon resonance. 相似文献