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1.
Yang Wang Tsukasa Hasegawa Hidetoshi Matsumoto Tsuyoshi Michinobu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(34):12019-12028
The direct arylation polycondensation (DArP) appeared as an efficient method for producing semiconducting polymers but often requires acceptor monomers with orienting or activating groups for the reactive carbon‐hydrogen (C‐H) bonds, which limits the choice of acceptor units. In this study, we describe a DArP for producing high‐molecular‐weight all‐acceptor polymers composed of the acceptor monomers without any orienting or activating groups via a modified method using Pd/Cu co‐catalysts. We thus obtained two isomeric all‐acceptor polymers, P1 and P2, which have the same backbone and side‐chains but different positions of the nitrogen atoms in the thiazole units. This subtle change significantly influences their optoelectronic, molecular packing, and charge‐transport properties. P2 with a greater backbone torsion has favorable edge‐on orientations and a high electron mobility μe of 2.55 cm2 V?1 s?1. Moreover, P2‐based transistors show an excellent shelf‐storage stability in air even after the storage for 1 month. 相似文献
2.
A.?N.?LipatnikovEmail authorView authors OrcID profile V.?A.?Sabelnikov N.?Chakraborty S.?Nishiki T.?Hasegawa 《Flow, Turbulence and Combustion》2018,100(1):75-92
The present work aims at modeling the entire convection flux \(\overline {\rho \mathbf {u}W}\) in the transport equation for a mean reaction rate \(\overline {\rho W}\) in a turbulent flow, which (equation) was recently put forward by the present authors. In order to model the flux, several simple closure relations are developed by introducing flow velocity conditioned to reaction zone and interpolating this velocity between two limit expressions suggested for the leading and trailing edges of the mean flame brush. Subsequently, the proposed simple closure relations for \(\overline {\rho \mathbf {u}W}\) are assessed by processing two sets of data obtained in earlier 3D Direct Numerical Simulation (DNS) studies of adiabatic, statistically planar, turbulent, premixed, single-step-chemistry flames characterized by unity Lewis number. One dataset consists of three cases characterized by different density ratios and is associated with the flamelet regime of premixed turbulent combustion. Another dataset consists of four cases characterized by different low Damköhler and large Karlovitz numbers. Accordingly, this dataset is associated with the thin reaction zone regime of premixed turbulent combustion. Under conditions of the former DNS, difference in the entire, \(\overline {\rho {u}W}\), and mean, \(\tilde {u}\overline {\rho W}\), convection fluxes is well pronounced, with the turbulent flux, \(\overline {\rho u^{\prime \prime }W^{\prime \prime }}\), showing countergradient behavior in a large part of the mean flame brush. Accordingly, the gradient diffusion closure of the turbulent flux is not valid under such conditions, but some proposed simple closure relations allow us to predict the entire flux \(\overline {\rho \mathbf {u}W}\) reasonably well. Under conditions of the latter DNS, the difference in the entire and mean convection fluxes is less pronounced, with the aforementioned simple closure relations still resulting in sufficiently good agreement with the DNS data. 相似文献
3.
Amphiphilic liquid‐crystalline 4‐miktoarm star copolymers with a siloxane junction leading to cylindrically nanostructured templates for a siloxane‐based nanodot array 下载免费PDF全文
Md Asadul Hoque Hideaki Komiyama Hiroki Nishiyama Keiji Nagai Takehiro Kawauchi Tomokazu Iyoda 《Journal of polymer science. Part A, Polymer chemistry》2016,54(9):1175-1188
Well‐defined A3B‐, A2B2‐, and AB3‐type 4‐miktoarm star copolymers (Mn = 10,500–16,200, Mw/Mn = 1.16–1.18) consisting of poly(ethylene oxide) (PEO) and polymethacrylate bearing an azobenzene mesogen (PMA(Az)) as the arms and cyclotetrasiloxane as the core unit were synthesized using a combined route composed of a thiol‐ene click reaction and atom transfer radical polymerization. Microphase‐separated structures of the star copolymers in thin films with a thickness of approximately 100 nm were investigated by GISAXS and TEM. The A3B‐type star‐(PEO)3[PMA(Az)]1 copolymer formed a more highly ordered PEO cylinder array with perpendicular alignment in the PMA(Az) matrix than that of the corresponding linear‐type block copolymer. The center‐to‐center distance of the PEO cylinders and the cylinder diameter were 13 and 4 nm, respectively. The highly ordered star‐(PEO)3[PMA(Az)]1 thin film was directly transferred to a siloxane‐based nanodot array by oxygen reactive ion etching. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1175–1188 相似文献
4.
Pd‐initiated polymerization of diazo compounds bearing dialkoxyphosphinyl group and hydrolysis of the resulting polymers and oligomers to afford phosphonic acid‐containing products 下载免费PDF全文
Hiroaki Shimomoto Akira Oda Motoki Kanayama Tomoya Sako Tomomichi Itoh Eiji Ihara Naohiro Hoshikawa Akihiko Koiwai Naoki Hasegawa 《Journal of polymer science. Part A, Polymer chemistry》2016,54(12):1742-1751
Pd‐initiated polymerization and oligomerization of diazo compounds containing a dialkoxyphosphinyl group are described. Polymerization of 2‐dialkoxyphosphinylethyl diazoacetates with π‐allylPdCl‐based initiating systems afforded C? C main chain polymers bearing phosphonate on each main chain carbon atom. The quantitative transformation of the side chain phosphonate to phosphonic acid resulted in the formation of water soluble polymers having the acid groups accumulated around their main chains, although the carbonyl ester linkage in the side chain was cleaved via intramolecular acid‐assisted hydrolysis in water at 80 °C. Pd‐initiated oligomerization of diethyl diazomethylphosphonate yielded an oligomeric product bearing diethoxyphosphiny groups directly attached to its main chain carbons, with unexpected incorporation of azo group in the main chain framework. Hydrolysis of the phosphonate of the oligomer afforded a water‐soluble product, which was revealed to show higher proton conductivity than poly(vinylphosphonic acid) under certain conditions. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1742–1751 相似文献
5.
Synthesis,Structure, Optical,and Electrochemical Properties of Triple‐ and Quadruple‐Decker Co‐facial Tetrathiafulvalene Arrays 下载免费PDF全文
Dr. Masashi Hasegawa Dr. Ken‐ichi Nakamura Saki Tokunaga Yumi Baba Ryota Shiba Prof. Dr. Takashi Shirahata Prof. Dr. Yasuhiro Mazaki Prof. Dr. Yohji Misaki 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(29):10090-10101
Understanding the details of the electronic structure in face‐to‐face arranged tetrathiafulvalenes (TTFs) is very important for the design of supramolecular functional materials and superior conductive organic materials. This article is a comprehensive study of the interactions among columnar stacked TTFs using trimeric (trimer) and tetrameric (tetramer) TTFs linked by alkylenedithio groups (‐S(CH2)nS‐, n=1–4) as models of triple‐ and quadruple‐decker TTF arrays. Single‐crystal X‐ray analyses of neutral trimeric TTFs revealed that the three TTF moieties are oriented in a zigzag arrangement. Cyclic voltammetry measurements (CV) reveal that the trimer and tetramer exhibited diverse reversible redox processes with multi‐electron transfers, depending on the length of the ‐S(CH2)nS‐ units and substituents. The electronic spectra of the radical cations, prepared by electrochemical oxidation, showed charge resonance (CR) bands in the NIR/IR region (1630–1850 nm), attributed to a mixed valence (MV) state of the triple‐ and quadruple‐decker TTF arrays. In the trimeric systems, the dicationic state (+2; 0.66 cation per TTF unit) was found to be a stable state, whereas the monocationic state (+1) was not observed in the electronic spectra. In the tetrameric system, substituent‐dependent redox processes were observed. Moreover, π‐trimers and π‐tetramers, which show a significant Davydov blueshift in the spectra, are formed in the tricationic (trimer) and tetracationic (tetramer) state. In addition, these attractive interactions are strongly dependent on the length of the linkage unit. 相似文献
6.
7.
Dr. Yoko Hasegawa Dr. Thomas Cantin Dr. Jonathan Decaens Dr. Samuel Couve-Bonnaire Prof. Dr. André B. Charette Prof. Dr. Thomas Poisson Prof. Dr. Philippe Jubault 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(47):e202201438
The first diastereo- and enantioselective cyclopropanation reactions of electron-deficient allenes with donor-acceptor and diacceptor diazo reagents are described. The desired enantioenriched alkylidenecyclopropanes (ACPs) were obtained in high yields with high diastereo- and enantioselectivities in the presence of Rh2((S)-TCPTAD)4 or Rh2((R)-BTPCP)4 catalysts (up to 95 % yield, >95 : 5 d.r. and 99 : 1 e.r.). This methodology gave a direct access to ACPs bearing multiple electron-deficient substituents and allows to further expand the availability of ACPs chemistry. Interestingly, during the examination of the scope of this reaction, the asymmetric intramolecular C−H insertion reaction into tert-butyl group was observed as a side reaction with up to 94 : 6 e.r. 相似文献
8.
Dr. Manussada Ratanasak Takumi Murata Taishin Adachi Prof. Jun-ya Hasegawa Prof. Tadashi Ema 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(58):e202202210
BPh3 catalyzes the N-methylation of secondary amines and the C-methylenation (methylene-bridge formation between aromatic rings) of N,N-dimethylanilines or 1-methylindoles in the presence of CO2 and PhSiH3; these reactions proceed at 30–40 °C under solvent-free conditions. In contrast, B(C6F5)3 shows little or no activity. 11B NMR spectra suggested the generation of [HBPh3]−. The detailed mechanism of the BPh3-catalyzed N-methylation of N-methylaniline ( 1 ) with CO2 and PhSiH3 was studied by using DFT calculations. BPh3 promotes the conversion of two substrates (N-methylaniline and CO2) into a zwitterionic carbamate to give three-component species [Ph(Me)(H)N+CO2−⋅⋅⋅BPh3]. The carbamate and BPh3 act as the nucleophile and Lewis acid, respectively, for the activation of PhSiH3 to generate [HBPh3]−, which is used to produce key CO2-derived species, such as silyl formate and bis(silyl)acetal, essential for the N-methylation of 1 . DFT calculations also suggested other mechanisms involving water for the generation of [HBPh3]− species. 相似文献
9.
Dr. Masashi Hasegawa Chika Hasegawa Yuki Nagaya Prof. Dr. Kazunori Tsubaki Prof. Dr. Yasuhiro Mazaki 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(59):e202202218
Chiral macrocyclic dimers, trimers, and tetramers composed of paraphenylene and tethered binaphthyl were synthesized, and their molecular structures and chiroptical properties were investigated. X-ray analysis and theoretical calculations revealed that multiple twisted molecular structures – dimers, trimers, and tetramers – adopt figure-of-eight, Möbius triangle, and concave rectangle structures, respectively. These homologues have large ϵ values in their UV-vis absorption spectra because of the π-conjugation of the naphthalene-phenylene-naphthalene frameworks. Owing to the shape-persistent ring structure and tethering with −OCH2CH2O−, high fluorescence quantum yields and a relatively high dissymmetry factor gCPL in circularly polarized luminescence (CPL) spectra were achieved. This results in CPL brightness (BCPL) of over 100, which is greater than that of the conventional organic CPL dye. 相似文献
10.
Masamura Shinnosuke Iwamoto Tetsu Sugitani Yoshiki Konishi Keiji Hara Naoyuki 《Nonlinear dynamics》2020,99(4):3155-3168
Nonlinear Dynamics - The present study experimentally investigates amplitude death in delay-coupled double-scroll circuits with a time-varying network topology that randomly changes at a regular... 相似文献