全文获取类型
收费全文 | 1734篇 |
免费 | 73篇 |
国内免费 | 12篇 |
专业分类
化学 | 1190篇 |
晶体学 | 1篇 |
力学 | 55篇 |
数学 | 226篇 |
物理学 | 347篇 |
出版年
2024年 | 6篇 |
2023年 | 20篇 |
2022年 | 47篇 |
2021年 | 57篇 |
2020年 | 66篇 |
2019年 | 60篇 |
2018年 | 40篇 |
2017年 | 33篇 |
2016年 | 87篇 |
2015年 | 68篇 |
2014年 | 71篇 |
2013年 | 103篇 |
2012年 | 113篇 |
2011年 | 143篇 |
2010年 | 67篇 |
2009年 | 94篇 |
2008年 | 117篇 |
2007年 | 113篇 |
2006年 | 105篇 |
2005年 | 93篇 |
2004年 | 63篇 |
2003年 | 41篇 |
2002年 | 55篇 |
2001年 | 12篇 |
2000年 | 22篇 |
1999年 | 15篇 |
1998年 | 10篇 |
1997年 | 11篇 |
1996年 | 13篇 |
1995年 | 8篇 |
1994年 | 7篇 |
1993年 | 8篇 |
1992年 | 2篇 |
1991年 | 3篇 |
1990年 | 6篇 |
1989年 | 5篇 |
1988年 | 4篇 |
1987年 | 6篇 |
1986年 | 2篇 |
1985年 | 5篇 |
1984年 | 4篇 |
1982年 | 1篇 |
1981年 | 4篇 |
1979年 | 2篇 |
1977年 | 1篇 |
1976年 | 3篇 |
1973年 | 1篇 |
1972年 | 1篇 |
1944年 | 1篇 |
排序方式: 共有1819条查询结果,搜索用时 9 毫秒
91.
Alejandro Benítez Johan J. SánchezMaría L. Arnal Alejandro J. Müller 《Polymer Degradation and Stability》2013
The mechanical properties of two linear low density and low density polyethylenes containing a pro-oxidant additive were monitored during accelerated aging (60 °C in a convection oven) and weather exposure. Tearing tests (trouser) were performed for the first time in polyethylenes subjected to oxo-degradation revealing a transition from an extensible to a non-extensible material, at exposure times when standard tensile tests were not able to detect any changes in the materials. The essential work of fracture (EWF) technique was also applied and the results were in agreement with those of trouser tests. The specific essential work of fracture first increased with exposure time until the sample experienced a transition to a less ductile state where EWF was no longer applicable. EWF and trouser tear tests were more sensitive detecting the onset of degradation probably because they employ notched specimens that impose more critical stress concentration conditions than conventional tensile tests. 相似文献
92.
Freiría A Bastida R del Carmen Fernández-Fernández M Macías A Valencia L Vicente M 《Inorganic chemistry》2005,44(4):930-934
We report here the first pentanuclear Ba(II) complex of a new tri-aza, tri-oxa macrocycle with two carboxymethyl "arms" pending from two N atoms, H2L2. The crystal structure corresponds to the formula [Ba5(H0.375L2)4(ClO4)(CH3CH2OH)(H2O)2](ClO4)2.5 x 9.5H2O and reveals the presence of four molecules of the ligand surrounding five Ba(II) ions, giving rise to an unusual structure with the metal ions inside a spherical organic cavity. 相似文献
93.
Alejandro Manchado Mercedes García Mateo M. Salgado David Díez Narciso M. Garrido 《Tetrahedron》2018,74(38):5240-5247
A novel 1,4-Phenyl radical rearrangement (1,4-PhRR) is described in a typical Barton decarboxylation procedure. While carrying out this reaction in presence of a N,N-disubstituted β-amino acid derivative, the decarboxyphenyl rearranged derivative is obtained, as well as in presence of β-N,N-acylamide. On the other hand, secondary amines give the β-lactam derivative without rearrangement, as well as N-Fmoc derivatives give the normal decarboxylation reaction. In regards of amines which are far away from the carboxylic group, such as δ-amino acid derivatives, the reaction occur through a typical Barton decarboxylation without rearrangement. The diversity of the reaction proves synthetic usefulness paving the way to interesting biologically active compounds. 相似文献
94.
Alejandro Valverde Amira ben Hassine Vernica Serafín Cristina Muoz‐San Martín María Pedrero María Garranzo‐Asensio Maria Gamella Noureddine Raouafi Rodrigo Barderas Paloma Yez‐Sedeo Susana Campuzano Jos M. Pingarrn 《Electroanalysis》2020,32(4):706-714
This paper reports the development of a dual immunosensor using magnetic microcarriers (MBs) and amperometric transduction at dual screen‐printed carbon electrodes (SPdCEs) for the simultaneous determination of two biomarkers: interleukin‐13 receptor α2 (IL‐13Rα2) and E‐cadherin (E‐CDH), with both extracellular and soluble fraction; oncogenic and tumor suppressor markers, respectively, of great relevance in metastatic processes. The implemented methodology involved the formation of sandwich‐type immunocomplexes using specific capture antibodies immobilized onto carboxylic acid magnetic microbeads (HOOC‐MBs), and biotinylated detector antibodies labeled with streptavidin?horseradish peroxidase conjugates (Strep‐HRP). The amperometric detection was performed by addition of hydrogen peroxide in the presence of hydroquinone (HQ) as the redox mediator. The dual immunosensing platform provided linear calibration ranges suitable for the determination of both biomarkers in liquid and solid clinical specimens as well as excellent selectivity against other cancer biomarkers. This simple handling dual bioplatform was applied to the determination of the soluble and extracellular fraction of the target biomarkers in serum and paraffined‐embedded tissues from colorectal cancer (CRC) patients diagnosed at different tumor grade. The obtained results reveal great potential of this configuration to improve the reliability in diagnosing metastatic CRC. 相似文献
95.
Dr. Reiko Ueoka Dr. Roy A. Meoded Alejandro Gran-Scheuch Dr. Agneya Bhushan Prof. Dr. Marco W. Fraaije Prof. Dr. Jörn Piel 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(20):7835-7839
Bacterial trans-acyltransferase polyketide synthases (trans-AT PKSs) are multimodular megaenzymes that biosynthesize many bioactive natural products. They contain a remarkable range of domains and module types that introduce different substituents into growing polyketide chains. As one such modification, we recently reported Baeyer–Villiger-type oxygen insertion into nascent polyketide backbones, thereby generating malonyl thioester intermediates. In this work, genome mining focusing on architecturally diverse oxidation modules in trans-AT PKSs led us to the culturable plant symbiont Gynuella sunshinyii, which harbors two distinct modules in one orphan PKS. The PKS product was revealed to be lobatamide A, a potent cytotoxin previously only known from a marine tunicate. Biochemical studies show that one module generates glycolyl thioester intermediates, while the other is proposed to be involved in oxime formation. The data suggest varied roles of oxygenation modules in the biosynthesis of polyketide scaffolds and support the importance of trans-AT PKSs in the specialized metabolism of symbiotic bacteria. 相似文献
96.
Silvia Gimnez-Santamarina Salvador Cardona-Serra Juan M. Clemente-Juan Alejandro Gaita-Ario Eugenio Coronado 《Chemical science》2020,11(39):10718
Molecular spin qubits are chemical nanoobjects with promising applications that are so far hampered by the rapid loss of quantum information, a process known as decoherence. A strategy to improve this situation involves employing so-called Clock Transitions (CTs), which arise at anticrossings between spin energy levels. At CTs, the spin states are protected from magnetic noise and present an enhanced quantum coherence. Unfortunately, these optimal points are intrinsically hard to control since their transition energy cannot be tuned by an external magnetic field; moreover, their resilience towards geometric distortions has not yet been analyzed. Here we employ a python-based computational tool for the systematic theoretical analysis and chemical optimization of CTs. We compare three relevant case studies with increasingly complex ground states. First, we start with vanadium(iv)-based spin qubits, where the avoided crossings are controlled by hyperfine interaction and find that these S = 1/2 systems are very promising, in particular in the case of vanadyl complexes in an L-band pulsed EPR setup. Second, we proceed with a study of the effect of symmetry distortions in a holmium polyoxotungstate of formula [Ho(W5O18)2]9− where CTs had already been experimentally demonstrated. Here we determine the relative importance of the different structural distortions that causes the anticrossings. Third, we study the most complicated case, a polyoxopalladate cube [HoPd12(AsPh)8O32]5− which presents an unusually rich ground spin multiplet. This system allows us to find uniquely favorable CTs that could nevertheless be accessible with standard pulsed EPR equipment (X-band or Q-band) after a suitable chemical distortion to break the perfect cubic symmetry. Since anticrossings and CTs constitute a rich source of physical phenomena in very different kinds of quantum systems, the generalization of this study is expected to have impact not only in molecular spin science but also in other related fields such as molecular photophysics and photochemistry.We employ a python computational tool to compare 3 relevant case studies with increasingly complex ground states: vanadyl complexes, Ho(iii) square antiprisms and Ho(iii) cubic structures. 相似文献
97.
José L. García Ruano Alejandro ParraLeyre Marzo Francisco YusteVirginia M. Mastranzo 《Tetrahedron》2011,67(16):2905-2910
Room temperature ultrasonic irradiation of neat mixtures of methyl sulfinates and primary or secondary amines (1.5 equiv) produced sulfinamides, which on m-CPBA oxidation (in dichloromethane) were converted into the corresponding sulfonamides. The two steps can be accomplished in one pot, in good overall yields, when using secondary amines, but primary amines give better sulfonamide yields when the peracid oxidation is effected on the purified sulfinamide. This constitutes a mild, efficient, and potentially scalable route to sulfonamides, which obviates the use of water sensitive, often lachrymatory sulfonyl chlorides and large reagent excesses. 相似文献
98.
A new variable selection algorithm is described, based on ant colony optimization (ACO). The algorithm aim is to choose, from a large number of available spectral wavelengths, those relevant to the estimation of analyte concentrations or sample properties when spectroscopic analysis is combined with multivariate calibration techniques such as partial least-squares (PLS) regression. The new algorithm employs the concept of cooperative pheromone accumulation, which is typical of ACO selection methods, and optimizes PLS models using a pre-defined number of variables, employing a Monte Carlo approach to discard irrelevant sensors. The performance has been tested on a simulated system, where it shows a significant superiority over other commonly employed selection methods, such as genetic algorithms. Several near infrared spectroscopic experimental data sets have been subjected to the present ACO algorithm, with PLS leading to improved analytical figures of merit upon wavelength selection. The method could be helpful in other chemometric activities such as classification or quantitative structure-activity relationship (QSAR) problems. 相似文献
99.
María Fernanda Manrique-de-la-Cuba Luis Leyva-Parra Diego Inostroza Prof. Badhin Gomez Dr. Alejandro Vásquez-Espinal Prof. Jorge Garza Dr. Osvaldo Yañez Prof. William Tiznado 《Chemphyschem》2021,22(10):906-910
We report the global minima structures of Li8Si8, Li10Si9, and Li12Si10 systems, in which silicon moieties maintain structural and chemical bonding characteristics similar to those of their building blocks: the aromatic clusters Td−Li4Si4 and C2v−Li6Si5. Electron counting rules, chemical bonding analysis, and magnetic response properties verify the silicon unit‘s aromaticity persistence. This study demonstrates the feasibility of assembling silicon-based nanostructures from aromatics clusters as building blocks. 相似文献
100.
Vicente M Bastida R Lodeiro C Macías A Parola AJ Valencia L Spey SE 《Inorganic chemistry》2003,42(21):6768-6779
The synthesis of a new oxaaza macrocyclic ligand, L, derived from O(1),O(7)-bis(2-formylphenyl)-1,4,7-trioxaheptane and tren containing an amine terminal pendant arm, and its metal complexation with alkaline earth (M = Ca(2+), Sr(2+), Ba(2+)), transition (M = Co(2+), Ni(2+), Cu(2+), Zn(2+), Cd(2+)), post-transition (M = Pb(2+)), and Y(3+) and lanthanide (M = La(3+), Er(3+)) metal ions are reported. Crystal structures of [H(2)L](ClO(4))(2).3H(2)O, [PbL](ClO(4))(2), and [ZnLCl](ClO(4)).H(2)O are also reported. In the [PbL] complex, the metal ion is located inside the macrocyclic cavity coordinated by all N(4)O(3) donor atoms while, in the [ZnLCl] complex, the metal ion is encapsulated only by the nitrogen atoms present in the ligand. pi-pi interactions in the [H(2)L](ClO(4))(2).3H(2)O and [PbL](ClO(4))(2) structures are observed. Protonation and Zn(2+), Cd(2+), and Cu(2+) complexation were studied by means of potentiometric, UV-vis, and fluorescent emission measurements. The 10-fold fluorescence emission increase observed in the pH range 7-9 in the presence of Zn(2+) leads to L as a good sensor for this biological metal in water solution. 相似文献