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11.
Nonlinear Dynamics - Classical method of Lyapunov exponents spectrum estimation for a n-th-order continuous-time, smooth dynamical system involves Gram–Schmidt orthonormalization and... 相似文献
12.
Dr. Maria Książek Dr. Marek Weselski Marcin Kaźmierczak Aleksandra Tołoczko Dr. Miłosz Siczek Dr. Piotr Durlak Dr. Juliusz A. Wolny Prof. Dr. Volker Schünemann Prof. Dr. Joachim Kusz Dr. Robert Bronisz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(63):14419-14434
Reaction of 1,2-di(tetrazol-2-yl)ethane (ebtz) with Fe(BF4)2⋅6 H2O in different nitriles yields one-dimensional coordination polymers [Fe(ebtz)2(RCN)2](BF4)2⋅nRCN (n=2 for R=CH3 ( 1 ) and n=0 for R=C2H5 ( 2 ) C3H7 ( 3 ), C3H5 ( 4 ), CH2Cl ( 5 )) exhibiting spin crossover (SCO). SCO in 1 and 3 – 5 is complete and occurs above 160 K. In 2 , it is shifted to lower temperatures and is accompanied by wide hysteresis (T1/2↓=78 K, T1/2↑=123 K) and proceeds extremely slowly. Isothermal (80 K) time-resolved single-crystal X-ray diffraction studies revealed a complex nature for the HS→LS transition in 2 . An initial, slow stage is associated with shrinkage of polymeric chains and with reduction of volume at 77 % (in relation to the difference between cell volumes VHS−VLS) whereas only 16 % of iron(II) ions change spin state. In the second stage, an abrupt SCO occurs, associated with breathing of the crystal lattice along the direction of the Fe–nitrile bonds, while the nitriles reorient. HS→LS switching triggered by light (808 nm) reveals the coupling of spin state and nitrile orientation. The importance of this coupling was confirmed by studies of [Fe(ebtz)2(C2H5CN/C3H7CN)2](BF4)2 mixed crystals ( 2 a , 2 b ), showing a shift of T1/2 to higher values and narrowing of the hysteresis loop concomitant with an increase of the fraction of butyronitrile. This increase reduces the capability of nitrile molecules to reorient. Density functional theory (DFT) studies of models of 1 – 5 suggest a particular possibility of 2 to adopt a low (140–145°) value of its Fe-N-C(propionitrile) angle. 相似文献
13.
Prof. Dr. Fa-Guang Zhang Xue-Qi Wang Yin Zhou Hong-Song Shi Zhe Feng Prof. Dr. Jun-An Ma Prof. Dr. Ilan Marek 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(67):15378-15396
Remote functionalization reactions have the power to transform a C−H (or C−C) bond at a distant position from a functional group. This Review summarizes recent advances and key breakthroughs in remote fluorination, trifluoromethylation, difluoromethylation, trifluoromethylthiolation, and fluoroalkenylation reactions. Several powerful strategies have emerged to control the reactivity and distal selectivity such as the undirected radical approach, the 1,5-hydrogen atom transfer, the metal migration, the use of distant directing groups, and the ring-opening reactions. These unconventional and predictable C−H (and C−C) functionalization transformations should allow for the preparation of a wide range of otherwise-difficult-to-access alkyl, aromatic, heteroaromatic, and structurally complex fluorides. 相似文献
14.
Mariia Svyntkivska Tomasz Makowski Ewa Piorkowska Marek Brzezinski Agata Herc Anna Kowalewska 《Molecules (Basel, Switzerland)》2021,26(5)
Electrospun nonwovens of poly(L-lactide) (PLLA) modified with multiwall carbon nanotubes (MWCNT) and linear ladder-like poly(silsesquioxane) with methoxycarbonyl side groups (LPSQ-COOMe) were obtained. MWCNT and LPSQ-COOMe were added to the polymer solution before the electrospinning. In addition, nonwovens of PLLA grafted to modified MWCNT were electrospun. All modified nonwovens exhibited higher tensile strength than the neat PLA nonwoven. The addition of 10 wt.% of LPSQ-COOMe and 0.1 wt.% of MWCNT to PLLA increased the tensile strength of the nonwovens 2.4 times, improving also the elongation at the maximum stress. 相似文献
15.
Dr. Katarzyna Trzeciak Dr. Ewelina Wielgus Dr. Sławomir Kaźmierski Mehrnaz Khalaji Prof. Assoc. Marta K. Dudek Prof. Dr. Marek J. Potrzebowski 《Chemphyschem》2023,24(7):e202200884
In this work, we present results for loading of well-defined binary systems (cocrystal, solid solution) and untreated materials (physical mixtures) into the voids of MCM-41 mesoporous silica particles employing three different filling methods. The applied techniques belong to the group of “wet methods” (diffusion supported loading – DiSupLo ) and “solvent-free methods” (mechanical ball-mill loading – MeLo , thermal solvent free – TSF ). As probes for testing the guest1-guest2 interactions inside the MCM-41 pores we employed the benzoic acid ( BA ), perfluorobenzoic acid ( PFBA ), and 4-fluorobenzoic acid ( 4-FBA ). The guests intermolecular contacts and phase changes were monitored employing magic angle spinning (MAS) NMR Spectroscopy techniques and powder X-ray diffraction (PXRD). Since mesoporous silica materials are commonly used in drug delivery system research, special attention has been paid to factors affecting guest release kinetics. It has been proven that not only the content and composition of binary systems, but also the loading technique have a strong impact on the rate of guests release. Innovative methods of visualizing differences in release kinetics are presented. 相似文献
16.
Based on rational design of the transition state analog inhibitors of glycosyltransferases, four model glycomimetics of this type, viz. benzyl 2-thio-α-dfructofuranoside 1-diethylphosphate (XIa), its β-anomer (XIb), and their ethyl 2-thio analogs — α-anomer (XIIa) and β-anomer (XIIb), were synthesized. In addition, fourteen precursors arising during the synthesis of the desired final model compounds (XI and XII), partially or fully acetylated benzyl and/or ethyl 2-thiofructofuranoside 1-diethyl phosphates, were isolated and characterized with the aim to prepare complete series of glycomimetics, representing donor UDP-GlcNAc designated for biological assays on human GnT’s, viz. GnT-I, Core2GnT, and GnT-V. 相似文献
17.
Substituting CF2 for O4′ in Components of Nucleic Acids: Towards Systems with Reduced Propensity to Form Abasic Lesions 下载免费PDF全文
Dr. Yevgen P. Yurenko Dr. Jan Novotný Prof. Dr. Vladimir Sklenář Prof. Dr. Radek Marek 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(49):17933-17943
Intrinsic structural features and energetics of nucleotides containing variously fluorinated sugars as potential building blocks of DNA duplexes and quadruplexes are explored systematically using the modern methods of density functional theory (DFT) and quantum chemical topology (QCT). Our results suggest that fluorination at the 2′‐β or 2′‐α,β positions somewhat stabilizes in vacuo the AI relative to the BI conformations. In contrast, substitution of the CF2 group for the O4′ atom (O4′‐CF2 modification) leads to a preference of the BI relative to AI DNA‐like conformers. All the studied modifications result in a noticeable increase in the stability of the glycosidic bond [estimated by the relaxed force constants (RFC) approach], with particularly encouraging results for the O4′‐CF2 derivative. Consequently, the O4′‐CF2 modified systems are suggested and explored as promising scaffolds for the development of duplex and quadruplex structures with reduced propensity to form abasic lesions and to undergo DNA damage. 相似文献
18.
Andrea Schenkmayerová Anikó Bertóková Jana Šefčovičová Vladimír Štefuca Marek Bučko Alica Vikartovská Peter Gemeiner Ján Tkáč Jaroslav Katrlík 《Analytica chimica acta》2015
A microbial biosensor for 2-phenylethanol (2-PE) based on the bacteria Gluconobacter oxydans was developed and applied in monitoring of a biotechnological process. The cells of G. oxydans were immobilized within a disposable polyelectrolyte complex gel membrane consisting of sodium alginate, cellulose sulphate and poly(methylene-co-guanidine) attached onto a miniaturized Clark oxygen electrode, forming whole cell amperometric biosensor. Measured changes in oxygen concentration were proportional to changes in 2-PE concentration. The biosensor sensitivity was 864 nA mM−1 (RSD = 6%), a detection limit of 1 μM, and the biosensor response towards 2-PE was linear in the range 0.02–0.70 mM. The biosensor preserved 93% of its initial sensitivity after 7 h of continuous operation and exhibited excellent storage stability with loss of only 6% of initial sensitivity within two months, when stored at 4 °C. The developed system was designed and successfully used for an off-line monitoring of whole course of 2-PE biooxidation process producing phenylacetic acid (PA) as industrially valuable aromatic compound. The biosensor measurement did not require the use of hazardous organic solvent. The biosensor response to 2-PE was not affected by interferences from PA and phenylacetaldehyde at concentrations present in real samples during the biotransformation and the results were in a very good agreement with those obtained via gas chromatography. 相似文献
19.
Jana Beinhauer Liangqiao Bian Hui Fan Marek Šebela Maciej Kukula Jose A. Barrera Kevin A. Schug 《Analytica chimica acta》2015
Estrone (E1), estradiols (α/β-E2), and estriol (E3) are four major metabolically active estrogens exerting strong biological activities at very low circulating concentrations. This paper reports a sensitive and efficient method with automated, on-line clean-up and detection to determine trace estrogens in a small volume of serum samples using liquid chromatography–electrospray ionization–tandem mass spectrometry directly, without off-line liquid–liquid or solid-phase extraction pretreatments. Serum aliquots (charcoal stripped fetal bovine serum, 100 μL) were spiked with four estrogen standards and their corresponding isotope-labeled internal standards, then bulk derivatized with 2-fluoro-1-methyl-pyridium p-toluenesulfonate (2-FMP) to establish the calibration curves and perform method validation. Calibration was established in the concentration ranges of 5–1000 pg mL−1, and demonstrated good linearity of R2 from 0.9944 to 0.9997 for the four derivatized estrogens. The lower detection limits obtained were 3–7 pg mL−1. Good accuracy and precision in the range of 86–112% and 2.3–11.9%, respectively, were observed for the quality control (QC) samples at low, medium, and high concentration levels. The stability tests showed that the derivatized serum samples were stable 8 h after derivatization at room temperature and at least to 48 h if stored at −20 °C. The method was applied to measure trace estrogens in real human and bovine serum samples, and three of four estrogen compounds studied were observed and quantified. 相似文献
20.