全文获取类型
收费全文 | 541篇 |
免费 | 14篇 |
国内免费 | 1篇 |
专业分类
化学 | 481篇 |
晶体学 | 6篇 |
力学 | 1篇 |
数学 | 24篇 |
物理学 | 44篇 |
出版年
2023年 | 6篇 |
2022年 | 38篇 |
2021年 | 40篇 |
2020年 | 17篇 |
2019年 | 8篇 |
2018年 | 10篇 |
2017年 | 8篇 |
2016年 | 27篇 |
2015年 | 15篇 |
2014年 | 33篇 |
2013年 | 41篇 |
2012年 | 32篇 |
2011年 | 44篇 |
2010年 | 21篇 |
2009年 | 21篇 |
2008年 | 29篇 |
2007年 | 30篇 |
2006年 | 28篇 |
2005年 | 14篇 |
2004年 | 20篇 |
2003年 | 19篇 |
2002年 | 15篇 |
2001年 | 2篇 |
2000年 | 3篇 |
1999年 | 5篇 |
1998年 | 8篇 |
1997年 | 5篇 |
1996年 | 2篇 |
1995年 | 7篇 |
1994年 | 1篇 |
1992年 | 2篇 |
1985年 | 1篇 |
1981年 | 3篇 |
1980年 | 1篇 |
排序方式: 共有556条查询结果,搜索用时 0 毫秒
61.
Heger D Nachtigallová D Surman F Krausko J Magyarová B Brumovský M Rubeš M Gladich I Klán P 《The journal of physical chemistry. A》2011,115(41):11412-11422
A combined experimental-computational approach was used to study the self-organization and microenvironment of 1-methylnaphthalene (1MN) deposited on the surface of artificial snow grains from vapors at 238 K. The specific surface area of this snow (1.1 × 10(4) cm(2) g(-1)), produced by spraying very fine droplets of pure water from a nebulizer into liquid nitrogen, was determined using valerophenone photochemistry to estimate the surface coverage by 1MN. Fluorescence spectroscopy at 77 K, in combination with molecular dynamics simulations, and density functional theory (DFT) and second-order coupled cluster (CC2) calculations, provided evidence for the occurrence of ground- and excited-state complexes (excimers) and other associates of 1MN on the snow grains' surface. Only weak excimer fluorescence was observed for a loading of 5 × 10(-6) mol kg(-1), which is ~2-3 orders of magnitude below monolayer coverage. However, the results indicate that the formation of excimers is favored at higher surface loadings (>5 × 10(-5) mol kg(-1)), albeit still being below monolayer coverage. The calculations of excited states of monomer and associated moieties suggested that a parallel-displaced arrangement is responsible for the excimer emission observed experimentally, although some other associations, such as T-shape dimer structures, which do not provide excimer emission, can still be relatively abundant at this surface concentration. The hydrophobic 1MN molecules, deposited on the ice surface, which is covered by a relatively flexible quasi-liquid layer at 238 K, are then assumed to be capable of dynamic motion resulting in the formation of energetically preferred associations to some extent. The environmental implications of organic compounds' deposition on snow grains and ice are discussed. 相似文献
62.
Nowicka B Bałanda M Gaweł B Ćwiak G Budziak A Łasocha W Sieklucka B 《Dalton transactions (Cambridge, England : 2003)》2011,40(12):3067-3073
Methanol adsorption into the porous 2D bimetallic coordination network {[Ni(cyclam)](3)[W(CN)(8)](2)}(n) (cyclam = 1,4,8,11-tetraazacyclotetradecane) causes significant modification of its structure and magnetic properties. Fully reversible transformations between the three states of the network: anhydrous, hydrated and methanol-modified are observed with the transition to the magnetic ordered state at T(c) equal to 4.9 K, 8.3 K and 11.4 K respectively. All three phases have a metamagnetic character but the methanol-modified one most easily turns to ferromagnetic and shows a hysteresis loop with coercivity field of 250 Oe. The differences in magnetic behaviour of the anhydrous and guest-induced forms of the compound are discussed in terms of changes in the structure: CN-bridge geometry and distance between the layers. 相似文献
63.
Piotr Kowalski Jolanta Jaśkowska Andrzej J. Bojarski Beata Duszyńska Adam Bucki Marcin Kołaczkowski 《Journal of heterocyclic chemistry》2011,48(1):192-198
The synthesis and evaluation as 5‐HT1A and 5‐HT7 serotonin receptor ligands of the two sets of O‐substituted hydroxybenzamides, structurally related to 2‐{3‐[4‐(2‐methoxyphenyl)piperazin‐1‐yl]propoxy}benzamide ( 1 ), (Ki 5‐HT1A = 21 nM, 5‐HT7 = 234 nM) are reported. To affect the affinity for 5‐HT1A and 5‐HT7 receptors, an amide moiety ( 2 , 3 , 4 , 5 , 6 ) and a hydrocarbon chain length ( 7 , 8 , 9 , 10 ) were modified. The serotonergic activity of compounds 2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 was generally higher in the case of 5‐HT1A receptors compared with 5‐HT7 ones; the most active 5‐HT1A ligands being meta‐isomer 2 (Ki = 7 nM) and both analogs of 1 with the longest spacer, i.e., penta‐ and hexa‐methylene derivatives 9 and 10 (Ki = 4 and 3 nM, respectively). The observed biological properties of compounds 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 were elucidated using molecular modeling procedures. J. Heterocyclic Chem., (2010). 相似文献
64.
Beata Podkościelna 《Journal of Thermal Analysis and Calorimetry》2011,104(2):725-730
The thermal stability of the ionic liquids (ILs) 1-n-butyl-3-methylimidazolium bromide, [BMIM]Br, and 1-n-octyl-3-methylimidazolium bromide, [OMIM]Br, was evaluated through thermogravimetry (TG). Long-term isothermal TG studies
revealed that both of these ILs exhibit appreciable decomposition even at temperatures significantly lower than the onset
decomposition temperature, previously determined from fast scan TG experiments. The long-term TG studies of both the ILs showed
linear mass loss as a function of time at each temperature of 10 °C interval in the range 533–573 K over a period of 10 h.
The kinetics of isothermal decomposition of ILs was analyzed using pseudo-zero-order rate expression. The activation energies
for the isothermal decomposition of [BMIM]Br and [OMIM]Br under nitrogen atmosphere are 219.86 and 212.50 kJ mol−1, respectively. The moisture absorption kinetics of these ILs at 25 °C and 30% relative humidity (RH) and at 85 °C and 85%
RH were also studied. Water uptake of ILs exposed at 25 °C/30%RH follows a simple saturation behavior in agreement with Weibull
model while that at 85 °C/85%RH fortuitously fit into the Henderson–Pabis model. 相似文献
65.
Simeonika Rangełowa‐Jankowska Dawid Jankowski Dr. Beata Grobelna Prof. Ignacy Gryczyński Prof. Zygmunt Gryczyński Dr. Robert Bogdanowicz Prof. Piotr Bojarski 《Chemphyschem》2011,12(13):2449-2452
The first observation of strong directional surface‐plasmon‐coupled emission (SPCE) of Rhodamine 110 in silica nanofilms deposited on silver nanolayers is reported. The preparation of the material is described in detail. The intensity of SPCE exceeds 10 times that of free space fluorescence and total linear light polarization in the SPCE ring is observed. A new experimental setup and an original data collection method is presented. Our material completely preserves its fluorescence properties for at least eight months. 相似文献
66.
Wileńska B Danikiewicz W Bugaj M Kamieńska-Trela K Krówczyńsk A 《European journal of mass spectrometry (Chichester, England)》2011,17(3):237-243
Electron ionization (EI) and positive electrospray ionization (ESI) mass spectra of selected diaryl enaminoketones and enaminothiones have been studied. In the EI mass spectra of both classes of compound, molecular ion peaks are accompanied by the peaks corresponding to the [M-H](+) ions. The formation of these ions can be rationalized by a cyclization reaction resulting in the formation of the respective isoxazolium and isothiazolium cations. Under positive ESI conditions, in the spectra recorded for the enaminoketones peaks corresponding to the [M+H](+), [M+Na](+) and [2M+Na](+) ions appeared, while in the spectra recorded for the enaminothiones, peaks corresponding to the [M-H](+) ions were dominant. These ions are most likely formed by oxidation of the neutral enaminothione molecules on the surface of the positively charged stainless steel capillary in the ESI ion source (anodic oxidation). 相似文献
67.
The oxidation process of 1-methoxy-4-(1-methylethyl)benzene catalysed by N-hydroxyphthalimide (NHPI) or NHPI in combination
with Cu(II), Co(II), Mn(II) and Fe(II) salts was studied. The effects of the amount of catalyst and the temperature were determined.
1-Methyl-1-(4-methoxyphenyl)ethyl hydroperoxide was obtained in a yield of 73 mol% when 1-methoxy-4-(1-methylethyl)benzene
was oxidised for 3 h at 60°C in acetonitrile as a solvent in the presence of NHPI. 1-(4-Methoxyphenyl)ethanone with high selectivity
up to 68–75 mol%, but low yield amounting to 11 mol% was obtained when 1-methoxy-4-(1-methylethyl)benzene was oxidised in
the presence of the NHPI/Cu(II) system at 120°C.
相似文献
68.
Aequationes mathematicae - For a family $$(\mathscr {A}_x)_{x \in (0,1)}$$ of integral quasi-arithmetic means satisfying certain measurability-type assumptions we search for an integral mean K such... 相似文献
69.
Dawid Maliszewski Agnieszka Wrbel Beata Kolesiska Justyna Frczyk Danuta Drozdowska 《Molecules (Basel, Switzerland)》2021,26(13)
A series of new analogs of nitrogen mustards (4a–4h) containing the 1,3,5-triazine ring substituted with dipeptide residue were synthesized and evaluated for the inhibition of both acetylcholinesterase (AChE) and β-secretase (BACE1) enzymes. The AChE inhibitory activity studies were carried out using Ellman’s colorimetric method, and the BACE1 inhibitory activity studies were carried out using fluorescence resonance energy transfer (FRET). All compounds displayed considerable AChE and BACE1 inhibition. The most active against both AChE and BACE1 enzymes were compounds A and 4a, with an inhibitory concentration of AChE IC50 = 0.051 µM; 0.055 µM and BACE1 IC50 = 9.00 µM; 11.09 µM, respectively. 相似文献
70.
Trichothecene mycotoxins are sesquiterpenoid compounds primarily produced by fungi in taxonomical genera such as Fusarium, Myrothecium, Stachybotrys, Trichothecium, and others, under specific climatic conditions on a worldwide basis. Fusarium mold is a major plant pathogen and produces a number of trichothecene mycotoxins including deoxynivalenol (or vomitoxin), nivalenol, diacetoxyscirpenol, and T-2 toxin, HT-2 toxin. Monogastrics are sensitive to vomitoxin, while poultry and ruminants appear to be less sensitive to some trichothecenes through microbial metabolism of trichothecenes in the gastrointestinal tract. Trichothecene mycotoxins occur worldwide however both total concentrations and the particular mix of toxins present vary with environmental conditions. Proper agricultural practices such as avoiding late harvests, removing overwintered stubble from fields, and avoiding a corn/wheat rotation that favors Fusarium growth in residue can reduce trichothecene contamination of grains. Due to the vague nature of toxic effects attributed to low concentrations of trichothecenes, a solid link between low level exposure and a specific trichothecene is difficult to establish. Multiple factors, such as nutrition, management, and environmental conditions impact animal health and need to be evaluated with the knowledge of the mycotoxin and concentrations known to cause adverse health effects. Future research evaluating the impact of low-level exposure on livestock may clarify the potential impact on immunity. Trichothecenes are rapidly excreted from animals, and residues in edible tissues, milk, or eggs are likely negligible. In chronic exposures to trichothecenes, once the contaminated feed is removed and exposure stopped, animals generally have an excellent prognosis for recovery. This review shows the occurrence of trichothecenes in food and feed in 2011–2020 and their toxic effects and provides a summary of the discussions on the potential public health concerns specifically related to trichothecenes residues in foods associated with the exposure of farm animals to mycotoxin-contaminated feeds and impact to human health. Moreover, the article discusses the methods of their detection. 相似文献