首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   1557篇
  免费   37篇
  国内免费   5篇
化学   1154篇
晶体学   9篇
力学   35篇
综合类   1篇
数学   203篇
物理学   197篇
  2023年   13篇
  2022年   30篇
  2021年   49篇
  2020年   42篇
  2019年   33篇
  2018年   30篇
  2017年   35篇
  2016年   47篇
  2015年   38篇
  2014年   52篇
  2013年   85篇
  2012年   91篇
  2011年   101篇
  2010年   68篇
  2009年   61篇
  2008年   88篇
  2007年   89篇
  2006年   69篇
  2005年   76篇
  2004年   66篇
  2003年   42篇
  2002年   51篇
  2001年   15篇
  2000年   15篇
  1999年   14篇
  1998年   10篇
  1997年   13篇
  1996年   14篇
  1995年   17篇
  1994年   12篇
  1993年   18篇
  1992年   15篇
  1991年   9篇
  1990年   10篇
  1989年   8篇
  1988年   11篇
  1987年   14篇
  1983年   13篇
  1982年   11篇
  1981年   9篇
  1980年   8篇
  1978年   10篇
  1977年   8篇
  1976年   11篇
  1975年   7篇
  1974年   8篇
  1973年   5篇
  1970年   5篇
  1968年   7篇
  1967年   5篇
排序方式: 共有1599条查询结果,搜索用时 31 毫秒
51.
Drought poses a serious threat to oilseed crops by lowering yield and crop failures under prolonged spells. A multi-year field investigation was conducted to enhance the drought tolerance in four genotypes of Camelina and canola by selenium (Se) application. The principal aim of the research was to optimize the crop yield by eliciting the physio-biochemical attributes by alleviating the adverse effects of drought stress. Both crops were cultivated under control (normal irrigation) and drought stress (skipping irrigation at stages i.e., vegetative and reproductive) conditions. Four different treatments of Se viz., seed priming with Se (75 μM), foliar application of Se (7.06 μM), foliar application of Se + Seed priming with Se (7.06 μM and 75 μM, respectively) and control (without Se), were implemented at the vegetative and reproductive stages of both crops. Sodium selenite (Na2SeO3), an inorganic compound was used as Se sources for both seed priming and foliar application. Data regarding physiochemical, antioxidants, and yield components were recorded as response variables at crop maturity. Results indicated that WP, OP, TP, proline, TSS, TFAA, TPr, TS, total chlorophyll contents, osmoprotectant (GB, anthocyanin, TPC, and flavonoids), antioxidants (APX, SOD, POD, and CAT), and yield components (number of branches per plant, thousand seed weight, seed, and biological yields were significantly improved by foliar Se + priming Se in both crops under drought stress. Moreover, this treatment was also helpful in boosting yield attributes under irrigated (non-stress) conditions. Camelina genotypes responded better to Se application as seed priming and foliar spray than canola for both years. It has concluded that Se application (either foliar or priming) can potentially alleviate adverse effects of drought stress in camelina and canola by eliciting various physio-biochemicals attributes under drought stress. Furthermore, Se application was also helpful for crop health under irrigated condition.  相似文献   
52.
The synthesis and photophysical properties of two novel multichromophoric compounds is presented. Their molecular design comprises a carbonyl‐bridged triarylamine core and either naphthalimides or 4‐(5‐hexyl‐2,2′‐bithiophene)naphthalimides as second chromophore in the periphery. The lateral chromophores are attached to the core via an amide linkage and a short alkyl spacer. The synthetic approach demonstrates a straightforward functionalization strategy for carbonyl‐bridged triarylamines. Steady‐state and time‐resolved spectroscopic investigations of these compounds, in combination with three reference compounds, provide clear evidence for energy transfer in both multichromophoric compounds. The direction of the energy transfer depends on the lateral chromophore used. Furthermore, the compound bearing the lateral 4‐(bithiophene)naphthaimides is capable of forming fluorescent gels at very low concentrations in the sub‐millimolar regime whilst retaining its energy transfer properties.  相似文献   
53.
This investigation aimed to study a “green” non-toxic biodegradable copper corrosion inhibitor in an acidic sodium sulphate solution. The methods used in the investigation of cysteine as a copper corrosion inhibitor in an acidic sodium sulphate solution were: potentiodynamic measurements, open circuit potential measurements, and chronoamperometric measurements. Optical microscopy was used in addition to electrochemical methods. Potentiodynamic measurements show that cysteine has good inhibitory properties in an acidic medium. Polarisation curves indicate that the presence of cysteine in a sulphate solution decreases the current density and that using various cysteine concentrations results in the formation of a protective film on the surface of the electrode due to the formation of the Cu(I)-cys complex. These results are confirmed by chronoamperometric measurements. Furthermore, it is clear from microphotographs that a protective film does form on copper electrode in the presence of cysteine. The Langmuir adsorption isotherm indicates that cysteine is chemisorbed on the surface of the electrode.  相似文献   
54.
We investigate activation of carbon dioxide by singly charged hydrated magnesium cations Mg .+(H2O)n, through infrared multiple photon dissociation (IRMPD) spectroscopy combined with quantum chemical calculations. The spectra of [MgCO2(H2O)n].+ in the 1250–4000 cm?1 region show a sharp transition from n=2 to n=3 for the position of the CO2 antisymmetric stretching mode. This is evidence for the activation of CO2 via charge transfer from Mg .+ to CO2 for n≥3, while smaller clusters feature linear CO2 coordinated end‐on to the metal center. Starting with n=5, we see a further conformational change, with CO2.? coordination to Mg2+ gradually shifting from bidentate to monodentate, consistent with preferential hexa‐coordination of Mg2+. Our results reveal in detail how hydration promotes CO2 activation by charge transfer at metal centers.  相似文献   
55.
Recently, fluorenylmethoxycarbonyl (Fmoc) amino acids (e.g. Fmoc–tyrosine or Fmoc–phenylalanine) have attracted growing interest in biomedical research and industry, with special emphasis directed towards the design and development of novel effective hydrogelators, biomaterials or therapeutics. With this in mind, a systematic knowledge of the structural and supramolecular features in recognition of those properties is essential. This work is the first comprehensive summary of noncovalent interactions combined with a library of supramolecular synthon patterns in all crystal structures of amino acids with the Fmoc moiety reported so far. Moreover, a new Fmoc‐protected amino acid, namely, 2‐{[(9H‐fluoren‐9‐ylmethoxy)carbonyl](methyl)amino}‐3‐{4‐[(2‐hydroxypropan‐2‐yl)oxy]phenyl}propanoic acid or N‐fluorenylmethoxycarbonyl‐O‐tert‐butyl‐N‐methyltyrosine, Fmoc‐N‐Me‐Tyr(t‐Bu)‐OH, C29H31NO5, was successfully synthesized and the structure of its unsolvated form was determined by single‐crystal X‐ray diffraction. The structural, conformational and energy landscape was investigated in detail by combined experimental and in silico approaches, and further compared to N‐Fmoc‐phenylalanine [Draper et al. (2015). CrystEngComm, 42 , 8047–8057]. Geometries were optimized by the density functional theory (DFT) method either in vacuo or in solutio. The polarizable conductor calculation model was exploited for the evaluation of the hydration effect. Hirshfeld surface analysis revealed that H…H, C…H/H…C and O…H/H…O interactions constitute the major contributions to the total Hirshfeld surface area in all the investigated systems. The molecular electrostatic potentials mapped over the surfaces identified the electrostatic complementarities in the crystal packing. The prediction of weak hydrogen‐bonded patterns via Full Interaction Maps was computed. Supramolecular motifs formed via C—H…O, C—H…π, (fluorenyl)C—H…Cl(I), C—Br…π(fluorenyl) and C—I…π(fluorenyl) interactions are observed. Basic synthons, in combination with the Long‐Range Synthon Aufbau Modules, further supported by energy‐framework calculations, are discussed. Furthermore, the relevance of Fmoc‐based supramolecular hydrogen‐bonding patterns in biocomplexes are emphasized, for the first time.  相似文献   
56.
The distribution of the temperature and the morphology of the charred material formed in the combustion of blends of poly(phenylene ether) (PPE) with high impact polystyrene (HIPS), carried out in the UL94 test, were examined. The effect of the fire retardant triphenyl phosphate is shown to be the decrease of time of burning, of temperature of the specimen and of zone involved in combustion, without apparent modification of the char structure. Hypothesis on gas and condensed phase fire retardant mechanisms are discussed.  相似文献   
57.
Globally, many developing countries are facing silent epidemics of nutritional deficiencies in human beings and animals. The lack of diversity in diet, i.e., cereal-based crops deficient in mineral nutrients is an additional threat to nutritional quality. The present review accounts for the significance of biofortification as a process to enhance the productivity of crops and also an agricultural solution to address the issues of nutritional security. In this endeavor, different innovative and specific biofortification approaches have been discussed for nutrient enrichment of field crops including cereals, pulses, oilseeds and fodder crops. The agronomic approach increases the micronutrient density in crops with soil and foliar application of fertilizers including amendments. The biofortification through conventional breeding approach includes the selection of efficient genotypes, practicing crossing of plants with desirable nutritional traits without sacrificing agricultural and economic productivity. However, the transgenic/biotechnological approach involves the synthesis of transgenes for micronutrient re-translocation between tissues to enhance their bioavailability. Soil microorganisms enhance nutrient content in the rhizosphere through diverse mechanisms such as synthesis, mobilization, transformations and siderophore production which accumulate more minerals in plants. Different sources of micronutrients viz. mineral solutions, chelates and nanoparticles play a pivotal role in the process of biofortification as it regulates the absorption rates and mechanisms in plants. Apart from the quality parameters, biofortification also improved the crop yield to alleviate hidden hunger thus proving to be a sustainable and cost-effective approach. Thus, this review article conveys a message for researchers about the adequate potential of biofortification to increase crop productivity and nourish the crop with additional nutrient content to provide food security and nutritional quality to humans and livestock.  相似文献   
58.
Speaker recognition is an important classification task, which can be solved using several approaches. Although building a speaker recognition model on a closed set of speakers under neutral speaking conditions is a well-researched task and there are solutions that provide excellent performance, the classification accuracy of developed models significantly decreases when applying them to emotional speech or in the presence of interference. Furthermore, deep models may require a large number of parameters, so constrained solutions are desirable in order to implement them on edge devices in the Internet of Things systems for real-time detection. The aim of this paper is to propose a simple and constrained convolutional neural network for speaker recognition tasks and to examine its robustness for recognition in emotional speech conditions. We examine three quantization methods for developing a constrained network: floating-point eight format, ternary scalar quantization, and binary scalar quantization. The results are demonstrated on the recently recorded SEAC dataset.  相似文献   
59.
Pyran-2-ones 3 undergo a novel Pd0-catalyzed 1,3-rearrangement to afford isomers 6 . The reaction proceeds via an η2-Pd complex, the pyramidalization of which (confirmed by quantum chemistry calculations) offers a favorable antiperiplanar alignment of the Pd−C and allylic C−O bonds ( C ), thus allowing the formation of an η3-Pd intermediate. Subsequent rotation and rate-limiting recombination with the carboxylate arm then gives isomeric pyran-2-ones 6 . The calculated free energies reproduce the observed kinetics semi-quantitatively.  相似文献   
60.
The reaction of N,C,N-chelated stibinidene ArSb ( 1 ) (Ar=C6H3-2,6-(CH=NtBu)2) with selected N-alkyl/aryl-maleimides RN(C(O)CH)2 (R=Me, tBu, Ph) gave the addition products with bridged bicyclic [2.2.1] structure containing an antimony atom at the bridgehead position, fused with a 6-membered benzene and a 5-membered N-alkyl/aryl-pyrrolidine ring. These compounds were completely characterized. More importantly, additional studies showed that these reactions are reversible in solution, thereby representing an unprecedented reversible activation of a C=C bond by an antimony(I) compound.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号