全文获取类型
收费全文 | 4138篇 |
免费 | 234篇 |
国内免费 | 16篇 |
专业分类
化学 | 3422篇 |
晶体学 | 16篇 |
力学 | 67篇 |
数学 | 425篇 |
物理学 | 458篇 |
出版年
2023年 | 42篇 |
2022年 | 107篇 |
2021年 | 176篇 |
2020年 | 141篇 |
2019年 | 120篇 |
2018年 | 59篇 |
2017年 | 56篇 |
2016年 | 175篇 |
2015年 | 179篇 |
2014年 | 163篇 |
2013年 | 236篇 |
2012年 | 337篇 |
2011年 | 372篇 |
2010年 | 210篇 |
2009年 | 172篇 |
2008年 | 291篇 |
2007年 | 257篇 |
2006年 | 254篇 |
2005年 | 181篇 |
2004年 | 189篇 |
2003年 | 148篇 |
2002年 | 125篇 |
2001年 | 27篇 |
2000年 | 29篇 |
1999年 | 26篇 |
1998年 | 19篇 |
1997年 | 21篇 |
1996年 | 24篇 |
1995年 | 20篇 |
1994年 | 16篇 |
1993年 | 5篇 |
1991年 | 6篇 |
1990年 | 6篇 |
1989年 | 9篇 |
1988年 | 5篇 |
1987年 | 8篇 |
1986年 | 10篇 |
1985年 | 19篇 |
1984年 | 18篇 |
1983年 | 16篇 |
1982年 | 17篇 |
1981年 | 18篇 |
1980年 | 10篇 |
1979年 | 8篇 |
1978年 | 7篇 |
1977年 | 13篇 |
1976年 | 7篇 |
1975年 | 6篇 |
1974年 | 7篇 |
1973年 | 4篇 |
排序方式: 共有4388条查询结果,搜索用时 31 毫秒
201.
Rosaria Cozzolino Laura De Magistris Paola Saggese Matteo Stocchero Antonella Martignetti Michele Di Stasio Antonio Malorni Rosa Marotta Floriana Boscaino Livia Malorni 《Analytical and bioanalytical chemistry》2014,406(19):4649-4662
Autism spectrum disorders (ASDs) are a group of neurodevelopmental disorders which have a severe life-long effect on behavior and social functioning, and which are associated with metabolic abnormalities. Their diagnosis is on the basis of behavioral and developmental signs usually detected before three years of age, and there is no reliable biological marker. The objective of this study was to establish the volatile urinary metabolomic profiles of 24 autistic children and 21 healthy children (control group) to investigate volatile organic compounds (VOCs) as potential biomarkers for ASDs. Solid-phase microextraction (SPME) using DVB/CAR/PDMS sorbent coupled with gas chromatography–mass spectrometry was used to obtain the metabolomic information patterns. Urine samples were analyzed under both acid and alkaline pH, to profile a range of urinary components with different physicochemical properties. Multivariate statistics techniques were applied to bioanalytical data to visualize clusters of cases and to detect the VOCs able to differentiate autistic patients from healthy children. In particular, orthogonal projections to latent structures discriminant analysis (OPLS-DA) achieved very good separation between autistic and control groups under both acidic and alkaline pH, identifying discriminating metabolites. Among these, 3-methyl-cyclopentanone, 3-methyl-butanal, 2-methyl-butanal, and hexane under acid conditions, and 2-methyl-pyrazine, 2,3-dimethyl-pyrazine, and isoxazolo under alkaline pH had statistically higher levels in urine samples from autistic children than from the control group. Further investigation with a higher number of patients should be performed to outline the metabolic origins of these variables, define a possible association with ASDs, and verify the usefulness of these variables for early-stage diagnosis. Figure
? 相似文献
202.
Xiaoge Qu Laura Rowe Emre Dikici Mark Ensor Sylvia Daunert 《Analytical and bioanalytical chemistry》2014,406(23):5639-5643
Bioluminescent labels can be especially useful for in vivo and live animal studies due to the negligible bioluminescence background in cells and most animals, and the non-toxicity of bioluminescent reporter systems. Significant thermal stability of bioluminescent labels is essential, however, due to the longitudinal nature and physiological temperature conditions of many bioluminescent-based studies. To improve the thermostability of the bioluminescent protein aequorin, we employed random and rational mutagenesis strategies to create two thermostable double mutants, S32T/E156V and M36I/E146K, and a particularly thermostable quadruple mutant, S32T/E156V/Q168R/L170I. The double aequorin mutants, S32T/E156V and M36I/E146K, retained 4 and 2.75 times more of their initial bioluminescence activity than wild-type aequorin during thermostability studies at 37 °C. Moreover, the quadruple aequorin mutant, S32T/E156V/Q168R/L170I, exhibited more thermostability at a variety of temperatures than either double mutant alone, producing the most thermostable aequorin mutant identified thus far. 相似文献
203.
Laura E. Muresan Adrian I. Cadis Ioana Perhaita Emil Indrea 《Central European Journal of Chemistry》2014,12(10):1023-1031
Yttrium silicate doped with cerium (Y2SiO5:Ce) was obtained from Y-Ce-Si based precursors prepared by the simultaneous addition of reagents (SimAdd) technique. The synthesis of the precursors was done in well controlled conditions using ammonium oxalate, ammonium carbonate or urea as precipitating agents. Results regarding the influence of precipitating agents on the morpho structural and photoluminescent characteristics of Y2SiO5:Ce are reported. The TG analysis in correlation with EGA, FT-IR and XRD investigations reveals the formation of oxalate, hydroxy-carbonate or hydroxy-nitrate based compounds, the same as the conversion of the precursors to well crystallized yttrium silicate. XRD patterns show that the precursors are amorphous except for the sample prepared with ammonium oxalate. Depending on the precipitation conditions, the phosphors phase composition varies from single phase (X2-Y2SiO5) to a mixture of phases (X2-Y2SiO5, X1-Y2SiO5, Y2O3). Under UV excitation, phosphors exhibit the specific blue emission of cerium with an intensity that varies from 175.8% (urea) to 96.0% (ammonium carbonate) and to 78.5% (ammonium oxalate). The emission intensity depends on the phase purity and order degree of the phosphors. PACS Classification codes:78.55 Hx, 81.20Fw 相似文献
204.
Resch Laura Karner Anna Sprengel Wolfgang Wrschum Roland Schennach Robert 《Cellulose (London, England)》2022,29(3):1357-1363
Cellulose - In this study, for the first time, the experimental technique of positron annihilation lifetime spectroscopy (PALS) has been applied to monitor in situ the microstructural changes of... 相似文献
205.
206.
Ricardo G. Alvim Petrina Georgala Lucas Nogueira Alexander J. Somma Karan Nagar Jasmine Thomas Laura Alvim Amelia Riegel Christopher Hughes Jie Chen Augusto B. Reis Souhil Lebdai Avigdor Scherz Steven Zanganeh Rui Gardner Kwanghee Kim Jonathan A. Coleman 《Molecules (Basel, Switzerland)》2021,26(12)
Purpose: Vascular targeted photodynamic therapy (VTP) is a nonsurgical tumor ablation approach used to treat early-stage prostate cancer and may also be effective for upper tract urothelial cancer (UTUC) based on preclinical data. Toward increasing response rates to VTP, we evaluated its efficacy in combination with concurrent PD-1 inhibitor/OX40 agonist immunotherapy in a urothelial tumor-bearing model. Experimental design: In mice allografted with MB-49 UTUC cells, we compared the effects of combined VTP with PD-1 inhibitor/OX40 agonist with those of the component treatments on tumor growth, survival, lung metastasis, and antitumor immune responses. Results: The combination of VTP with both PD-1 inhibitor and OX40 agonist inhibited tumor growth and prolonged survival to a greater degree than VTP with either immunotherapeutic individually. These effects result from increased tumor infiltration and intratumoral proliferation of cytotoxic and helper T cells, depletion of Treg cells, and suppression of myeloid-derived suppressor cells. Conclusions: Our findings suggest that VTP synergizes with PD-1 blockade and OX40 agonist to promote strong antitumor immune responses, yielding therapeutic efficacy in an animal model of urothelial cancer. 相似文献
207.
Dr. Andre Nicolai Petelski Josefina Marquez Silvana Carina Pamies Prof. Dr. Gladis Laura Sosa Prof. Dr. Nélida María Peruchena 《Chemphyschem》2021,22(7):665-674
Due to their potential binding sites, barbituric acid (BA) and its derivatives have been used in metal coordination chemistry. Yet their abilities to recognize anions remain unexplored. In this work, we were able to identify four structural features of barbiturates that are responsible for a certain anion affinity. The set of coordination interactions can be finely tuned with covalent decorations at the methylene group. DFT-D computations at the BLYP-D3(BJ)/aug-cc-pVDZ level of theory show that the C−H bond is as effective as the N−H bond to coordinate chloride. An analysis of the electron charge density at the C−H⋅⋅⋅Cl− and N−H⋅⋅⋅Cl− bond critical points elucidates their similarities in covalent character. Our results reveal that the special acidity of the C−H bond shows up when the methylene group moves out of the ring plane and it is mainly governed by the orbital interaction energy. The amide and carboxyl groups are the best choices to coordinate the ion when they act together with the C−H bond. We finally show how can we use this information to rationally improve the recognition capability of a small cage-like complex that is able to coordinate NaCl. 相似文献
208.
Francesca Cal Chiara Roberta Girelli Federica Angil Laura Del Coco Lucia Mazzi Daniele Barbini Francesco Paolo Fanizzi 《Molecules (Basel, Switzerland)》2021,26(8)
Considering the growing number of extra virgin olive oil (EVOO) producers in the world, knowing the influence of olive oils with different geographical origins on the characteristics of the final blend becomes an interesting goal. The present work is focused on commercial organic EVOO blends obtained by mixing multiple oils from different geographical origins. These blends have been studied by 1H-NMR spectroscopy supported by multivariate statistical analysis. Specific characteristics of commercial organic EVOO blends originated by mixing oils from Italy, Tunisia, Portugal, Spain, and Greece were found to be associated with the increasing content of the Italian component. A linear progression of the metabolic profile defined characteristics for the analysed samples—up to a plateau level—was found in relation to the content of the main constituent of the Italian oil, the monocultivar Coratina. The Italian constituent percentage appears to be correlated with the fatty acids (oleic) and the polyphenols (tyrosol, hydroxytyrosol, and derivatives) content as major and minor components respectively. These results, which highlight important economic aspects, also show the utility of 1H-NMR associated with chemometric analysis as a powerful tool in this field. Mixing oils of different national origins, to obtain blends with specific characteristics, could be profitably controlled by this methodology. 相似文献
209.
Chiara Cavaliere Anna Laura Capriotti Andrea Cerrato Laura Lorini Carmela Maria Montone Francesco Valentino Aldo Lagan Mauro Majone 《Molecules (Basel, Switzerland)》2021,26(3)
Polyhydroxyalkanoates (PHAs) are well-known biodegradable plastics produced by various bacterial strains, whose major drawback is constituted by the high cost of their synthesis. Producing PHAs from mixed microbial cultures and employing organic wastes as a carbon source allows us to both reduce cost and valorize available renewable resources, such as food waste and sewage sludge. However, different types of pollutants, originally contained in organic matrices, could persist into the final product, thus compromising their safety. In this work, the exploitation of municipal wastes for PHA production is evaluated from the environmental and health safety aspect by determining the presence of polycyclic aromatic hydrocarbons (PAHs) in both commercial and waste-based PHA samples. Quantification of PAHs by gas chromatography-mass spectrometry on 24 PHA samples obtained in different conditions showed very low contamination levels, in the range of ppb to a few ppm. Moreover, the contaminant content seems to be dependent on the type of PHA stabilization and extraction, but independent from the type of feedstock. Commercial PHA derived from crops, selected for comparison, showed PAH content comparable to that detected in PHAs derived from organic fraction of municipal solid waste. Although there is no specific regulation on PAH maximum levels in PHAs, detected concentrations were consistently lower than threshold limit values set by regulation and guidelines for similar materials and/or applications. This suggests that the use of organic waste as substrate for PHA production is safe for both the human health and the environment. 相似文献
210.
Laura A. Kranendonk Robert Huber Scott T. Sanders 《Proceedings of the Combustion Institute》2007,31(1):783-790
Using a novel Fourier-domain mode-locking (FDML) laser scanning 1330-1380 nm, we have developed a gas thermometer based on absorption spectroscopy that is appropriate for combustion gases at essentially arbitrary conditions. The path-integrated measurements are particularly useful in homogeneous environments, and here we present measurements in a controlled piston engine and a shock tube. Engine measurements demonstrate a RMS temperature precision of ±3% at 1500 K and 200 kHz bandwidth; the precision is improved dramatically by averaging. Initial shock tube measurements place the absolute accuracy of the thermometer within ∼2% to 1000 K. The sensor performs best when significant H2O vapor is present, but requires only at 300 K, at 1000 K, or at 3000 K for 2% accurate thermometry, assuming a 4 kHz measurement bandwidth (200 kHz scans with 50 averages). The sensor also provides H2O mole fraction and shows potential for monitoring gas pressure based on the broadening of spectral features. To aid in designing other sensors based on high-temperature, high-pressure H2O absorption spectroscopy, a database of measured spectra is included. 相似文献