全文获取类型
收费全文 | 1697篇 |
免费 | 86篇 |
国内免费 | 5篇 |
专业分类
化学 | 1458篇 |
晶体学 | 11篇 |
力学 | 33篇 |
数学 | 125篇 |
物理学 | 161篇 |
出版年
2024年 | 1篇 |
2023年 | 25篇 |
2022年 | 33篇 |
2021年 | 58篇 |
2020年 | 62篇 |
2019年 | 59篇 |
2018年 | 39篇 |
2017年 | 48篇 |
2016年 | 82篇 |
2015年 | 78篇 |
2014年 | 84篇 |
2013年 | 123篇 |
2012年 | 154篇 |
2011年 | 153篇 |
2010年 | 103篇 |
2009年 | 92篇 |
2008年 | 114篇 |
2007年 | 111篇 |
2006年 | 81篇 |
2005年 | 76篇 |
2004年 | 44篇 |
2003年 | 38篇 |
2002年 | 32篇 |
2001年 | 14篇 |
2000年 | 8篇 |
1999年 | 11篇 |
1998年 | 11篇 |
1997年 | 9篇 |
1996年 | 5篇 |
1995年 | 2篇 |
1994年 | 7篇 |
1993年 | 2篇 |
1992年 | 4篇 |
1991年 | 4篇 |
1990年 | 3篇 |
1989年 | 2篇 |
1987年 | 1篇 |
1986年 | 1篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1980年 | 4篇 |
1978年 | 1篇 |
1977年 | 2篇 |
1976年 | 1篇 |
1975年 | 2篇 |
1965年 | 1篇 |
排序方式: 共有1788条查询结果,搜索用时 15 毫秒
81.
Martin Franc Jana Sobotníková Pavel Coufal Zuzana Bosáková 《Journal of separation science》2014,37(17):2278-2283
Fused‐silica capillary columns for high‐performance liquid chromatography with 320 and 250 μm inner diameter were prepared by slurry packing with 5 and 3 μm Nucleosil C18 stationary phase. Different types of mechanical and monolithic outlet frits were used and their influence on the resulting column performance was evaluated. Columns with quartz wool exhibited symmetrical peaks and low theoretical plate height, and the preparation time was short. The performance of monolithic frits varied based on type of monolith, length of the frit, and silanization procedure. The best frit performed similarly to the quartz wool ones, but the preparation took several hours. Their main advantage lies in the possibility of on‐column detection, because the detection window can be burnt immediately behind the frit. 相似文献
82.
Dr. Giambattista Testolin Dr. Jana Richter Antje Ritter Dr. Hans Prochnow Prof. Dr. Jesko Köhnke Prof. Dr. Mark Brönstrup 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(54):e202201297
The rise of antibiotic resistance causes a serious health care problem, and its counterfeit demands novel, innovative concepts. The combination of photopharmacology, enabling a light-controlled reversible modulation of drug activity, with antibiotic drug design has led to first photoswitchable antibiotic compounds derived from established scaffolds. In this study, we converted cystobactamids, gyrase-inhibiting natural products with an oligoaryl scaffold and highly potent antibacterial activities, into photoswitchable agents by inserting azobenzene in the N-terminal part and/or an acylhydrazone moiety near the C-terminus, yielding twenty analogs that contain mono- as well as double-switches. Antibiotic and gyrase inhibition properties could be modulated 3.4-fold and 5-fold by light, respectively. Notably, the sensitivity of photoswitchable cystobactamids towards two known resistance factors, the peptidase AlbD and the scavenger protein AlbA, was light-dependent. While irradiation of an analog with an N-terminal azobenzene with 365 nm light led to less degradation by AlbD, the AlbA-mediated inactivation was induced. This provides a proof-of-principle that resistance towards photoswitchable antibiotics can be optically controlled. 相似文献
83.
Jan Zelenka Dr. Aleksandr Pereverzev Dr. Ullrich Jahn Prof. Dr. Jana Roithová 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(28):e202104493
Photocatalytic generation of nitrenes and radicals can be used to tune or even control their reactivity. Photocatalytic activation of sulfonyl azides leads to the elimination of N2 and the resulting reactive species initiate C−H activations and amide formation reactions. Here, we present reactive radicals that are generated from sulfonyl azides: sulfonyl nitrene radical anion, sulfonyl nitrene and sulfonyl amidyl radical, and test their gas phase reactivity in C−H activation reactions. The sulfonyl nitrene radical anion is the least reactive and its reactivity is governed by the proton coupled electron transfer mechanism. In contrast, sulfonyl nitrene and sulfonyl amidyl radicals react via hydrogen atom transfer pathways. These reactivities and detailed characterization of the radicals with vibrational spectroscopy and with DFT calculations provide information necessary for taking control over the reactivity of these intermediates. 相似文献
84.
Jana ic
labur Marko Brajer Sandra Voa Ante Gali Sanja Radman Suzana Rimac-Brn
i Qiang Xia Zhenzhou Zhu Nabil Grimi Francisco J. Barba Nataa Hulak 《Molecules (Basel, Switzerland)》2021,26(7)
Spices are a popular food of plant origin, rich in various phytochemicals and recognized for their numerous properties. The aim of the study was to evaluate the antioxidant and antimicrobial activity, as well as the content of specialized metabolites, of aqueous extracts of three spice species––garlic (Allium sativum L.), ginger (Zingiber officinalle L.) and turmeric (Curcuma longa L.)––prepared by green extraction methods. Ultrasound treatment increased the chromaticity parameter b value of turmeric and ginger extracts, thus indicating a higher yellow color predominantly due to curcuminoids characteristic of these species. Ultrasound-assisted extraction significantly increased the content of total soluble solids, phenolic compounds, total carotenoids and vitamin C. The temperature of the system was also an important factor, with the highest (70 °C) conditions in ultrasound-assisted extraction having a positive effect on thermolabile compounds (vitamin C, phenolics, total carotenoids). For example, turmeric extract treated with ultrasound at 70 °C had up to a 67% higher vitamin C content and a 69.4% higher total carotenoid content compared to samples treated conventionally at the same temperature, while ginger extracts had up to 40% higher total phenols. All different concentrations of spice extracts were not sufficient for complete inhibition of pathogenic bacterial strains of Salmonella, L. monocytogenes and S. aureus; however, only garlic extracts had an effect on slowing down the growth and number of L. monocytogenes colonies. Spice extracts obtained by ultrasonic treatment contained a significantly higher level of bioactive compounds and antioxidant capacity, suggesting that the extracts obtained have significant nutritional potential and thus a significant possibility for phytotherapeutic uses. 相似文献
85.
Branched chain amino acids (BCAAs), alanine and glutamine are determined in human plasma by capillary electrophoresis with contactless conductivity detection (CE/C4D). The baseline separation of five amino acids from other plasma components is achieved on the short capillary effective length of 18 cm in 3.2 mol/L acetic acid with addition of 13% v/v methanol as background electrolyte. Migration times range from 2.01 min for valine to 2.84 min for glutamine, and LODs for untreated plasma are in the interval 0.7–0.9 μmol/L. Sample treatment is based on the addition of acetonitrile to only 15 μL of plasma and supernatant is directly subjected to CE/C4D. Circulating amino acids are measured in patients with pancreatic cancer and cancer cachexia during oral glucose tolerance test. It is shown that patients with pancreatic cancer and cancer cachexia syndrome exhibit low basal circulating BCAAs and glutamine levels and loss of their insulin-dependent suppression. 相似文献
86.
Jana Holubová Zdeněk Černošek Eva Černošková 《Journal of Thermal Analysis and Calorimetry》2014,116(2):699-702
Thermal properties and structure of bulk glasses of (As2S3)1?x(Sb4S4)x system (x varies from 0 to 60 mol%) were studied by differential scanning calorimetry and Raman spectroscopy. It was found that with increasing Sb content the glasses can be sorted out to the three groups. The structure of glasses with x ≤ 10 is build-up mainly from AsS3/2 pyramidal units and the well-known crystallization resistance of As2S3 can explain the reluctance of these undercooled liquids against crystallization. In glasses with a higher content of antimony, i.e., 10 < x ≤ 30 mol%, the vibration characteristics of As4S4 clusters appear. Undercooled melts of these glasses crystallize forming both β-As4S4 and high-temperature phases of Sb2S3. Structure of glasses with the highest antimony content (x > 30 mol%) is based on SbS3/2 structural units significantly lowering stability of their undercooled melts from which only Sb2S3 crystallizes. 相似文献
87.
88.
A General Method for Preparing Bridged Organosilanes with Pendant Functional Groups and Functional Mesoporous Organosilicas
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Prof. Jana Hodačová Dr. Guillaume Toquer Dr. Xavier Cattoën Dr. Michel Wong Chi Man 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(33):10371-10382
New organosilica precursors containing two triethoxysilyl groups suitable for the organosilica material formation through the sol‐gel process were designed and synthesised. These precursors display alkyne or azide groups for attaching targeted functional groups by copper‐catalysed azide–alkyne cycloaddition (CuAAC) and can be used for the preparation of functional organosilicas following two strategies: 1) the functional group is first appended by CuAAC under anhydrous conditions, then the functional material is prepared by the sol‐gel process; 2) the precursor is first subjected to the sol‐gel process, producing porous, clickable bridged silsesquioxanes or periodic mesoporous organosilicas (PMOs), then the desired functional groups are attached by means of CuAAC. Herein, we show the feasibility of both approaches. A series of bridged bis(triethoxysilane)s with different pending organic moieties was prepared, demonstrating the compatibility of the first approach with many functional groups. In particular, we demonstrate that organic functional molecules bearing only one derivatisation site can be used to produce bridged organosilanes and bridged silsesquioxanes. In the second approach, clickable PMOs and porous bridged silsesquioxanes were prepared from the alkyne‐ or azide‐containing precursors, and thereafter, functionalised with complementary model azide‐ or alkyne‐containing molecules. These results confirmed the potential of this approach as a general methodology for preparing functional organosilicas with high loadings of functional groups. Both approaches give rise to a wide range of new functional organosilica materials. 相似文献
89.
Xavier Cattoën Achraf Noureddine Jonas Croissant Nirmalya Moitra Kristýna Bürglová Jana Hodačová Olivia de los Cobos Martine Lejeune Fabrice Rossignol Delphine Toulemon Sylvie Bégin-Colin Benoît P. Pichon Laurence Raehm Jean-Olivier Durand Michel Wong Chi Man 《Journal of Sol-Gel Science and Technology》2014,70(2):245-253
The combination of the copper-catalyzed alkyne-azide cycloaddition (CuAAC) reaction with sol–gel processing enables the versatile preparation of sol–gel materials under different shapes with targeted functionalities through a diversity-oriented approach. In this account, the development of the CuAAC reaction under anhydrous conditions for the synthesis of sol–gel precursors and for the assembling of magnetic nanoparticles on self-assembled monolayers is related, as well as the use of the classical CuAAC methodologies for the functionalization of mesoporous silica nanoparticles and microdots arrays. Coupling CuAAC and Sol–Gel will result in simplified preparations of multifunctional materials with controlled morphologies. 相似文献
90.
In this work, we compare labeling by two negatively charged fluorescent labels, 8-aminopyrene-1,3,6-trisulfonic acid (APTS) and 8-(2-hydrazino-2-oxoethoxy)pyrene-1,3,6-trisulfonic acid (Cascade Blue hydrazide [CBH]). Effectiveness of the labeling chemistries were investigated by 4-hydroxybenzaldehyde and maltoheptaose followed by LC/UV-MS and CE/LIF analysis, respectively. The reaction yield of APTS labeling was determined to be only ∼10%. This is due to reduction of almost 90% of the analyte by sodium cyanoborohydride to alcohol, which cannot be further labeled via reductive amination. However, the CBH labeling provides ∼90% reaction yield based on the LC/UV-MS measurements. The significantly higher labeling yield was also confirmed by CE/LIF measurements. Finally, the more effective hydrazone formation technique of CBH was characterized and applied for N-linked glycan analysis by CE/LIF. 相似文献