全文获取类型
收费全文 | 2131篇 |
免费 | 177篇 |
国内免费 | 4篇 |
专业分类
化学 | 1894篇 |
晶体学 | 16篇 |
力学 | 33篇 |
数学 | 124篇 |
物理学 | 245篇 |
出版年
2023年 | 16篇 |
2022年 | 34篇 |
2021年 | 39篇 |
2020年 | 45篇 |
2019年 | 57篇 |
2018年 | 34篇 |
2017年 | 28篇 |
2016年 | 89篇 |
2015年 | 99篇 |
2014年 | 107篇 |
2013年 | 173篇 |
2012年 | 140篇 |
2011年 | 174篇 |
2010年 | 137篇 |
2009年 | 103篇 |
2008年 | 128篇 |
2007年 | 116篇 |
2006年 | 100篇 |
2005年 | 83篇 |
2004年 | 71篇 |
2003年 | 81篇 |
2002年 | 71篇 |
2001年 | 47篇 |
2000年 | 40篇 |
1999年 | 11篇 |
1998年 | 11篇 |
1997年 | 7篇 |
1996年 | 17篇 |
1995年 | 13篇 |
1994年 | 11篇 |
1993年 | 9篇 |
1992年 | 8篇 |
1990年 | 7篇 |
1989年 | 6篇 |
1988年 | 6篇 |
1987年 | 7篇 |
1985年 | 7篇 |
1984年 | 10篇 |
1983年 | 7篇 |
1982年 | 12篇 |
1981年 | 11篇 |
1980年 | 8篇 |
1979年 | 5篇 |
1978年 | 13篇 |
1977年 | 9篇 |
1976年 | 11篇 |
1975年 | 10篇 |
1974年 | 7篇 |
1958年 | 7篇 |
1957年 | 6篇 |
排序方式: 共有2312条查询结果,搜索用时 15 毫秒
71.
Fanny dOrly Laura Trapiella-Alfonso Camille Lescot Marie Pinvidic Bich-Thuy Doan Anne Varenne 《Molecules (Basel, Switzerland)》2021,26(15)
There is a challenging need for the development of new alternative nanostructures that can allow the coupling and/or encapsulation of therapeutic/diagnostic molecules while reducing their toxicity and improving their circulation and in-vivo targeting. Among the new materials using natural building blocks, peptides have attracted significant interest because of their simple structure, relative chemical and physical stability, diversity of sequences and forms, their easy functionalization with (bio)molecules and the possibility of synthesizing them in large quantities. A number of them have the ability to self-assemble into nanotubes, -spheres, -vesicles or -rods under mild conditions, which opens up new applications in biology and nanomedicine due to their intrinsic biocompatibility and biodegradability as well as their surface chemical reactivity via amino- and carboxyl groups. In order to obtain nanostructures suitable for biomedical applications, the structure, size, shape and surface chemistry of these nanoplatforms must be optimized. These properties depend directly on the nature and sequence of the amino acids that constitute them. It is therefore essential to control the order in which the amino acids are introduced during the synthesis of short peptide chains and to evaluate their in-vitro and in-vivo physico-chemical properties before testing them for biomedical applications. This review therefore focuses on the synthesis, functionalization and characterization of peptide sequences that can self-assemble to form nanostructures. The synthesis in batch or with new continuous flow and microflow techniques will be described and compared in terms of amino acids sequence, purification processes, functionalization or encapsulation of targeting ligands, imaging probes as well as therapeutic molecules. Their chemical and biological characterization will be presented to evaluate their purity, toxicity, biocompatibility and biodistribution, and some therapeutic properties in vitro and in vivo. Finally, their main applications in the biomedical field will be presented so as to highlight their importance and advantages over classical nanostructures. 相似文献
72.
Jean Claude Didelot Tomani Olivier Bonnet Alain Nyirimigabo William Deschamps Alembert Tiabou Tchinda Olivia Jansen Allison Ledoux Marie Jeanne Mukazayire Luc Vanhamme Michel Frdrich Raymond Muganga Jacob Souopgui 《Molecules (Basel, Switzerland)》2021,26(9)
Malaria remains one of the leading causes of death in sub-Saharan Africa, ranked in the top three infectious diseases in the world. Plants of the Eriosema genus have been reported to be used for the treatment of this disease, but scientific evidence is still missing for some of them. In the present study, the in vitro antiplasmodial activity of the crude extract and compounds from Eriosema montanum Baker f. roots were tested against the 3D7 strain of Plasmodium falciparum and revealed using the SYBR Green, a DNA intercalating compound. The cytotoxicity effect of the compounds on a human cancer cell line (THP-1) was assessed to determine their selectivity index. It was found that the crude extract of the plant displayed a significant antiplasmodial activity with an IC50 (µg/mL) = 17.68 ± 4.030 and a cytotoxic activity with a CC50 (µg/mL) = 101.5 ± 12.6, corresponding to a selective antiplasmodial activity of 5.7. Bioactivity-guided isolation of the major compounds of the roots’ crude extract afforded seven compounds, including genistein, genistin and eucomic acid. Under our experimental conditions, using Artemisinin as a positive control, eucomic acid showed the best inhibitory activity against the P. falciparum 3D7, a well-known chloroquine-sensitive strain. The present results provide a referential basis to support the traditional use of Eriosema species in the treatment of malaria. 相似文献
73.
Dorra Aissaoui-Zid Mohamed-Chiheb Saada Wassim Moslah Marie Potier-Cartereau Aude Lemettre Houcemeddine Othman Marc Gaysinski Zaineb Abdelkafi-Koubaa Soumaya Souid Naziha Marrakchi Christophe Vandier Khadija Essafi-Benkhadir Najet Srairi-Abid 《Molecules (Basel, Switzerland)》2021,26(24)
Glioblastoma is an aggressive cancer, against which medical professionals are still quite helpless, due to its resistance to current treatments. Scorpion toxins have been proposed as a promising alternative for the development of effective targeted glioblastoma therapy and diagnostic. However, the exploitation of the long peptides could present disadvantages. In this work, we identified and synthetized AaTs-1, the first tetrapeptide from Androctonus australis scorpion venom (Aa), which exhibited an antiproliferative effect specifically against human glioblastoma cells. Both the native and synthetic AaTs-1 were endowed with the same inhibiting effect on the proliferation of U87 cells with an IC50 of 0.56 mM. Interestingly, AaTs-1 was about two times more active than the anti-glioblastoma conventional chemotherapeutic drug, temozolomide (TMZ), and enhanced its efficacy on U87 cells. AaTs-1 showed a significant similarity with the synthetic peptide WKYMVm, an agonist of a G-coupled formyl-peptide receptor, FPRL-1, known to be involved in the proliferation of glioma cells. Interestingly, the tetrapeptide triggered the dephosphorylation of ERK, p38, and JNK kinases. It also enhanced the expression of p53 and FPRL-1, likely leading to the inhibition of the store operated calcium entry. Overall, our work uncovered AaTs-1 as a first natural potential FPRL-1 antagonist, which could be proposed as a promising target to develop new generation of innovative molecules used alone or in combination with TMZ to improve glioblastoma treatment response. Its chemical synthesis in non-limiting quantity represents a valuable advantage to design and develop low-cost active analogues to treat glioblastoma cancer. 相似文献
74.
Wan H Holmén AG Wang Y Lindberg W Englund M Någård MB Thompson RA 《Rapid communications in mass spectrometry : RCM》2003,17(23):2639-2648
A high-throughput pKa screening method based on pressure-assisted capillary electrophoresis (CE) and mass spectrometry (MS) is presented. Effects of buffer type and ionic strength on sensitivity and pKa values were investigated. Influence of dimethyl sulfoxide (DMSO) concentration present in the sample on effective mobility measurement was examined. A series of ten volatile buffers, covering a pH range from 2.5 to 10.5 with the same ionic strength, was employed. The application of volatile background electrolytes resulted in significant signal increase as compared with commonly used non-volatile phosphate buffers. In general, the CE/MS system provided a ten-fold higher sensitivity than conventional UV detection. The newly developed CE/MS method offers high-throughput capacity by pooling a number of compounds into a single sample. Simultaneous measurement of more than 50 compounds was readily achieved in less than 150 min. The measured pKa values are consistent with the published data obtained from the CE/UV method and are also in good agreement with data generated by other methods. Other advantages of using CE/MS for pKa screening are illustrated with typical examples, including poorly soluble compounds and non-UV-absorbing compounds. 相似文献
75.
Several novel pentamethylcyclopentadienyl complexes of general formula [(C5Me5)IrL3][BF4]2 were prepared including the tris(solvent) precursors [(C5Me5)M(acetone)2(H2O)][BF4]2 (M = Rh, Ir) (1a,b). The X-ray molecular structures of 1a,b were determined at low temperature. Complexes 1a,b are isostructural, and both compounds crystallize in the monoclinic space group P2(1)/c with a = 10.157(3) A, b = 14.038(9) A, c = 16.335(2) A, beta = 99.73(2) degrees, and Z = 4 for 1a and with a = 10.107(9) A, b = 13.994(16) A, c = 15.996(34) A, beta = 99.61(12) degrees, and Z = 4 for 1b. The coordinated water molecule is hydrogen bonded to both BF4(-) anions. Reaction of 1a,b with pyridine (py) afforded the related tris(pyridine) complexes [(C5Me5)M(eta1-(N)-py)3][BF4]2 (M = Rh, Ir) (2a,b). Complex 2b was characterized by X-ray crystallography, monoclinic space group P2(1)/c with a = 8.665(3) A, b = 19.687(7) A, c = 18.408(5) A, beta = 94.17(3) degrees, and Z = 4. Moreover, we prepared the novel neutral compounds (C5Me5)M(eta2-NO3)(eta1-NO3) (M = Rh, Ir) (4a,b) where the anions are bonded to the metal center instead of a coordinating solvent as confirmed by X-ray study on the iridium complex 4b. The latter crystallizes in the orthorhombic space group Pcab with a = 13.032(4) A, b = 14.370(11) A, c = 14.839(18) A, and Z = 8. 相似文献
76.
77.
Safaa El‐din H. Etaiw Hassan Marie Elsayed M. Shalaby Rabie S. Farag Fatma A. Elsharqawy 《应用有机金属化学》2019,33(9)
Orange prismatic crystals of the supramolecular coordination polymer (SCP) ∞3[Cu(CN)2(Me3Sn)(Pyz)], SCP 1 , were synthesized using a self‐assembly method under ambient conditions. Nanosized 1 was obtained using the same molar ratio in water by ultrasonic irradiation. SCP 1 was characterized using single‐crystal X‐ray diffraction, elemental analysis, thermal analysis and Fourier transform infrared spectroscopy. SCP 1 and its nanosized 1 particles were also examined using powder X‐ay diffraction and scanning electron microscopy. The luminescence emission of SCP 1 was studied as well as its use as a sensor for the detection of common organic solvents and metal ions. Also, the catalytic activities of nanosized 1 towards various organic dyes were investigated under ambient conditions, UV irradiation and ultrasonic irradiation. Nanosized 1 as a heterogeneous nanoparticle catalyst exhibits high catalytic activity for the degradation of eosin‐Y and acid blue dyes. The mechanism of degradation investigated using various scavenger techniques is proposed and discussed. The catalytic oxidation process is mainly caused by ?OH radicals. 相似文献
78.
Mikkelsen Ø Skogvold SM Schrøder KH Gjerde MI Aarhaug TA 《Analytical and bioanalytical chemistry》2003,377(2):322-326
Evaluation of different solid electrode systems for detection of zinc, lead, cobalt, and nickel in process water from metallurgical nickel industry with use of differential pulse stripping voltammetry has been performed. Zinc was detected by differential pulse anodic stripping voltammetry (DPASV) on a dental amalgam electrode as intermetallic Ni–Zn compound after dilution in ammonium buffer solution. The intermetallic compound was observed at –375 mV, and a linear response was found in the range 0.2–1.2 mg L–1 (r2=0.98) for 60 s deposition time. Simultaneous detection of nickel and cobalt in the low g L–1 range was successfully performed by use of adsorptive cathodic stripping voltammetry (AdCSV) of dimethylglyoxime complexes on a silver–bismuth alloy electrode, and a good correlation was found with corresponding AAS results (r2=0.999 for nickel and 0.965 for cobalt). Analyses of lead in the g L–1 range in nickel-plating solution were performed with good sensitivity and stability by DPASV, using a working electrode of silver together with a glassy carbon counter electrode in samples diluted 1:3 with distilled water and acidified with H2SO4 to pH 2. A new commercial automatic at-line system was tested, and the results were found to be in agreement with an older mercury drop system. The stability of the solid electrode systems was found to be from one to several days without any maintenance needed. 相似文献
79.
80.
Ayda Khadhri Intidhar Bouali Chedia Aouadhi Marie‐Christine Lagel Eric Masson Antonio Pizzi 《Biomedical chromatography : BMC》2019,33(11)
This study aimed to investigate the effect of the maturation process of sweet marjoram (Origanum majorana L.) on essential oil composition, the phenolic profile of ethanolic extract and their antioxidant capacities. The essential oil composition was studied at three stages of maturity by GC–MS. Thirty compounds were detected representing 100% of the total essential oil. p‐Menth‐1‐en‐4‐ol was the major compound (37.15–76.94%) followed by cyclohexanol‐3,3,5 trimethyl (5.41–15.99%) and α‐terpineol (0.94–11.34%). During the maturation process, an accumulation of oxygenated monoterpenes was observed. The phenolic composition was studied using matrix‐assisted laser desorption/ionization time of flight. The analysis showed the presence of short flavonoid monomers at all stages of maturation. The antioxidant capacity of ethanolic extracts and essential oils was evaluated using the DPPH assay, iron chelating power and reducing power assay. The highest phenolic content and antioxidant capacity were found at flowering stage. These findings on essential oil composition, phenolic profile and antioxidant capacity of O. majorana at three different stages of development provide more information on how these secondary metabolites are accumulated. 相似文献