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941.
Damien Mahaut Dr. Aurélien Chardon Loïc Mineur Prof. Guillaume Berionni Prof. Benoît Champagne 《Chemphyschem》2021,22(19):1958-1966
The activation or heterolytic splitting of methane, a challenging substrate usually restricted to transition metals, has so far proven elusive in experimental frustrated Lewis pair (FLP) chemistry. In this article, we demonstrate, using density functional theory (DFT), that 1-aza-9-boratriptycene is a conceptually simple intramolecular FLP for the activation of methane. Systematic comparison with other FLP systems allows to gain insight into their reactivity with methane. The thermodynamics and kinetics of methane activation are interpreted by referring to the analysis of the natural charges and by employing the distortion-interaction/activation strain (DIAS) model. These showed that the nature of the Lewis base influences the selectivity over the reaction pathway, with N Lewis bases favoring the deprotonation mechanism and P bases the hydride abstraction one. The lower barrier of activation for 1-aza-9-boratriptycene and the higher products stability are due to a better interaction energy than its counterparts, itself due to electrostatic interactions with the methane moiety, favorable orbital overlaps allowed by the side-attack, and space proximity between the B and N atoms. 相似文献
942.
Luk Petera Klaudia Mrazikova Lukas Nejdl Kristyna Zemankova Marketa Vaculovicova Adam Pastorek Svatopluk Civis Petr Kubelik Alan Heays Giuseppe Cassone Jiri Sponer Martin Ferus Judit Sponer 《Molecules (Basel, Switzerland)》2021,26(8)
Synthesis of RNA nucleobases from formamide is one of the recurring topics of prebiotic chemistry research. Earlier reports suggest that thymine, the substitute for uracil in DNA, may also be synthesized from formamide in the presence of catalysts enabling conversion of formamide to formaldehyde. In the current paper, we show that to a lesser extent conversion of uracil to thymine may occur even in the absence of catalysts. This is enabled by the presence of formic acid in the reaction mixture that forms as the hydrolysis product of formamide. Under the reaction conditions of our study, the disproportionation of formic acid may produce formaldehyde that hydroxymethylates uracil in the first step of the conversion process. The experiments are supplemented by quantum chemical modeling of the reaction pathway, supporting the plausibility of the mechanism suggested by Saladino and coworkers. 相似文献
943.
Fashina Bidemi Novák František Kučerík Jiří 《Journal of Thermal Analysis and Calorimetry》2021,145(6):3031-3039
Journal of Thermal Analysis and Calorimetry - In arid soils, humic acids (HAs) are used as amendments to improve water uptake from the atmosphere. This method of harvesting water involves several... 相似文献
944.
Marcelina Strzpek-Gomka Katarzyna Gawe-Bben Apostolis Angelis Beata Antosiewicz Zuriyadda Sakipova Kaldanay Kozhanova Kazimierz Gowniak Wirginia Kukula-Koch 《Molecules (Basel, Switzerland)》2021,26(4)
Growing scientific evidence indicates that Achillea biebersteinii is a valuable source of active ingredients with potential cosmetic applications. However, the data on its composition and pharmacological properties are still insufficient. This study aims to optimize the extraction procedure of the plant material, evaluate its phytochemical composition, and compare anti-tyrosinase potential of A. biebersteinii extracts obtained by various methods. In order to identify compounds responsible for the tyrosinase inhibitory activity of A. biebersteinii, the most active anti-tyrosinase extract was fractionated by column chromatography. The fractions were examined for their skin lightening potential by mushroom and murine tyrosinase inhibitory assays and melanin release assay. HPLC-ESI-Q-TOF-MS/MS analysis of the total extract revealed the presence of several phenolic acids, flavonoids, flavonoid glucosides, and carboxylic acid. Among them, fraxetin-8-O-glucoside, quercetin-O-glucopyranose, schaftoside/isoschaftoside, gmelinin B, 1,3-dicaffeoylquinic acid (1,3-DCQA), and ferulic acid were found in the fractions with the highest skin lightening potential. Based on obtained qualitative and quantitative analysis of the fractions, it was assumed that the caffeoylquinic acid derivatives and dicaffeoylquinic acid derivatives are more likely responsible for mushroom tyrosinase inhibitory activity of A. biebersteinii extracts and fractions. Ferulic acid was proposed as the most active murine tyrosinase inhibitor, responsible also for the reduced melanin release from B16F10 murine melanoma cells. 相似文献
945.
Fakhara Sabir Gbor Katona Edina Pallagi Dorina Gabriella Dob Hussein Akel Dniel Berkesi Zoltn Knya Ildik Cska 《Molecules (Basel, Switzerland)》2021,26(5)
The present study aimed to develop n-propyl gallate (PG)-encapsulated liposomes through a novel direct pouring method using the quality-by-design (QbD) approach. A further aim was to coat liposomes with hyaluronic acid (HA) to improve the stability of the formulation in nasal mucosa. The QbD method was used for the determination of critical quality attributes in the formulation of PG-loaded liposomes coated with HA. The optimized formulation was determined by applying the Box–Behnken design to investigate the effect of composition and process variables on particle size, polydispersity index (PDI), and zeta potential. Physiochemical characterization, in vitro release, and permeability tests, as well as accelerated stability studies, were performed with the optimized liposomal formulation. The optimized formulation resulted in 90 ± 3.6% encapsulation efficiency, 167.9 ± 3.5 nm average hydrodynamic diameter, 0.129 ± 0.002 PDI, and −33.9 ± 4.5 zeta potential. Coated liposomes showed significantly improved properties in 24 h in an in vitro release test (>60%), in vitro permeability measurement (420 μg/cm2) within 60 min, and also in accelerated stability studies compared to uncoated liposomes. A hydrogen-peroxide-scavenging assay showed improved stability of PG-containing liposomes. It can be concluded that the optimization of PG-encapsulated liposomes coated with HA has great potential for targeting several brain diseases. 相似文献
946.
M. Dubničková E. A. Kuzmina V. N. Chausov I. Ravnachka A. V. Boreyko E. A. Krasavin 《Physics of Particles and Nuclei Letters》2016,13(2):274-278
The modulatory effects of lipid A (diphosphoryl lipid A (DLA) and monophosphoryl lipid A (MLA)) on apoptosis induction and DNA structure damage (single and double-strand breaks (SSBs and DSBs, respectively)) in peripheral human blood lymphocytes are studied for 60Co gamma-irradiation. It is shown that in the presence of these agents the amount of apoptotic cells increases compared with the irradiated control samples. The effect is most strongly pronounced for DLA. In its presence, a significant increase is observed in the number of radiation-induced DNA SSBs and DSBs. Possible mechanisms are discussed of the modifying influence of the used agents on radiation-induced cell reactions 相似文献
947.
采用基于拉普拉斯算符聚焦形貌恢复方法,提出了模拟目标深度测量的数值模型。数值模拟的核心是基于通过几何光学预测的理想图像的卷积与透镜广义孔径函数的多色点扩散函数,即用聚焦误差替代抛物线圆柱形貌或高斯函数。该模型可以使用基于聚焦形貌恢复方法的传感器真实组件参数、光源光谱、光学系统离差、相机的光谱灵敏度。提出了光学系统离差(消球差、消色差、色差)对确定目标表面形貌的精确度和可靠性的影响。结果表明,该模型可以有效提高实验效率,缩短时滞,降低成本。 相似文献
948.
Kucerka N Pencer J Nieh MP Katsaras J 《The European physical journal. E, Soft matter》2007,23(3):247-254
The influence of cholesterol on the structure of unilamellar-vesicle (ULV) phospholipid bilayers is studied using small-angle
neutron scattering. ULVs made up of short-, mid- and long-chain monounsaturated phospholipids (diCn :1PC, n = 14 , 18, 22, respectively) are examined over a range (0-45mol %) of cholesterol concentrations. Cholesterol's effect on
bilayer structure is characterized through changes to the lipid's transmembrane thickness, lateral area and headgroup hydration.
For all three lipids, analysis of the experimental data shows that the addition of cholesterol results in a monotonic increase
of these parameters. In the case of the short- and mid-chain lipids, this is an expected result, however, such a finding was
unexpected for the long-chain lipid. This implies that cholesterol has a pronounced effect on the lipid's hydrocarbon chain
organization. 相似文献
949.
N. Vujičić S. Vdović D. Aumiler T. Ban H. Skenderović G. Pichler 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2007,41(3):447-454
We present direct observation of the velocity-selective optical pumping of
the Cs ground state hyperfine levels induced by the femtosecond (fs) laser
oscillator centered at either D2 (6 2S1/2↦6 2P3/2,
852 nm) or D1 (6
P1/2, 894 nm) cesium
line. We utilized previously developed modified direct frequency comb
spectroscopy (DFCS) which uses a fixed frequency comb for the excitation and
a weak cw scanning probe laser centered at the 133Cs 6
2S1/2↦6 2P3/2 transition (D2 line) for ground
levels population monitoring. The frequency comb excitation changes the
usual Doppler absorption profile into a specific periodic, comblike
structure. The mechanism of the velocity selective population transfer
between the Cs ground state hyperfine levels induced by fs pulse train
excitation is verified in a theoretical treatment of the multilevel atomic
system subjected to a pulse train resonant field interaction. 相似文献
950.
Michael Eastwood Petr Somberg Vladimír Sou
ek 《Journal of Geometry and Physics》2007,57(12):2539-2546
Using deformation theory, Braverman and Joseph constructed certain primitive ideals in the enveloping algebras of the simple Lie algebras. Except in the case sl(2,C), there is a special value of the deformation parameter giving an ideal of infinite codimension. For the classical Lie algebras, the uniqueness of the special value is equivalent to the existence of tensors with very particular properties. The existence of these tensors was concluded abstractly by Braverman and Joseph but here we present explicit formulae. This allows a rather direct computation of the special value of the deformation parameter. 相似文献