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1.
CaII Binding Regulates and Dominates the Reactivity of a Transition‐Metal‐Ion‐Dependent Diesterase from Mycobacterium tuberculosis 下载免费PDF全文
Dr. Marcelo M. Pedroso Prof. James A. Larrabee Dr. Fernanda Ely Shuhui E. Gwee Dr. Nataša Mitić Prof. David L. Ollis Prof. Lawrence R. Gahan Prof. Gerhard Schenk 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(3):999-1009
The diesterase Rv0805 from Mycobacterium tuberculosis is a dinuclear metallohydrolase that plays an important role in signal transduction by controlling the intracellular levels of cyclic nucleotides. As Rv0805 is essential for mycobacterial growth it is a promising new target for the development of chemotherapeutics to treat tuberculosis. The in vivo metal‐ion composition of Rv0805 is subject to debate. Here, we demonstrate that the active site accommodates two divalent transition metal ions with binding affinities ranging from approximately 50 nm for MnII to about 600 nm for ZnII. In contrast, the enzyme GpdQ from Enterobacter aerogenes, despite having a coordination sphere identical to that of Rv0805, binds only one metal ion in the absence of substrate, thus demonstrating the significance of the outer sphere to modulate metal‐ion binding and enzymatic reactivity. CaII also binds tightly to Rv0805 (Kd≈40 nm ), but kinetic, calorimetric, and spectroscopic data indicate that two CaII ions bind at a site different from the dinuclear transition‐metal‐ion binding site. CaII acts as an activator of the enzymatic activity but is able to promote the hydrolysis of substrates even in the absence of transition‐metal ions, thus providing an effective strategy for the regulation of the enzymatic activity. 相似文献
2.
3.
Strong Direct Magnetic Coupling in a Dinuclear CoII Tetrazine Radical Single‐Molecule Magnet 下载免费PDF全文
Toby J. Woods Dr. Maria Fernanda Ballesteros‐Rivas Sergei M. Ostrovsky Andrew V. Palii Oleg S. Reu Sophia I. Klokishner Dr. Kim R. Dunbar 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(29):10302-10305
The ligand‐centered radical complex [(CoTPMA)2‐μ‐bmtz.?](O3SCF3)3 ? CH3CN (bmtz=3,6‐bis(2′‐pyrimidyl)‐1,2,4,5‐tetrazine, TPMA=tris‐(2‐pyridylmethyl)amine) has been synthesized from the neutral bmtz precursor. Single‐crystal X‐ray diffraction studies have confirmed the presence of the ligand‐centered radical. The CoII complex exhibits slow paramagnetic relaxation in an applied DC field with a barrier to spin reversal of 39 K. This behavior is a result of strong antiferromagnetic metal–radical coupling combined with positive axial and strong rhombic anisotropic contributions from the CoII ions. 相似文献
4.
Roberto Kawakami Harrop Galvão Sófacles Figueredo Carreiro Soares Marcelo Nascimento Martins Maria Fernanda Pimentel Mário César Ugulino Araújo 《Analytica chimica acta》2015
This paper proposes a new method for calibration transfer, which was specifically designed to work with isolated variables, rather than the full spectrum or spectral windows. For this purpose, a univariate procedure is initially employed to correct the spectral measurements of the secondary instrument, given a set of transfer samples. A robust regression technique is then used to obtain a model with low sensitivity with respect to the univariate correction residuals. The proposed method is employed in two case studies involving near infrared spectrometric determination of specific mass, research octane number and naphthenes in gasoline, and moisture and oil in corn. In both cases, better calibration transfer results were obtained in comparison with piecewise direct standardization (PDS). The proposed method should be of a particular value for use with application-targeted instruments that monitor only a small set of spectral variables. 相似文献
5.
Effects of Ultraviolet Radiation (UVA+UVB) and Copper on the Morphology,Ultrastructural Organization and Physiological Responses of the Red Alga Pterocladiella capillacea 下载免费PDF全文
Éder C. Schmidt Marianne Kreusch Marthiellen R. de L. Felix Debora T. Pereira Giulia B. Costa Carmen Simioni Luciane C. Ouriques Francine L. Farias‐Soares Neusa Steiner Fungyi Chow Fernanda Ramlov Marcelo Maraschin Zenilda L. Bouzon 《Photochemistry and photobiology》2015,91(2):359-370
The effect of ultraviolet (UV) radiation and copper (Cu) on apical segments of Pterocladiella capillacea was examined under two different conditions of radiation, PAR (control) and PAR+UVA+UVB (PAR+UVAB), and three copper concentrations, ranging from 0 (control) to 0.62, 1.25 and 2.50 μm . Algae were exposed in vitro to photosynthetically active radiation (PAR) at 70 μmol photons m?2 s?1, PAR + UVB at 0.35 W m?2 and PAR +UVA at 0.70 W m?2 during a 12‐h photocycle for 3 h each day for 7 days. The effects of radiation and copper on growth rates, content of photosynthetic pigments and photosynthetic performance were analyzed. In addition, samples were processed for light and transmission electron microscopy. The content of photosynthetic pigments decreased after exposure to radiation and Cu. Compared with PAR radiation and copper treatments modified the kinetics patterns of the photosynthesis/irradiance curve. The treatments also caused changes in the ultrastructure of cortical and subcortical cells, including increased cell wall thickness and accumulation of plastoglobuli, as well as changes in the organization of chloroplasts. The results indicate that the synergistic interaction between UV radiation and Cu in P. capillacea, led to the failure of protective mechanisms and causing more drastic changes and cellular imbalances. 相似文献
6.
Bruno Fernandes Ana C. Correia Fernanda Cosme Fernando M. Nunes 《Natural product research》2015,29(1):37-45
The purpose of this work was to study the volatile composition of vine leaves and vine leaf infusion prepared from vine leaves collected at 30 and 60 days after grape harvest of two Vitis vinifera L. species. Eighteen volatile compounds were identified by gas chromatography–mass spectrometry in vine leaves and in vine leaf infusions. It was observed that the volatile compounds present in vine leaves are dependent on the time of harvest, with benzaldehyde being the major volatile present in vine leaves collected at 30 days after harvesting. There are significant differences in the volatile composition of the leaves from the two grape cultivars, especially in the sample collected at 60 days after grape harvest. This is not reflected in the volatile composition of the vine leaf infusion made from this two cultivars, the more important being the harvesting date for the volatile profile of vine leaf infusion than the vine leaves grape cultivar. 相似文献
7.
do Nascimento Ticiano Gomes Borges Arthur Luy Tavares Ferreira de Almeida Lara Mendes Ribeiro Êurica Adélia Nogueira Silva Fernanda Geny Calheiros da Costa Silva Valdemir do Nascimento Prata Ana Paula Basílio-Júnior Irinaldo Diniz Goulart Marília Oliveira Fonseca Morilla Demetrius Peireira de Freitas Johnnatan Duarte Aragão Cícero Flávio Soares 《Journal of Thermal Analysis and Calorimetry》2022,147(21):11949-11963
Journal of Thermal Analysis and Calorimetry - This work prepared and characterized microcapsule of Uncaria tomentosa (UT) in order to standardize a spray-dryer Uncaria tomentosa extract. The UT... 相似文献
8.
Nouemsi Soubgui Epiphanie Tene Fongang Rufin Theophile Kamseu Elie Oum Lissouck Rene Andreola Fernanda Boubakar Likiby Rossignol Sylvie Leonelli Cristina 《Journal of Thermal Analysis and Calorimetry》2021,145(6):3003-3018
Journal of Thermal Analysis and Calorimetry - The influence of drying on the microstructure, physical and chemical properties of some tropical wood species has been investigated using... 相似文献
9.
In this work, an inductive method to construct complete caps in affine spaces is provided. Using this tool, for odd and q odd, complete caps smaller than all already known ones are obtained. 相似文献
10.
María Fernanda Manrique-de-la-Cuba Luis Leyva-Parra Diego Inostroza Prof. Badhin Gomez Dr. Alejandro Vásquez-Espinal Prof. Jorge Garza Dr. Osvaldo Yañez Prof. William Tiznado 《Chemphyschem》2021,22(10):906-910
We report the global minima structures of Li8Si8, Li10Si9, and Li12Si10 systems, in which silicon moieties maintain structural and chemical bonding characteristics similar to those of their building blocks: the aromatic clusters Td−Li4Si4 and C2v−Li6Si5. Electron counting rules, chemical bonding analysis, and magnetic response properties verify the silicon unit‘s aromaticity persistence. This study demonstrates the feasibility of assembling silicon-based nanostructures from aromatics clusters as building blocks. 相似文献