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61.
Caetano P. Sabino Martha S. Ribeiro Mark Wainwright Carolina dos Anjos Fábio P. Sellera Milena Dropa Nathalia B. Nunes Guilherme T. P. Brancini Gilberto U. L. Braga Victor E. Arana-Chavez Raul O. Freitas Nilton Lincopan Maurício S. Baptista 《Photochemistry and photobiology》2023,99(2):742-750
The unbridled dissemination of multidrug-resistant pathogens is a major threat to global health and urgently demands novel therapeutic alternatives. Antimicrobial photodynamic therapy (aPDT) has been developed as a promising approach to treat localized infections regardless of drug resistance profile or taxonomy. Even though this technique has been known for more than a century, discussions and speculations regarding the biochemical mechanisms of microbial inactivation have never reached a consensus on what is the primary cause of cell death. Since photochemically generated oxidants promote ubiquitous reactions with various biomolecules, researchers simply assumed that all cellular structures are equally damaged. In this study, biochemical, molecular, biological and advanced microscopy techniques were employed to investigate whether protein, membrane or DNA damage correlates better with dose-dependent microbial inactivation kinetics. We showed that although mild membrane permeabilization and late DNA damage occur, no correlation with inactivation kinetics was found. On the other hand, protein degradation was analyzed by three different methods and showed a dose-dependent trend that matches microbial inactivation kinetics. Our results provide a deeper mechanistic understanding of aPDT that can guide the scientific community toward the development of optimized photosensitizing drugs and also rationally propose synergistic combinations with antimicrobial chemotherapy. 相似文献
62.
New Copper,Palladium and Nickel Catalytic Systems: An Evolution towards More Efficient Procedures
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Raul SanMartin María Teresa Herrero Esther Domínguez 《Chemical record (New York, N.Y.)》2016,16(3):1082-1095
Metal‐catalysed reactions are a fundamental tool in synthetic chemistry. Increasingly challenging transformations can be accomplished only by means of certain metal catalysts. However, there still remains the need for a substantial decrease of the amount of catalyst, for better reuse or recycling of such active species, and for the avoidance of relatively toxic solvents in favour of environmentally friendly media. These facts apply to copper‐, palladium‐, and nickel‐catalysed cross‐coupling reactions, direct arylations, and oxidative processes. This account summarises our research on the last reactions, featuring an evolution towards more sustainable procedures in this field. 相似文献
63.
Rimer JD Roth DD Vlachos DG Lobo RF 《Langmuir : the ACS journal of surfaces and colloids》2007,23(5):2784-2791
We show that germania nanoparticle self-assembly in basic aqueous solutions occurs at a critical aggregation concentration (CAC) corresponding to a 1:1 GeO2/OH- molar ratio. A combination of pH, conductivity, and small-angle X-ray scattering (SAXS) measurements was used to monitor the effect of incremental additions of germanium (IV) ethoxide to basic solutions of sodium hydroxide or tetraalkylammonium cations. Plots of pH versus total germania concentration at varying alkalinities generated a phase diagram with three distinct regions. The diagram was analyzed with a thermodynamic model based on the chemical equilibria of germania speciation and dissociation. The model, which uses the GeO-H dissociation constant (pK = 7.1) as the single fitting parameter, quantitatively captures trends in the CAC and pH. SAXS patterns reveal that the germania nanoparticles have either a cubic or a spherical geometry of dimension approximately 1 nm that is independent of solution pH and cation. On the basis of these and other literature findings, we propose that the germania nanoparticle structure is that of the cubic octamer (double four-membered ring, Ge8O12(OH)8), which is common among condensed GeO2 materials and building units in [Ge,Si]-zeolites. Comparisons between germania and silica solutions show distinct differences in their phase behavior and nanoparticle structure. The results presented here, in combination with previous studies of siliceous solutions, provide a framework for ongoing studies of combined germania-silica phase behavior, which is part of an overarching effort to understand the influence of heteroatoms in the growth and structure direction of zeolites. 相似文献
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65.
In this Letter we discuss light neutrino dipole moments, computed in the neutrino-mass extended Standard Model, as a possible source for neutrino condensates which may cause cosmological constant observed today. 相似文献
66.
Synthetic efforts toward the chlorinated aza-propellane alkaloid acutumine (1) are described. The key vicinal quaternary centers were constructed by a photochemical [2 + 2] cycloaddition reaction of a furanyl-tetrahydroindolone. Dihydroxylation of the [2 + 2] product enabled a tandem retro-aldol/intramolecular ketalization reaction, which revealed the aza-propellane core of 1 while generating an unusual, caged, pentacyclic hemiketal product. 相似文献
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68.
Hudson MR Queen WL Mason JA Fickel DW Lobo RF Brown CM 《Journal of the American Chemical Society》2012,134(4):1970-1973
Low-pressure adsorption of carbon dioxide and nitrogen was studied in both acidic and copper-exchanged forms of SSZ-13, a zeolite containing an 8-ring window. Under ideal conditions for industrial separations of CO(2) from N(2), the ideal adsorbed solution theory selectivity is >70 in each compound. For low gas coverage, the isosteric heat of adsorption for CO(2) was found to be 33.1 and 34.0 kJ/mol for Cu- and H-SSZ-13, respectively. From in situ neutron powder diffraction measurements, we ascribe the CO(2) over N(2) selectivity to differences in binding sites for the two gases, where the primary CO(2) binding site is located in the center of the 8-membered-ring pore window. This CO(2) binding mode, which has important implications for use of zeolites in separations, has not been observed before and is rationalized and discussed relative to the high selectivity for CO(2) over N(2) in SSZ-13 and other zeolites containing 8-ring windows. 相似文献
69.
Katrin Meier Raul Cardoso‐Gil Ulrich Burkhardt Caroline Curfs Michael Hanfland Yuri Grin PD Dr. Ulrich Schwarz 《无机化学与普通化学杂志》2012,638(10):1446-1451
The rare‐earth metal germanides RE2Ge9 (RE = Nd, Sm) have been prepared by thermal decomposition of the metastable high‐pressure phases REGe5 at ambient pressure. The compounds adopt an orthorhombic unit cell with a = 396.34(4) pm; b = 954.05(8) pm and c = 1238.4(1) pm for Nd2Ge9 and a = 395.46(7) pm; b = 946.4(2) pm and c = 1232.1(3) pm for Sm2Ge9. Crystal structure refinements reveal space group Pmmn (No. 59) for Nd2Ge9. The atomic pattern resembles an ordered defect variety of the pentagermanide motif REGe5 (RE = La; Nd, Sm, Gd, Tb) comprising corrugated germanium layers. These condense into a three‐dimensional network interconnected by eight‐coordinated germanium atoms. The resulting framework channels along [100] enclose the neodymium atoms. With respect to the atomic arrangement of the pentagermanides, half of the interlayer germanium atoms are eliminated in an ordered way so that occupied and empty germanium columns alternate along [001]. The rare‐earth metal atoms of both types of compounds, REGe5 and RE2Ge9, exhibit the electronic states 4f 3 and 4f 5 (oxidation state +3) for neodymium and samarium, respectively, evidencing that the modification of the germanium network leaves the electron configuration of the metal atoms unaffected. 相似文献
70.