The Biochemical Mechanisms of Antimicrobial Photodynamic Therapy†

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.     

The Influence of the Electrodeposition Conditions on the Electroanalytical Performance of the Bismuth Film Electrode for Lead Determination

The bismuth film is a great promise as a suitable material to replace the mercury electrodes due to its low toxicity and good cathodic potential range. This work studies the influence of the electrodeposition conditions in the morphology and electroanalytical performance of the bismuth film electrodeposited onto copper electrode. The bismuth films were obtained in nitric or hydrochloric acid solutions with and without the presence of sodium citrate. The films were characterized by field emission scanning electron microscopy (FE‐SEM) and scanning electron microscopy with energy dispersive X‐ray spectrometry (SEM‐EDX). The microscopic analysis of the bismuth film obtained in HCl solution with sodium citrate (BIFE‐Cit) showed more homogeneous structure with higher content of bismuth than the film obtained in HCl only (BiFE‐HCl). The BiFE‐Cit exhibited a better analytical performance for lead with good adherence to the copper substrate.     

Cationic and anionic environments in LiTFSI-doped di-ureasils with application in solid-state electrochromic devices

Fourier Transform mid-infrared and Raman spectroscopies were used to investigate the cation/polymer, cation/urea bridge, cation/anion and hydrogen bonding interactions in poly(oxyethylene) (POE)/siloxane di-ureasil networks prepared by the sol–gel route and doped with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). Materials with compositions 200 ?n ? 5 (where n expresses the molar ratio OCH₂CH₂/Li⁺) were studied. The Li⁺ ions coordinate to the urea carbonyl oxygen atoms over the whole range of salt concentration considered. Bonding to the ether oxygen atoms of the POE chains occurs at n ? 40, although a significant fraction of the POE chains remain non-coordinated. In these high salt content samples, the cations interact with the anions forming contact ion pairs. “Free” ions are probably the main charge carriers at the room temperature conductivity maximum of these ormolytes.     

The meta and para OH Substitution Effect on C-Phenyl-Nitrilimine Bond-Shift Isomers

The geometric and electronic structure of 1,3-dipolar species, in particular of nitrile imines, can be surprisingly intricate. A particular example is the C-phenyl-nitrilimine, which exists as two energy minima that constitute bond-shift isomers. To examine the effect of substituents in the phenyl ring, here we investigate the meta and para OH substituted derivatives. These two nitrile imines were generated in an argon matrix by UV-irradiation of 2H-tetrazole precursors and found to photoisomerize to carbodiimides via 1H-diazirines. The different effects of the OH substitution in meta and para positions on the bond-shift isomerism are rationalized with the support of Natural Resonance Theory and Hirshfeld atomic charges. The understanding of how substitution affects the structural characteristics of C-phenyl-nitrilimines, opens a door to modulate the chemistry of those compounds (e. g. in cycloaddition reactions) by appropriate tuning of their substitution (substituent type and position).     

Synthesis and characterization of nanostructured iron compounds prepared from the decomposition of iron pentacarbonyl dispersed into carbon materials with varying porosities

This work describes the production and characterization of carbon-iron nanocomposites obtained from the decomposition of iron pentacarbonyl (Fe(CO)₅) mixed with different carbon materials: a high surface area activated carbon (AC), powdered graphite (G), milled graphite (MG), and carbon black (CB). The nanocomposites were prepared either under argon or in ambient atmosphere, with a fixed ratio of Fe(CO)₅ (4.0 mL) to carbon precursor (2.0 g). The images of scanning electron microscopy and the analysis of textural properties indicated the presence of nanostructured Fe compounds homogeneously dispersed into the different classes of pores of the carbon matrices. The elemental Fe content was always larger for samples prepared in ambient atmosphere, reaching values in the range of 20–32 wt%. On the other hand, samples prepared under argon showed reduced Fe content, with values in the range 5–10 wt% for samples prepared from precursors with low surface area (G, MG, and CB) and a much higher value (~19 wt%) for samples prepared from the precursor of high surface area (AC). Mössbauer spectroscopy and X-ray diffractometry showed that the nanoparticles were mostly composed of iron oxides in the case of the samples prepared in oxygen-rich ambient atmosphere and also for the AC-derived nanocomposite prepared under argon, which is consistent with the large oxygen content of this precursor. For the other precursors, with reduced or no oxygen content, metallic iron and iron carbides were found to be the dominant phases in samples prepared under oxygen-free atmosphere. The samples prepared in ambient atmosphere and the AC-derived sample prepared under argon exhibited superparamagnetic behavior at room temperature, as revealed by temperature-dependent magnetization curves and Mössbauer spectroscopy.     

Microbiological assay for ceftazidime injection

A simple, sensitive, and specific biodiffusion assay for the antibacterial ceftazidime was developed using a strain of Staphylococcus epidermidis (ATCC 12228) as the test organism. Ceftazidime was measured in powder for injection at concentrations ranging from 100 to 400 microg/mL. The calibration graph for ceftazidime was linear (r2 = 1), and the method validation showed that it was precise (relative standard deviation = 0.415) and accurate. The results obtained by biodiffusion assay were statistically calculated by linear parallel model and by means of regression analysis and were verified using analysis of variance. It was concluded that the microbiological assay is satisfactory for in vitro quantification of the antibacterial activity of ceftazidime in pharmaceuticals.     

Transition metal bisdithiolene complexes based on extended ligands with fused tetrathiafulvalene and thiophene moieties: new single-component molecular metals

The gold and nickel bisdithiolene complexes based on new highly extended ligands incorporating fused tetrathiafulvalene and thiophene moieties (alpha-tdt=thiophenetetrathiafulvalenedithiolate and dtdt=dihydro- thiophenetetrathiafulvalenedithiolate), were prepared and characterised by using cyclic voltammetry, single crystal X-ray diffraction, EPR, magnetic susceptibility and electrical transport measurements. These complexes, initially obtained under anaerobic conditions as diamagnetic gold monoanic [nBu(4)N][Au(alpha-tdt)(2)] (4), [nBu(4)N][Au(dtdt)(2)] (3) and nickel dianionic species [(nBu(4)N)(2)][Ni(alpha-tdt)(2)] (8), [(nBu(4)N)(2)][Ni(dtdt)(2)] (7), can be easily oxidised to the stable neutral state just by air or iodine exposure. The monoanionic complexes crystallise in at least two polymorphs, all of which have good cation and anion segregation in alternated layers, the anion layers making a dense 2D network of short SS contacts. All of the neutral complexes, obtained as microcrystalline or quasi amorphous fine powder, present relatively large magnetic susceptibilities that correspond to effective magnetic moments in the range 1-3 mu(B) indicative of high spin states and very high electrical conductivity that in case of the Ni compound can reach sigma(RT) approximately 250 S cm(-1) with a clear metallic behaviour. These compounds are new examples of the still rare single-component molecular metals.     

FTIR Spectroscopy as a Tool to Study Age-Related Changes in Cardiac and Skeletal Muscle of Female C57BL/6J Mice

Studying aging is important to further understand the molecular mechanisms underlying this physiological process and, ideally, to identify a panel of aging biomarkers. Animals, in particular mice, are often used in aging studies, since they mimic important features of human aging, age quickly, and are easy to manipulate. The present work describes the use of Fourier Transform Infrared (FTIR) spectroscopy to identify an age-related spectroscopic profile of the cardiac and skeletal muscle tissues of C57BL/6J female mice. We acquired ATR-FTIR spectra of cardiac and skeletal muscle at four different ages: 6; 12; 17 and 24 months (10 samples at each age) and analyzed the data using multivariate statistical tools (PCA and PLS) and peak intensity analyses. The results suggest deep changes in protein secondary structure in 24-month-old mice compared to both tissues in 6-month-old mice. Oligomeric structures decreased with age in both tissues, while intermolecular β-sheet structures increased with aging in cardiac muscle but not in skeletal muscle. Despite FTIR spectroscopy being unable to identify the proteins responsible for these conformational changes, this study gives insights into the potential of FTIR to monitor the aging process and identify an age-specific spectroscopic signature.     

Gas transport in vulcanized natural rubber‐cellulose. II. Composites

This work reports the transport of carbon dioxide, oxygen, and nitrogen in amorphous membranes of vulcanized natural rubber reinforced with regenerated cellulose. The values of the permeability coefficient of carbon dioxide, oxygen, and nitrogen in the composites with 25% of cellulose, measured at 25 °C and 15 cmHg of pressure, are roughly one‐third of those measured in the same conditions for these gases in natural rubber. The isotherms representing the variation of both the permeability and diffusion coefficients of the gases with pressure present a relatively sharp increase in the region of low pressures, attributed to changes in the free volume. The analysis of the permeability characteristics of the membranes in terms of the free‐volume theory suggests that gas transport is severely hindered in both the cellulose phase and the cellulose–rubber interphase of the composites. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 393–402, 2000     

Water‐Accelerated Organometallic Chemistry: Alkyne Carboalumination – Sulfinimine Addition and Asymmetric Synthesis of Allylic Amines

Carboalumination of alkynes in the presence of catalytic Cp₂ZrCl₂ and H₂O affords vinyl‐alane intermediates, which serve as nucleophiles in the subsequent addition to enantiomerically enriched (tert‐butyl)‐ and (para‐tolyl)sulfinimines. This new in situ protocol produces two new C C bonds. Chiral allylic sulfinamides are obtained in high diastereoselectivity and in good yield. Cleavage of the chiral auxiliary leads to synthetically useful allylic amine building blocks, and facile oxidative degradation of the alkene moiety can be used as an approach toward amino acid derivatives and for assignment of absolute configuration.