A new Rose Bengal glycopolymer: Photosensitization in two stages.

Antimicrobial photodynamic therapy is a promising alternative to deal with antimicrobial resistance. However, both the low specificity and low local oxygen molecular concentrations decrease the antimicrobial efficiency limiting its use. An interesting approach to the problem is the use of molecules that can react reversibly with singlet oxygen by the formation of reversible endoperoxides, such as naphthalene, anthracene and pyridone derivatives.

Photoinduced behaviour of N,N-bidentate manganese(I) and rhenium(I) tricarbonyl complexes for singlet oxygen generation and CO release.

The combined action of singlet oxygen (O) and photoinduced carbon monoxide (CO) released by tricarbonyl metal complexes is a promising synergic treatment against multi-resistant bacterial infections. In this work, we explore the use of a polydentate ligand (bpm = 2,2-bipyrimidine) that offers the opportunity to accommodate two metal centers exhibiting both singlet oxygen generation and carbon monoxide releasing properties in a single molecule. A series of monometallic ([(bpm)M(CO)Br]; M = Mn, Re) and homo or hetero bimetallic ([Br(CO)M(bpm)M'(CO)Br]; M = Mn, Re) compounds were synthesized in moderate to good yields by modulating the metal precursor or the stoichiometry, also the syn:anti isomers ratio for the bimetallic complexes was dependent on the experimental conditions used.

Cells immersed in collagen matrices show a decrease in plasma membrane fluidity as the matrix stiffness increases.

Cells are constantly adapting to maintain their identity in response to the surrounding media's temporal and spatial heterogeneity. The plasma membrane, which participates in the transduction of external signals, plays a crucial role in this adaptation. Studies suggest that nano and micrometer areas with different fluidities at the plasma membrane change their distribution in response to external mechanical signals.

Synthesis and Photophysical Characterizations of Pyrroloquinolone Photosensitizers for Singlet Oxygen Production.

A series of pyrroloquinolone photosensitizers bearing different halogen substituents (Cl, Br, I) on the heterocyclic framework was studied. These structures were readily prepared through a multi-step synthetic sequence involving an oxidative protocol as an important step to access the quinolone framework. Spectroscopic characterizations and computational investigations were carried out to study the dyes before and after the oxidative step.

Photochemistry of P,N-bidentate rhenium(i) tricarbonyl complexes: reactive species generation and potential application for antibacterial photodynamic therapy.

In this work, we describe the photoisomerization of facial rhenium(i) tricarbonyl complexes bearing P,N-bidentate pyridyl/phosphine ligands with different chelating rings and anions: RePNBr, RePNTfO, and RePNNBr, which are triggered under irradiation at 365 nm in solutions. The apparent photodegradation rate constants ( ) depend on the coordinating ability of the solvent, being lowest in acetonitrile. The value increases as the temperature rises, suggesting a reactive IL excited state thermally populated from the MLCT excited state involved.

LAURDAN since Weber: The Quest for Visualizing Membrane Heterogeneity.

Any chemist studying the interaction of molecules with lipid assemblies will eventually be confronted by the topic of membrane bilayer heterogeneity and may ultimately encounter the heterogeneity of natural membranes. In artificial bilayers, heterogeneity is defined by phase segregation that can be in the nano- and micrometer range. In biological bilayers, heterogeneity is considered in the context of small (10-200 nm) sterol and sphingolipid-enriched heterogeneous and highly dynamic domains.

Fatty Acid Conjugates of Toluidine Blue O as Amphiphilic Photosensitizers: Synthesis, Solubility, Photophysics and Photochemical Properties.

Toluidine blue O (TBO) is a water-soluble photosensitizer that has been used in photodynamic antimicrobial and anticancer treatments, but suffers from limited solubility in hydrophobic media. In an effort to incrementally increase TBO's hydrophobicity, we describe the synthesis of hexanoic (TBOC6) and myristic (TBOC14) fatty acid derivatives of TBO formed in low to moderate percent yields by condensation with the free amine site. Covalently linking 6 and 14 carbon chains led to modifications of not only TBO's solubility, but also its photophysical and photochemical properties.

Unusual Oxidative Dealkylation Strategy toward Functionalized Phenalenones as Singlet Oxygen Photosensitizers and Photophysical Studies.

A series of functionalized 6-alkoxy phenalenones was prepared through an unprecedented oxidative dealkylation of readily available phenalene precursors. The starting phenalenes were efficiently synthesized an aminocatalyzed annulation/-alkylation strategy starting from simple substrates. The spectroscopic properties of some phenalenones were investigated in different solvents.

Carminic Acid Linked to Silica Nanoparticles as Pigment/Antioxidant Bifunctional Excipient for Pharmaceutical Emulsions.

The incorporation of pigments and natural polyphenols into inorganic matrices, resulting in a hybrid material that improves the resistance and chemical stability of the pigments and the antioxidant capacity of the materials, has been of great interest to the pharmaceutical, chemical and food industries. The aim of this work was to prepare and characterize a bifunctional pigment-antioxidant nanomaterial-based carminic acid-decorated solid core-mesoporous shell silica nanoparticles, evaluating its properties as a pigment, its antioxidant capacity and its properties as a chemical stabilizer of emulsions. The chemical stability of oil-in-water (O/W) Pickering emulsions was evaluated determining the stability of vitamin E solubilized in the oil phase.

Nanoantioxidant-Based Silica Particles as Flavonoid Carrier for Drug Delivery Applications.

Nanosystems used in pharmaceutical formulations have shown promising results in enhancing the administration of drugs of difficult formulations. In particular, porous silica nanoparticles have demonstrated excellent properties for application in biological systems; however, there are still several challenges related to the development of more effective and biocompatible materials. An interesting approach to enhance these nanomaterials has been the development of nanoantioxidant carriers.

CAPRYDAA, an anthracene dye analog to LAURDAN: a comparative study using cuvette and microscopy.

We synthesized an anthracene derivative with solvatochromic properties to be used as a molecular probe for membrane dynamics and supramolecular organization. A nine carbon atom acyl chain and a dimethylamino substitution were introduced at positions 2 and 6 of the anthracene ring, respectively. This derivative, 2-nonanoyl-6-(dimethylamino)anthracene (termed CAPRYDAA), is a molecular probe designed to mimic the well-known membrane probe LAURDAN's location and response in the lipid membranes.

Development and Characterization of Florfenicol-Loaded BSA Nanoparticles as Controlled Release Carrier.

Florfenicol (FLO) is a broad-spectrum fluorinated antibiotic used for the treatment of bacterial diseases such as bovine respiratory disease (BRD) in cattle. FLO is a poorly soluble drug in aqueous solution, and its encapsulation in various nanovehicles has been reported to be less than 30%. In this context, the use of bovine serum albumin (BSA) as a nanocarrier for FLO is an interesting approach.

Mechanism of Visible-Light Photooxidative Demethylation of Toluidine Blue O.

Experiments and theoretical calculations by density functional theory (DFT) have been carried out to examine a self-sensitized type I photooxidation of toluidine blue O (TBO). This study attempts to build a connection between visible-light photolysis and demethylation processes of methylamine compounds, such as TBO. We show that controlled photoinduced mono- and double-demethylation of TBO can be achieved.

Spectral and Kinetic Study of 3-Styrylquinoxalin-2(1 H)-ones Photoreduced by N-Phenylglycine and Amines.

The photoreduction by amines and N-phenylglycine, NPG, of six styrylquinoxalin-2(1 H)-ones derivatives substituted in the styryl moiety, R-SQ, was studied by using flash photolysis. The photoreaction is initiated via a single electron transfer from the electron donor (amines or NPG) to R-SQ excited triplet state, R-SQ*, with the formation of a triplet state radical ion pair or a charge transfer exciplex, [CRIP/CTE]. These species live longer than the respective R-SQ* and have very similar transient spectra.

Phytoestrogen coumestrol: Antioxidant capacity and its loading in albumin nanoparticles.

Coumestrol is a polyphenol with promising therapeutic applications as phytoestrogen, antioxidant and potential cancer chemoprevention agent. The presence of two hydroxyl groups on its chemical structure, with orientation analogous to estradiol, is responsible of both, its antioxidant capacity and its estrogenic activity. However, several studies show that the interaction of polyphenols with food and plasma proteins reduces their antioxidant efficacy.

Antioxidant Nanomaterial Based on Core⁻Shell Silica Nanospheres with Surface-Bound Caffeic Acid: A Promising Vehicle for Oxidation-Sensitive Drugs.

The design of efficient, biocompatible, and easily prepared vehicles for drug delivery is a subject of great interest for medicine and pharmaceutical sciences. To achieve the above goals, surface functionalization is critical. Here, we report a hybrid nanocarrier consisting of core⁻shell silica nanospheres and the antioxidant caffeic acid linked to the surface, to evaluate their in vitro antioxidant capacity, their capability to protect oxidation-sensitive compounds incorporated in nanoparticles, and to study the interaction with bovine serum albumin protein.

Scanning fluorescence correlation spectroscopy comes full circle.

In this article, we review the application of fluorescence correlation spectroscopy (FCS) methods to studies on live cells. We begin with a brief overview of the theory underlying FCS, highlighting the type of information obtainable. We then focus on circular scanning FCS.

Study of rabbit erythrocytes membrane solubilization by sucrose monomyristate using laurdan and phasor analysis.

The study of surfactant and bio membranes interaction is particularly complex due to the diversity in lipid composition and the presence of proteins in natural membranes. Even more difficult is the study of this interaction in vivo since cellular damage may complicate the interpretation of the results, therefore for most of the studies in this field either artificial or model systems are used. One of the model system most used to study biomembranes are erythrocytes due to their relatively simple structure (they lack nuclei and organelles having only the plasma membrane), their convenient experimental manipulation and availability.

An HPLC Method for the Determination of Isoflavones and the Evaluation of Their Antioxidant Capacity in Both Homogeneous and Microheterogeneous Systems.

In this work, we developed an HPLC method to simultaneously quantify and hence evaluate the stability, distribution, and antioxidant capacity of six isoflavones: genistein, genistin, daidzein, daidzin, glycitin, and biochanin A. Isoflavones have been described as having an important estrogenic activity to treat menopausal symptoms and can reduce postmenopausal bone loss and also participate in the prevention of cardiovascular diseases. These beneficial properties are believed derived from their capacity to act as free-radical scavengers.

The binuclear dual emitter [Br(CO)Re(PN)(NP)Re(CO)Br] (PN): 3-chloro-6-(4-diphenylphosphinyl)butoxypyridazine, a new bridging P,N-bidentate ligand resulting from the ring opening of tetrahydrofuran.

Lithium diphenylphosphide unexpectedly provokes the ring-opening of tetrahydrofuran (THF) and by reaction with 3,6-dichloropyridazine leads to the formation of the ligand 3-chloro-6-(4-diphenylphosphinyl)butoxypyridazine (P⋯N), which was isolated. The reaction of this ligand with the (Re(CO)(THF)Br) dimer yields the novel complex [Br(CO)Re(μ-3-chloro-6-(4-diphenylphosphinyl)butoxypyridazine)Re(CO)Br] (BrRe(P⋯N)(N⋯P)ReBr), which was crystallized in the form of a chloroform solvate, (CHBrClNOPRe)·(CHCl). The monoclinic crystal (P2/n) displays a bimetallic cage structure with a symmetry inversion centre in the middle of the rhenium to rhenium line.

Morin Flavonoid Adsorbed on Mesoporous Silica, a Novel Antioxidant Nanomaterial.

Morin (2´,3, 4´,5,7-pentahydroxyflavone) is a flavonoid with several beneficial health effects. However, its poor water solubility and it sensitivity to several environmental factors avoid its use in applications like pharmaceutical and cosmetic. In this work, we synthetized morin-modified mesoporous silica nanoparticles (AMSNPs-MOR) as useful material to be used as potential nanoantioxidant.

Potential use of nanocarriers with pentacyclic triterpenes in cancer treatments.

Ursolic, oleanolic and betulinic acids are representative pentacyclic triterpenoids found in various plants and fruits. Despite having marked antitumor potentials, the very poor water solubility of these triterpenes hinders treatment development. Nanotechnology can enhance solubility, stability, bioavailability and phytochemical delivery, improving the therapeutic efficiency of triterpenes.

Flavonoids in Microheterogeneous Media, Relationship between Their Relative Location and Their Reactivity towards Singlet Oxygen.

In this work, the relationship between the molecular structure of three flavonoids (kaempferol, quercetin and morin), their relative location in microheterogeneous media (liposomes and erythrocyte membranes) and their reactivity against singlet oxygen was studied. The changes observed in membrane fluidity induced by the presence of these flavonoids and the influence of their lipophilicity/hydrophilicity on the antioxidant activity in lipid membranes were evaluated by means of fluorescent probes such as Laurdan and diphenylhexatriene (DPH). The small differences observed for the value of generalized polarization of Laurdan (GP) curves in function of the concentration of flavonoids, indicate that these three compounds promote similar alterations in liposomes and erythrocyte membranes.

Structuration in the interface of direct and reversed micelles of sucrose esters, studied by fluorescent techniques.

Background: Reactors found in nature can be described as micro-heterogeneous systems, where media involved in each micro-environment can behave in a markedly different way compared with the properties of the bulk solution. The presence of water molecules in micro-organized assemblies is of paramount importance for many chemical processes, ranging from biology to environmental science. Self-organized molecular assembled systems are frequently used to study dynamics of water molecules because are the simplest models mimicking biological membranes.