Enhancing Photothermal Energy Transduction through Inter- and Intramolecular Interactions of Multiple Two-Photon Dyes Appended onto Calix[4]arene.

Organic dyes-based photothermal agents (OPTAs) have received increasing attention as alternative to inorganic materials due to their higher biocompatibility and extensive diversification. Maximizing nonradiative deexcitation channels is crucial to improve the photothermal conversion efficiency (PCE) of OPTAs. This is typically achieved through individual molecular design or collective enhancement using supramolecular strategies.

Interaction of the Immune System TIM-3 Protein with a Model Cellular Membrane Containing Phosphatidyl-Serine Lipids.

T cell transmembrane, Immunoglobulin, and Mucin (TIM) are important immune system proteins which are especially present in T-cells and regulated the immune system by sensing cell engulfment and apoptotic processes. Their role is exerted by the capacity to detect the presence of phosphatidyl-serine lipid polar head in the outer leaflet of cellular membranes (correlated with apoptosis). In this contribution by using equilibrium and enhanced sampling molecular dynamics simulation we unravel the molecular bases and the thermodynamics of TIM, and in particular TIM-3, interaction with phosphatidyl serine in a lipid bilayer.

Enhanced stability and photothermal efficiency of Indocyanine Green J-aggregates by nanoformulation with Calix[4]arene for photothermal therapy of cancers.

Photothermal therapy (PTT) is a method of growing attention, owing to its controllable process, high efficiency and minimal side effect. Indocyanine Green (ICG) is as Food and Drug Administration (FDA) approved agent that stands on the frontline of further developments of PTT toward clinics. However, the applicability of ICG-mediated PTT is limited by the rapid in vivo clearance and photo-degradation of ICG.

Modelling the effects of / photoisomerization of a cyclocurcumin analogue on the properties of cellular lipid membranes.

The use of photosensitive molecules capable of isomerizing under light stimuli, and thus induce perturbation in biological systems, is becoming increasingly popular for potential light-activated chemotherapeutic purposes. We recently show that a cyclocurcumin derivative (CCBu), may be suitable for light-activated chemotherapy and may constitute a valuable alternative to traditional photodynamic therapy, due to its oxygen-independent mechanism of action, which allows the treatment of hypoxic solid tumors. In particular, we have shown that the / photoisomerization of CCBu correlates with strong perturbations of model lipid bilayers.

Perturbation of Lipid Bilayers by Biomimetic Photoswitches Based on Cyclocurcumin.

The use of photoswitches which may be activated by suitable electromagnetic radiation is an attractive alternative to conventional photodynamic therapy. Here, we report all-atom molecular dynamics simulation of a biomimetic photoswitch derived from cyclocurcumin and experiencing / photoisomerization. In particular, we show that the two isomers interact persistently with a lipid bilayer modeling a cellular membrane.

Biomimetic Photo-Switches Softening Model Lipid Membranes.

We report the synthesis and characterization of a novel photo-switch based on biomimetic cyclocurcumin analogous and interacting with the lipid bilayer, which can be used in the framework of oxygen-independent light-induced therapy. More specifically, by using molecular dynamics simulations and free energy techniques, we show that the inclusion of hydrophobic substituents is needed to allow insertion in the lipid membrane. After having confirmed experimentally that the substituents do not preclude the efficient photoisomerization, we show through UV-vis and dynamic light scattering measurements together with compression isotherms that the chromophore is internalized in both lipid vesicles and monomolecular film, respectively, inducing their fluidification.

Don't help them to bury the light. The interplay between intersystem crossing and hydrogen transfer in photoexcited curcumin revealed by surface-hopping dynamics.

Curcumin is a natural compound extracted from turmeric (), which has shown remarkable anti-inflammatory, antibacterial, and possibly anticancer properties. The intense absorption in the visible domain and the possibility of intersystem crossing make curcumin attractive also for photodynamic therapy purposes. In the present contribution, we unravel, thanks to non-adiabatic surface hopping dynamics, the interplay between intersystem crossing and hydrogen transfer in the enol form, .

Synthesis and Photoswitching Properties of Bioinspired Dissymmetric γ-Pyrone, an Analogue of Cyclocurcumin.

Cyclocurcumin (CC), a turmeric curcuminoid with potential therapeutic properties, is also a natural photoswitch that may undergo / photoisomerization under UV light. To be further exploited in relevant biological applications, photoactivation under near-infrared (NIR) irradiation is required. Such requirement can be met through opportune chemical modifications, by favoring two-photon absorption (TPA) probability.

Imprinting isolated single iron atoms onto mesoporous silica by templating with metallosurfactants.

Hypothesis: One of the main drawbacks of metal-supported materials, traditionally prepared by the impregnation of metal salts onto pre-synthesized porous supports, is the formation of large and unevenly dispersed particles. Generally, the larger are the particles, the lower is the number of catalytic sites. Maximum atom exposure can be reached within single-atom materials, which appear therefore as the next generation of porous catalysts.

Trans-to-cis photoisomerization of cyclocurcumin in different environments rationalized by computational photochemistry.

Cyclocurcumin is a turmeric component that has attracted much less attention compared to the well-known curcumin. In spite of the less deep characterization of its properties, cyclocurcumin has shown promising anticancer effects when used in combination with curcumin. Especially, due to its peculiar molecular structure, cyclocurcumin can be regarded as an almost ideal photoswitch, whose capabilities can also be exploited for relevant biological applications.

Improved tribological properties, thermal and colloidal stability of poly-α-olefins based lubricants with hydrophobic MoS submicron additives.

Hypothesis: Newtonian liquids, usually used as base oil lubricants, exhibit low viscosity under extreme thermal conditions, needed for the functioning of wind turbines. This is directly affecting the colloidal stability and the tribological properties of the formulations containing additives, such as MoS. Here, it was hypothesized that the surface hydrophobization of MoS particles will allow for an increased colloidal stability of the resulting formulations, for temperatures as high as 80 °C.

A multicenter cross-sectional study of episiotomy practice in Romania.

Rationale, Aims, And Objectives: The aim of this study was to focus attention on episiotomy practice in Romanian maternity units in order to identify factors associated with the very high rate of the procedure in Romania and to consider strategies to reduce it.

Methods: In this clustered cross-sectional study, a total of 11 863 patients were recorded in eight Romanian maternity units to assess the prevalence of episiotomy. A random effects Poisson model was used to estimate the prevalence rate in univariate and multivariate models.

Lipid-coated mesoporous silica microparticles for the controlled delivery of β-galactosidase into intestines.

β-Galactosidase has been drawing increasing attention for the treatment of lactose intolerance, but its delivery has been impeded by degradation under gastric conditions. We have demonstrated that the coating of mesoporous silica microparticles (diameter ≈ 9 µm, pore size ≈ 25 nm) with dioleoylphosphatidylcholine membranes significantly improved the loading capability and protected the enzymes from the loss of function under simulated gastric conditions. Once the particles are transferred to simulated intestinal conditions, the digestion of phosphatidylcholine with pancreatin led to the release of functional β-galactosidase.

In situ follow-up of hybrid alginate-silicate microbeads formation by linear rheology.

Hybrid alginate-silicate microbeads of about 10-20 μm were synthesized by combining alginate crosslinking, silica condensation in a one pot approach using a food grade emulsion as template. A fine tuning of the formulation composition (alginate, silica and calcium sources) is necessary in order to obtain core-shell microbeads instead of unshaped and irregular fragments or even perforated spherical beads. Importantly, in situ linear rheology provides insights into the reaction mechanism as a result of the rheological fingerprint profile obtained during beads formation.

Original behavior of L. rhamnosus GG encapsulated in freeze-dried alginate-silica microparticles revealed under simulated gastrointestinal conditions.

The probiotic bacteria L. rhamnosus GG (LGG) were encapsulated into core-shell alginate-silica microbeads of about 500 μm through a double step synthesis involving micro-ionogel formation by electrospraying and silica coating by the sol-gel process. Formulating microparticles with sucrose as a cryoprotectant allowed maintaining bacterial viability and cultivability upon freeze-drying for weeks, as determined by plate counting.

SPR screening of metal chelating peptides in a hydrolysate for their antioxidant properties.

There is a growing need in the industrial sector (health, nutrition and cosmetic) to discover new biomolecules with various physico-chemical and bioactive properties. Various beneficial effects of peptides - notably those produced from protein hydrolysis - are reported in the literature. The antioxidant activity involves various mechanisms, among them metal chelation, studied by UV-visible spectrophotometry.

Silica-based systems for oral delivery of drugs, macromolecules and cells.

According to the US Food and Drug Administration and the European Food Safety Authority, amorphous forms of silica and silicates are generally recognized to be safe as oral delivery ingredients in amounts up to 1500mg per day. Silica is used in the formulation of solid dosage forms, e.g.

Effect of Meso vs Macro Size of Hierarchical Porous Silica on the Adsorption and Activity of Immobilized β-Galactosidase.

β-Galactosidase (β-Gal) is one of the most important enzymes used in milk processing for improving their nutritional quality and digestibility. Herein, β-Gal has been entrapped into a meso-macroporous material (average pore size 9 and 200 nm, respectively) prepared by a sol-gel method from a silica precursor and a dispersion of solid lipid nanoparticles in a micelle phase. The physisorption of the enzyme depends on the concentration of the feed solution and on the pore size of the support.

Core-shell alginate@silica microparticles encapsulating probiotics.

Lactobacillus rhamnosus GG (LGG) was encapsulated in core-shell alginate-silica microcapsules by coating the electrosprayed ionogel with a silica shell via hydrolysis/condensation of alkoxysilane precursors. The viability of encapsulated LGG highly depends on the mineralisation conditions (in aqueous or organic phases), identified as a critical step. More importantly, due to the unswelling of silica and to its mesoporosity that allows nutriment-metabolite diffusion, it was possible to avoid cell leakage and additionally insure bacterial growth inside the microcapsules.

Spin State As a Probe of Vesicle Self-Assembly.

A novel system of paramagnetic vesicles was designed using ion pairs of iron-containing surfactants. Unilamellar vesicles (diameter ≈ 200 nm) formed spontaneously and were characterized by cryogenic transmission electron microscopy, nanoparticle tracking analysis, and light and small-angle neutron scattering. Moreover, for the first time, it is shown that magnetization measurements can be used to investigate self-assembly of such functionalized systems, giving information on the vesicle compositions and distribution of surfactants between the bilayers and the aqueous bulk.

Core-shell microcapsules of solid lipid nanoparticles and mesoporous silica for enhanced oral delivery of curcumin.

Newly designed microcapsules (MC) combining a core of solid lipid nanoparticle (SLN) and a mesoporous silica shell have been developed and explored as oral delivery system of curcumin (CU). CU-loaded MC (MC-CU) are 2 μm sized and have a mesoporous silica shell of 0.3 μm thickness with a wormlike structure as characterized by small angle X-ray scattering (SAXS), nitrogen adsorption/desorption and transmission electron microscopy (TEM) measurements.

Teenage Pregnancies: Risk Factors and Associated Neonatal Outcomes in an Eastern-European Academic Perinatal Care Center.

Objectives: This study aims to compare women with early (13-16 years), late teenage (17-19 years), and adult (25-29 years) pregnancies regarding pregnancy risk factors and reproductive outcomes.

Methods: An observational study, utilizing medical charts and direct interview, conducted in an academic hospital during January 2011 and December 2012. Our sample comprised 395 teenage and 736 adult pregnancies.

Metallo-solid lipid nanoparticles as colloidal tools for meso-macroporous supported catalysts.

Meso-macroporous silica containing iron oxide nanoparticles (15-20 nm) was synthesized by formulating solid lipid nanoparticles and metallosurfactant as both template and metal source. Because of the high active surface area of the catalyst, the material exhibits an excellent performance in a Fenton-like reaction for methylene blue (MB) degradation, even at low amount of iron oxide (5% TOC after 14 h).

pH-controlled delivery of curcumin from a compartmentalized solid lipid nanoparticle@mesostructured silica matrix.

Silicalization of curcumin-loaded solid lipid nanoparticle (SLN)/micelle dispersions afforded a compartmentalized nanovector, with both macro- and mesostructured domains. SLNs act as reservoirs of curcumin (CU), while mesopores act as pathways to control drug release. Moreover, the release sustainability depends on the nature of the solid lipid (cetyl palmitate vs.