Investigation of J-Aggregates of 2,3,7,8,12,13,17,18-Octabromo-5,10,15,20-tetrakis(4-sulfonatophenyl) Porphyrin in Aqueous Solutions.

The highly distorted water-soluble 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (Br8TPPS44-) is readily protonated under acidic pH, forming the diacid H2Br8TPPS42- and subsequently the zwitterionic H4Br8TPPS4, which eventually evolves into J-aggregates. These latter species exhibit a relevant bathochromic shift with respect to the monomer with a quite sharp band due to motional narrowing. The depolarization ratio measured in resonant light scattering spectra allows estimating a tilt angle of ~20° of the porphyrins in the J-aggregate. The kinetic parameters are obtained by applying a model based on the initial slow nucleation step, leading to a nucleus containing m monomers, followed by fast autocatalytic growth. The kc values for this latter step increase on decreasing the acid concentration and on increasing the porphyrin concentration, with a strong power-law dependence. No spontaneous symmetry breaking or transfer of chirality from chiral inducers is observed. Both Atomic Force Microscopy (AFM) and Dynamic Light Scattering (DLS) point to the presence, in both the solid and solution phases, of globular-shaped aggregates with sizes close to 130 nm. Density functional theory (DFT) calculations performed on simplified models show that (i) upon protonation, the saddled conformation of the porphyrin ring is slightly altered, and a further rotation of the aryl rings occurs, and (ii) the diacid species is more stable than the parent unprotonated porphyrin. Time-dependent DFT analysis allows comparing the UV/Vis spectra for the two species, showing a consistent red shift upon protonation, even if larger than the experimental one. The simulated Raman spectrum agrees with the experimental spectrum acquired on solid samples.

Linear and Nonlinear Optical Responses of Nitrobenzofurazan-Sulfide Derivatives: DFT-QTAIM Investigation on Twisted Intramolecular Charge Transfer.

In this study, we report on the green fluorescence exhibited by nitrobenzofurazan-sulfide derivatives (NBD-Si, i = 1-4). The optical responses of these studied compounds in a polar methanol solvent were simulated by the use of time-dependent density functional theory (TD-DFT) employing the Becke-3-Parameter-Lee-Yang-Parr (B3LYP) functional along with the 6-31G(d,p) basis set. The computed energy and oscillator strength (f) results complement the experimental results. The band gap was calculated as the difference between the lowest unoccupied molecular orbital (LUMO) and the highest occupied molecular orbital (HOMO). Additionally, the density of states (DOS) was computed, providing a comprehensive understanding of the fundamental properties of these materials and further corroborating the experimental data. When the experimental data derived from ultraviolet/visible (UV/visible) and fluorescence spectroscopic techniques and those from simulated spectra are analyzed, the extracted values match up adequately. In addition, the NBD-sulfide compounds exhibit a large Stokes shift up to 85 nm in a polar methanol solvent. They are hypothesized to represent a novel paradigm of excited-state intramolecular charge transfer (ICT). To understand the intrinsic optical properties of NBD-Si materials, an ICT was identified, and its direction within the molecule was evaluated using the ratio of ßvect and ßtotal, values extracted from the computed nonlinear optical (NLO) properties. Moreover, the reduced density gradient (RDG)-based noncovalent interactions (NCIs) were employed to characterize the strength and type of NBD-Si interactions. Furthermore, noncovalent interactions were identified and categorized using the Quantum Theory of Atoms in Molecules (QTAIM) analysis. Ultimately, the combination of Hirshfeld surface analysis and DFT calculations was utilized to enhance the characterization and rationalization of these NCIs.

Curcumin I-SMA nanomicelles as promising therapeutic tool to tackle bacterial infections.

Renewed interest towards natural substances has been pushed by the widespread diffusion of antibiotic resistance. Curcumin I is the most active and effective constituent of curcuminoids extracted from Curcuma longa and, among other beneficial effects, attracted attention for its antimicrobial potential. Since the poor pharmacokinetic profile hinders its efficient utilization, in the present paper, we report encapsulation of curcumin I in poly(styrene-co-maleic acid) (SMA-CUR) providing a nanomicellar system with improved aqueous solubility and bioavailability. SMA-CUR was characterized by means of size, zeta potential, polydispersity index, atomic force microscopy (AFM), drug release studies, spectroscopic properties and stability. SMA-CUR nanoformulation displayed exciting antimicrobial properties compared to free curcumin I towards Gram-positive and Gram-negative clinical isolates.

Supramolecular assemblies based on polymeric cyclodextrin nanosponges and a cationic porphyrin with antimicrobial photodynamic therapy action.

Within of the increasing requirement of alternative approaches to fight emerging infections, nano-photosensitisers (nanoPS) are currently designed with the aim to optimize the antimicrobial photodynamic (aPDT) efficacy. The utilize of less expensive nanocarriers prepared by simple and eco-friendly methodologies and commercial photosensitisers are highly desiderable. In this direction, here we propose a novel nanoassembly composed of water soluble anionic polyester ß-CD nanosponges (ß-CD-PYRO hereafter named ßNS) and the cationic 5,10,15,20-tetrakis(1-methylpyridinium-4- yl)porphine (TMPyP). Nanoassemblies were prepared in ultrapure water by mixing PS and ßNS, by exploiting their mutual electrostatic interaction, and characterized by various spectroscopic techniques such as UV/Vis, Steady-State and Time Resolved Fluorescence, Dynamic Light Scattering and ζ-potential. NanoPS produce appreciable amount of single oxygen similar to free porphyrin and a prolonged stability after 6 days of incubations in physiological conditions and following photoirradiation. Antimicrobial photodynamic action against fatal hospital-acquired infections such as P. aeruginosa and S. aureus was investigated by pointing out the ability of cationic porphyrin loaded- CD nanosponges to photo-kill bacterial cells at prolonged time of incubation and following irradiation (MBC99 = 3.75 µM, light dose = 54.82 J/cm2).

Early Stages of Aluminum-Doped Zinc Oxide Growth on Silicon Nanowires.

Aluminum-doped zinc oxide (AZO) is an electrically conductive and optically transparent material with many applications in optoelectronics and photovoltaics as well as in the new field of plasmonic metamaterials. Most of its applications contemplate the use of complex and nanosized materials as substrates onto which the AZO forms the coating layer. Its morphological characteristics, especially the conformality and crystallographic structure, are crucial because they affect its opto-electrical response. Nevertheless, it was difficult to find literature data on AZO layers deposited on non-planar structures. We studied the AZO growth on silicon-nanowires (SiNWs) to understand its morphological evolution when it is formed on quasi one-dimensional nanostructures. We deposited by sputtering different AZO thicknesses, leading from nanoclusters until complete incorporation of the SiNWs array was achieved. At the early stages, AZO formed crystalline nano-islands. These small clusters unexpectedly contained detectable Al, even in these preliminary phases, and showed a wurtzite crystallographic structure. At higher thickness, they coalesced by forming a conformal polycrystalline shell over the nanostructured substrate. As the deposition time increased, the AZO conformal deposition led to a polycrystalline matrix growing between the SiNWs, until the complete array incorporation and planarization. After the early stages, an interesting phenomenon took place leading to the formation of hook-curved SiNWs covered by AZO. These nanostructures are potentially very promising for optical, electro-optical and plasmonic applications.

Light Emission Properties of Thermally Evaporated CH3NH3PbBr3 Perovskite from Nano- to Macro-Scale: Role of Free and Localized Excitons.

Over the past decade, interest about metal halide perovskites has rapidly increased, as they can find wide application in optoelectronic devices. Nevertheless, although thermal evaporation is crucial for the development and engineering of such devices based on multilayer structures, the optical properties of thermally deposited perovskite layers (spontaneous and amplified spontaneous emission) have been poorly investigated. This paper is a study from a nano- to micro- and macro-scale about the role of light-emitting species (namely free carriers and excitons) and trap states in the spontaneous emission of thermally evaporated thin layers of CH3NH3PbBr3 perovskite after wet air UV light trap passivation. The map of light emission from grains, carried out by SNOM at the nanoscale and by micro-PL techniques, clearly indicates that free and localized excitons (EXs) are the dominant light-emitting species, the localized excitons being the dominant ones in the presence of crystallites. These species also have a key role in the amplified spontaneous emission (ASE) process: for higher excitation densities, the relative contribution of localized EXs basically remains constant, while a clear competition between ASE and free EXs spontaneous emission is present, which suggests that ASE is due to stimulated emission from the free EXs.

Effect of Chemical Surface Texturing on the Superhydrophobic Behavior of Micro-Nano-Roughened AA6082 Surfaces.

Superhydrophobic surfaces on 6082 aluminum alloy substrates are tailored by low-cost chemical surface treatments coupled to a fluorine-free alkyl-silane coating deposition. In particular, three different surface treatments are investigated: boiling water, HF/HCl, and HNO3/HCl etching. The results show that the micro-nano structure and the wetting behavior are greatly influenced by the applied surface texturing treatment. After silanization, all the textured surfaces exhibit a superhydrophobic behavior. The highest water contact angle (WCA, ≈180°) is obtained by HF/HCl etching. Interestingly, the water sliding angle (WSA) is affected by the anisotropic surface characteristics. Indeed, for the HF/HCl and the HNO3/HCl samples, the WSA in the longitudinal direction is lower than the transversal one, which slightly affects the self-cleaning capacity. The results point out that the superhydrophobic behavior of the aluminum alloys surface can be easily tailored by performing a two-step procedure: (i) roughening treatment and (ii) surface chemical silanization. Considering these promising results, the aim of further studies will be to improve the knowledge and optimize the process parameters in order to tailor a superhydrophobic surface with an effective performance in terms of stability and durability.

Stimuli-Responsive Internally Ion-Paired Supramolecular Polymer Based on a Bis-pillar[5]arene Dicarboxylic Acid Monomer.

A novel bis-pillar[5]arene dicarboxylic acid self-assembles in the presence of 1,12-diaminododecane to yield overall neutral, internally ion-paired supramolecular polymers. Their aggregation, binding mode, and morphology can be tuned by external stimuli such as solvent polarity, concentration, and base treatment.

Eco-Friendly 1,3-Dipolar Cycloaddition Reactions on Graphene Quantum Dots in Natural Deep Eutectic Solvent.

Due to their outstanding physicochemical properties, the next generation of the graphene family-graphene quantum dots (GQDs)-are at the cutting edge of nanotechnology development. GQDs generally possess many hydrophilic functionalities which allow their dispersibility in water but, on the other hand, could interfere with reactions that are mainly performed in organic solvents, as for cycloaddition reactions. We investigated the 1,3-dipolar cycloaddition (1,3-DCA) reactions of the C-ethoxycarbonyl N-methyl nitrone 1a and the newly synthesized C-diethoxyphosphorylpropilidene N-benzyl nitrone 1b with the surface of GQDs, affording the isoxazolidine cycloadducts isox-GQDs 2a and isox-GQDs 2b. Reactions were performed in mild and eco-friendly conditions, through the use of a natural deep eutectic solvent (NADES), free of chloride or any metal ions in its composition, and formed by the zwitterionic trimethylglycine as the -bond acceptor, and glycolic acid as the hydrogen-bond donor. The results reported in this study have for the first time proved the possibility of performing cycloaddition reactions directly to the p-cloud of the GQDs surface. The use of DES for the cycloaddition reactions on GQDs, other than to improve the solubility of reactants, has been shown to bring additional advantages because of the great affinity of these green solvents with aromatic systems.

Effect of Hematite Doping with Aliovalent Impurities on the Electrochemical Performance of α-Fe2O3@rGO-Based Anodes in Sodium-Ion Batteries.

The effect of the type of dopant (titanium and manganese) and of the reduced graphene oxide content (rGO, 30 or 50 wt %) of the α-Fe2O3@rGO nanocomposites on their microstructural properties and electrochemical performance was investigated. Nanostructured composites were synthesized by a simple one-step solvothermal method and evaluated as anode materials for sodium ion batteries. The doping does not influence the crystalline phase and morphology of the iron oxide nanoparticles, but remarkably increases stability and Coulombic efficiency with respect to the anode based on the composite α-Fe2O3@rGO. For fixed rGO content, Ti-doping improves the rate capability at lower rates, whereas Mn-doping enhances the electrode stability at higher rates, retaining a specific capacity of 56 mAhg-1 at a rate of 2C. Nanocomposites with higher rGO content exhibit better electrochemical performance.

Sulfobutylether-ß-cyclodextrin/5,10,15,20-tetrakis(1-methylpyridinium-4-yl)porphine nanoassemblies with sustained antimicrobial phototherapeutic action.

Nowadays, novel less-expensive nanoformulations for in situ-controlled and safe delivery of photosensitisers (PSs) against opportunistic pathogens in body-infections areas need to be developed. Antimicrobial photodynamic therapy (aPDT) is a promising approach to treat bacterial infections that are recalcitrant to antibiotics. In this paper, we propose the design and characterization of a novel nanophototherapeutic based on the trade cyclodextrin CAPTISOL® (sulfobutylether-beta-cyclodextrin, SBE-ßCD) and 5,10,15,20-tetrakis(1-methylpyridinium-4-yl)porphine tetrakis(p-toluenesulfonate) (TMPyP) to fabricate efficient biocompatible systems for aPDT. Spherical nanoassemblies of about 360 nm based on CAPTISOL®/TMPyP supramolecular complexes with 1:1 stoichiometry and apparent equilibrium binding constant (Kb â‰… 1.32 × 105 M-1) were prepared with entrapment efficiency of â‰… 100% by simple mixing in aqueous media and freeze-drying. These systems have been characterized by complementary spectroscopy and microscopy techniques. Time resolved fluorescence pointed out the strong interaction of porphyrin monomer within nanoassemblies (τ2 â‰… 11 ns with an amount of ca 90%) and scarce self-aggregation of porphyrins have been observed. Singlet oxygen comparative determination (Ï•Δ CAPTISOL®/TMPyP = 0.58) assessed their photodynamic potential. Release and photostability studies have been carried out under physiological conditions pointing out the role of CAPTISOL® to sustain porphyrin release for more than 2 weeks and to protect PS from photodegradation. Finally, photoantimicrobial activity of nanoassemblies vs free porphyrin have been investigated against Gram-negative P. aeruginosa, E. coli and Gram-positive S. aureus. The proposed nanosystems were able to photokill both Gram-positive and -negative bacterial cells similarly to TMPyP at MBC90 = 6 µM of TMPyP and at 42 J/cm2 light dose. However, with respect to the less selective free TMPyP in biological sites, nanoassemblies exhibit sustained release properties and a higher photostability thus optimizing the PDT effect at the site of action. These results can open routes for in vivo translational studies on nano(photo)drugs and nanotheranostics based on less expensive formulations of CD and PS.