Search Results (355)

Studying nanoscale self-assembly in real time using external stimuli unlocks new opportunities for dynamic and adaptive materials. While electrostatic self-assembly is well-established, real-time monitoring of its structural evolution under light irradiation remains largely unexploited. In this study, we employ light-responsive azobenzene dyes (Acid Yellow 38, AY38) and pH-sensitive polyamidoamine (PAMAM) dendrimers to investigate the kinetics of electrostatic self-assembly under UV irradiation. Using a custom in situ small-angle neutron scattering (SANS) setup, we track the real-time morphological transformations of self-assembled structures with sub-minute resolution. We introduce two distinct pathways: method A (pre-irradiated cis-AY38 for controlled, slow kinetics) and method B (direct UV-induced self-assembly, fast kinetics). The results reveal that trans-cis isomerization kinetics dictate the rate of self-assembly, influencing aggregate stability, ζ-potential evolution, and final morphology. Structural analysis using dynamic and static light scattering (DLS and SLS) and SANS elucidates a transition from spherical to ellipsoidal morphologies governed by electrostatic and dipole-dipole interactions. These findings establish photoisomerization-driven self-assembly as a robust mechanism for tunable nanoscale architectures, paving the way for adaptive photonic materials, targeted drug delivery, and reconfigurable nanostructures. Full article

Virus filtration is an essential unit operation used to validate clearance of adventitious virus during the manufacture of biopharmaceutical products such as monoclonal antibodies. Obtaining at least a 10,000-fold reduction in virus particles in the permeate is challenging as monoclonal antibodies are about half the size of the virus particles. Minute virus of mice, FDA-recommended model adventitious virus, was labeled with a fluorescent dye. Laser scanning confocal microscopy was used to determine the location of virus entrapment within the virus filtration membrane. Three different hollow fiber membranes made of regenerated cellulose and polyvinylidene fluoride were tested. Feed streams consisted of MVM spiked in buffer and MVM spiked in 5 g L⁻¹ bovine serum albumin known to contain aggregates similar in size to the MVM. After filtering the feed, a buffer flush was used, with and without 30 min pause before the buffer flush. For all virus filters, a 30 min process pause led to broadening and movement of the virus entrapment zone deeper into the membrane. The presence of aggregates led to greater broadening of the entrapment zone. Both effects could lead to reduced virus clearance. Visualization of virus entrapment helps improve understanding of the behavior of virus filtration membranes. Full article

This study investigated the dielectric and photocatalytic properties of green-synthesized titanium dioxide nanoparticles (TiO₂ NPs), which are widely utilized semiconductor materials known for their excellent optical, structural, and electronic characteristics. The TiO₂ NPs were synthesized via a green precipitation method from the aqueous extract of Cymbopogon proximus. A comprehensive set of analytical techniques—UV–Vis spectroscopy, XRD, FTIR, TEM, EDX, and DLS—was employed to determine their optical response, crystalline structure, functional groups, morphology, elemental composition, and particle size distribution. UV–Vis analysis revealed a characteristic absorption peak at 327 nm, and the band gap energy, calculated via the Tauc plot method, was 3.16 eV. The XRD results confirmed the formation of a tetragonal TiO₂ phase with an average crystallite size of approximately 4 nm. TEM images further supported the spherical to quasitetragonal morphology and revealed that the aggregated clusters formed conjoint nanostructures. The photocatalytic activity of the TiO₂ NPs was evaluated using a 0.5 mM RhB dye solution under UV–visible irradiation. The synthesized nanoparticles achieved a photodegradation efficiency of 97% after 50 h, with a corresponding rate constant of 0.073402 h⁻¹, indicating their potential for effective photocatalytic pollutant removal. Furthermore, the dielectric behavior of the TiO₂ NPs was examined at room temperature. The material exhibited a high dielectric constant at low frequencies due to interfacial (Maxwell–Wagner) polarization, along with frequency-dependent AC conductivity attributed to charge-carrier hopping mechanisms. These dielectric properties, combined with strong photocatalytic performance, underscore the suitability of green-synthesized TiO₂ NPs for applications in environmental remediation, energy-storage devices, and advanced technologies. Full article

Fluorescence fluctuation spectroscopy (FFS) techniques rely on determination of monomeric molecular brightness, i.e., the fluorescence intensity of a single, non-aggregated fluorophore, as a critical reference for estimating protein oligomer size. By comparing measured molecular brightness of fluorescently labeled proteins of interest to this monomeric brightness benchmark, FFS enables inference of oligomerization states. However, widely used fluorescent proteins often exhibit self-association, compromising monomeric brightness calibration and introducing errors in brightness-derived oligomer-size estimates. This study compares two strategies for determining monomeric brightness: the conventional fluctuation-based method and a more recently proposed average-intensity-based alternative. The comparison uses two model fluorophores, a fluorescent protein (mCitrine) and the small-molecule dye Janelia Fluor 525 (JF₅₂₅) conjugated to HaloTag. Our results show strong agreement between intensity- and fluctuation-derived brightness values only in the minimally aggregating JF₅₂₅–HaloTag benchmark. In contrast, in the mCitrine samples, where aggregation is more prevalent, only the intensity-based method maintains a consistent estimate across sample preparation, while the fluctuation-based method overestimates brightness when aggregation effects become pronounced. This robustness makes the intensity-based approach a valuable cross-check for monomeric brightness calibration. Our results support a combined strategy, using both methods to improve the reliability of monomeric brightness calibration and protein oligomerization analysis in FFS. Full article

Squaraine dyes are a class of organic compounds that exhibit some characteristics inherent to those of an “ideal photosensitizer”, such as high absorption at near-infrared-close wavelengths and to produce reactive oxygen species. The introduction of amines into their squaric ring, although known to increase the phototoxicity of squaraines, can improve dyes’ water solubility and induce bathochromic shifts compared to their unsubstituted derivatives, interesting effects in biological contexts. In this work, four new squaraines were synthesized and structurally, photophysically, and photochemically characterized (including absorption and aggregation, fluorescence, light stability, and singlet oxygen generation). Their potential as fluorescent probes for albumin detection was assessed through both in silico and in vitro approaches, as well as their suitability as potential photosensitizers for photodynamic therapy. For this last purpose, the 663 nm light-induced effects of the new dyes were evaluated against the PC-3 prostate cancer cell line, while their photocytotoxicity toward normal human dermal fibroblasts was also assessed using the MTT assay, to determine their potential tumor-selective effects. Low singlet oxygen quantum yields suggest that type I reactions predominate in generating cytotoxicity. Overall, the findings indicate that the designed squaraines exhibit moderate yet favorable interactions with albumin protein while demonstrating selective photodynamic effects toward prostate adenocarcinoma cancer cells, highlighting their potential as protein-assisted, tumor-targeted photosensitizers, providing a basis for further mechanistic studies. Full article

The effectiveness of periodate-assisted photocatalysis in removing the cationic dye Safranin O (SO) was evaluated using a UV/TiO₂/IO₄⁻ process operated at room temperature under near-neutral pH conditions. Under base conditions ([IO₄⁻] = 0.15 mM, [TiO₂] = 0.4 g/L, [SO] = 10 mg/L), the ternary system achieved a pseudo-first-order rate constant of 0.6212 min⁻¹, outperforming the UV/TiO₂ and UV/IO₄⁻ processes by approximately 21- and 29-fold, respectively. This yielded a synergy ratio of about 12 compared to the sum of the binary processes. Targeted quenching experiments revealed the operative pathways. Strong inhibition by ascorbic acid and phenol indicates that interfacial holes and ^•OH are key oxidants. Methanol caused a moderate slowdown, consistent with ^•OH and hole scavenging. Benzoquinone and oxalate suppressed removal by intercepting the electron and O₂^•− pathways, respectively. Dichromate markedly inhibited the process via optical screening and competition for electrons. Azide had little effect, suggesting a minor role for singlet oxygen. Matrix studies showed progressively slower kinetics from deionized water to mineral water to seawater. This was due to halides, sulfate, alkalinity, and TiO₂ aggregation driven by ionic strength. Additional tests confirmed that the dominant modulators of performance were humic acid (site fouling and light screening), chloride and sulfate (radical speciation and surface effects), nitrite (near-diffusion radical quenching), and bicarbonate at pH 8.3 (conversion of ^•OH to CO₃^•−). Nonionic surfactants (Tween 80, Triton X-100) also depressed SO removal through micellar sequestration and competitive adsorption on TiO₂. The study confirms the potential of UV/TiO₂/IO₄⁻ as a tunable AOP capable of delivering rapid and reliable dye degradation under a wide range of water quality conditions. The mechanistic mapping unifies two roles for IO₄⁻, an electron acceptor that inhibits recombination and a photochemical precursor of iodine centered and ^•OH radicals and connect these roles to the observed synergy and to the trend across deionized water, mineral water, and seawater. The scavenger outcomes assign the main oxidant flux to holes and ^•OH radicals with a contributory electron or O₂^•− branch from IO₄⁻ reduction. Full article

Due to their excellent physicochemical properties, the nanoparticles (NPs) have been utilized in various potential applications, including environmental remediation, energy storage, and nanomedicine. In this work, the ultrasonic and manual stirring approaches were used to integrate yttrium oxide (Y₂O₃) nanoparticles (NPs) into reduced graphene oxide (RGO) and carbon nanotubes (CNTs) to enhance their photocatalytic and anticancer properties. Pure Y₂O₃NPs, Y₂O₃/RGO NCs, and Y₂O₃/CNTs NCs were characterized using different analytical techniques, such as XRD, SEM, EDX with Elemental Mapping, FTIR, UV-Vis, PL, and DLS to investigate their improved structural, surface morphological, chemical bonding, optical, and surface charge properties. XRD data confirmed the successful integration of Y₂O₃into RGO and CNTs, with minor changes in crystallite sizes. SEM images with EDX analysis revealed that Y₂O₃NPs were uniformly distributed on RGO and CNTs, reducing aggregation. Chemical bonding and interactions between Y₂O₃and carbon materials were investigated using Fourier Transform Infrared (FTIR) analysis. UV and PL results suggest that the optical studies showed a shift in absorption peaks upon integration with RGO and CNTs. This indicates enhanced light absorption and modifications to the band gap between (3.79–4.40 eV) for the obtained samples. In the photocatalytic experiment, the degradation efficiency of bromophenol blue (BPB) dye for Y₂O₃RGO NCs was up to 87.3%, outperforming pure Y₂O₃NPs (45.83%) and Y₂O₃/CNTs NCs (66.78%) after 120 min of UV irradiation. Additionally, the MTT assay demonstrated that Y₂O₃/RGO NCs exhibited the highest anticancer activity against MG-63 bone cancer cells with an IC50 value of 45.7 µg/mL compared to Y₂O₃CNTs NCs and pure Y₂O₃NPs. This work highlights that Y₂O₃/RGO NCs could be used in significant applications, including environmental remediation and in vivo cancer therapy studies. Full article

Using an environmentally friendly approach, we successfully synthesized an asymmetric monomethine cyanine dye, 7-chloro-1-ethyl-4-((3-ethylbenzo[d]thiazol-2(3H)-ylidene)methyl) quinolin-1-ium iodide, named CHLoris (CHL), via a modified Knoevenagel-type condensation. The reaction was carried out mechanochemically in an ethanol–water medium using 1-ethyl-2-methylbenzothiazolium iodide and 4,7-dichloro-1-ethylquinolin-1-ium iodide in the presence of sodium carbonate as a base and catalytic amounts of Hünig’s base. The UV/VIS absorption spectra of CHL in both the buffer solution and ethanol revealed the formation of aggregates in aqueous media. Density Functional Theory (DFT) and Time-Dependent DFT (TDDFT) calculations were employed to support the experimental findings further and provide insights into the self-association behavior of CHL in an aqueous solution. The photophysical properties of the dye were examined in the presence of DNA and RNA, and its performance was compared to that of the commercial dye Thiazole Orange (TO) under identical conditions. The results show that CHL is more sensitive towards RNA. Full article

Photodynamic inactivation and antimicrobial photodynamic therapy (PDI/APDT) based on the toxic properties of reactive oxygen species (ROS), which are generated by a number of photoexcited dyes, are promising for preventing and treating infections, especially those associated with drug-resistant pathogens. The negatively charged bacterial cell surface attracts polycationic photosensitizers, which contribute to the vulnerability of the bacterial plasma membrane to ROS. The integrity of the plasma membrane is critical for the viability of the bacterial cell. Polycationic phthalocyanines are regarded as promising photosensitizers due to their high quantum yields of ROS generation (mainly singlet oxygen), high extinction coefficients in the far-red spectral range, and low dark toxicity. For application in PDI/APDT, the wide range of possibilities of modifying the chemical structure of phthalocyanines is particularly valuable, especially by introducing various peripheral and non-peripheral substituents into the benzene rings. Depending on the type and location of such substituents, it is possible to obtain photosensitizers with different photophysical properties, photochemical activity, solubility in an aqueous medium, biocompatibility, and tropism for certain structures of photoinactivation targets. In this study, we tested novel water-soluble Zn (II) phthalocyanines bearing four 4-((diethylmethylammonium)methyl)phenoxy substituents with symmetric and asymmetric charge distributions for photodynamic antibacterial activity and compared them with those of water-soluble octacationic zinc octakis(cholinyl)phthalocyanine. The obtained results allow us to conclude that the studied tetracationic aryloxy-substituted Zn(II) phthalocyanines effectively bind to the oppositely charged cell wall of the Gram-negative bacteria E. coli. This finding is supported by data on bacteria’s zeta potential neutralization in the presence of phthalocyanine derivatives and fluorescence microscopy images of stained bacterial cells. Asymmetric substitution influences the aggregation and fluorescent characteristics but has little effect on the ability of the studied tetracationic phthalocyanines to sensitize the bioluminescent E. coli K12 TG1 strain. Both symmetric and asymmetric aryloxy-substituted phthalocyanines are no less effective in PDI than the water-soluble zinc octakis(cholinyl)phthalocyanine, a photosensitizer with proven antibacterial activity, and have significant potential for further studies as antibacterial photosensitizers. Full article

This study investigates the impacts of the gas environment, water matrix, and reactive species on the TiO₂-mediated photocatalytic degradation of safranin O (SO), a dye commonly found in wastewater. A slurry reactor (UVA, 365 nm) was used to quantify SO oxidation while systematically varying the SO concentration (5–40 mg/L), the TiO₂ loading (0–3 g/L), the temperature (15–45 °C), and the pH (2–12). The dissolved gases (air, nitrogen, and argon) and matrices (deionized water, mineral water, and seawater) were also examined. Eight mechanistic probes (ascorbic acid, methanol, azide, nitrite, benzoquinone, oxalate, sucrose, and phenol) were used to identify active oxidants. UVA/TiO₂ achieved rapid decolorization in approximately 90 min at 10 mg/L of SO and 0.4 g/L of TiO₂. Decolorization rates decreased with increasing SO concentration due to active-site competition and inner-filter effects. Rates also exhibited a bell-shaped dependence on TiO₂ loading due to light scattering and aggregation at high solids concentrations. Temperature exhibited a non-monotonic profile with an optimum around 25 °C, and the pH displayed an optimum range with maximal removal occurring around pH 10 and declining at pH 12. Air saturation outperformed N₂ and Ar, indicating that O₂ is the terminal electron acceptor. Photocatalytic performance decreased in the order deionized water > mineral water > seawater, owing to bicarbonate/chloride scavenging and ionic-strength effects. Scavenger tests converged on ^•OH dominance, with measurable contributions from superoxide/hydrogen peroxide (O₂^•−/H₂O₂) and valence-band holes (h⁺); singlet oxygen (¹O₂) played a minor role. These findings underscore the critical interplay between operational and environmental factors and offer a practical framework for scaling TiO₂-based SO abatement in real waters. Full article

The rational design of advanced functional materials with tailored fluorescence hinges on a profound understanding of the complex interplay between a molecule’s intrinsic structure and its local solid-state environment. This work systematically investigates these factors by employing a dual approach that combines targeted molecular synthesis with the subsequent modulation of the fluorophore’s properties within polymer matrices. First, a series of phenylhydrazone derivatives was synthesized, providing compounds with intense, solid-state fluorescence in the blue spectrum (421–494 nm). It was demonstrated that their photophysical properties were intricately linked to the substituent’s nature, which simultaneously modulated their intramolecular electron density and conformational rigidity while also governing their specific intermolecular packing in the solid state. Subsequently, we investigated the role of the supramolecular environment by embedding two fluorophores with distinct electronic profiles into electrospun poly (N-vinylpyrrolidone) (PVP) and polystyrene (PS) matrices. Our results reveal that the polymer matrix is not a passive host but an active component; it governs dye aggregation, induces significant blue shifts, and most critically, can impart exceptional thermal stability. Specifically, the PVP matrix shielded the embedded dyes from thermal quenching, maintaining robust fluorescence up to 100 °C. By combining molecular-level synthesis with matrix-level engineering, this work demonstrates a powerful strategy for the rational design of emissive materials, where properties like color and operational stability can be deliberately tuned for demanding applications in optoelectronics and sensing. Full article

Alzheimer’s disease (AD) is characterized by amyloid-beta (Aβ) plaque accumulation and neurodegeneration. This study identified gyrophoric acid, a lichen-derived phenolic metabolite, as a dual-action Aβ42 inhibitor preventing aggregation and disassembling of mature Aβ42 fibrils. Integrated in silico studies revealed that gyrophoric acid was a strong thermodynamic stabilizer of Aβ42 (MM–GBSA: −27.3 kcal/mol) via entropically driven hydrophobic interactions and disruption of aggregation-prone conformations (100 ns MD simulations). Through biochemical analysis of the fluorescent dye thioflavin T (ThT), gyrophoric acid induced rapid Aβ42 fibril disassembly within 5 h, with time-lapse confocal microscopy quantitatively confirming the near-complete dissolution of large aggregates by 24 h. ADMET profiling revealed favorable pharmacokinetics (moderate oral absorption: 48.5–57.3%; low toxicity) and Lipinski’s rule compliance. These results establish gyrophoric acid as a promising natural bioactive compound for anti-AD therapeutics with a unique hydrophobic-stabilization mechanism. Full article

The recycling of glass presently poses several challenges, predominantly to the heterogeneous chemical compositions of various glass types, along with the waste glass particle size distribution, both of which critically influence the efficiency and feasibility of recycling operations. Numerous studies have elucidated the potential of converting non-recyclable glass waste into valuable materials thanks to the up-cycling strategies, including stoneware, glass wool fibres, glass foams, glass-ceramics, and geopolymers. Among the promising alternatives for improving waste valorisation of glass, alkali-activated materials (AAMs) emerge as a solution. Waste glasses can be employed both as aggregates and as precursors, with a focus on its application as the sole raw material for synthesis. This overview systematically explores the optimisation of precursor selection from a sustainability standpoint, specifically addressing the mild alkali activation process (<3 mol/L) of waste glasses. The molecular mechanisms governing the hardening process associated with this emerging class of materials are elucidated. Formulating sustainable approaches for the valorisation of glass waste is becoming increasingly critical in response to the rising quantities of non-recyclable glass and growing priority on circular economy principles. In addition, the paper highlights the innovative prospects of alkali-activated materials derived from waste glass, emphasising their emerging roles beyond conventional structural applications. Environmentally relevant applications for alkali-activated materials are reported, including the adsorption of dyes and heavy metals, immobilisation of nuclear waste, and an innovative technique for hardening as microwave-assisted processing. Full article

Applying physico-analytical methods to whole hair fibers enables investigation of hair dye performance. Light microscopy, SEM imaging and EDX mapping of intact hair fibers, as well as TEM imaging of microtome cuts, provided insights into the distribution, size, shape and growth patterns of the dyeing species and particles, thus demonstrating the correlation between silver nanoparticles (AgNPs) and dye impression. Yak hair fibers were treated with a polyphenol-containing Reseda luteola L. extract (RE), which had been acidified using either hydrochloric acid (HCl) or citric acid (CA), and subsequently exposed to silver nitrate (AgNO₃), resulting in the formation of quasi-spherical silver nanoparticles (AgNPs) that were depicted several microns deep inside the hair fiber, regardless of the additive used. The particles appeared to aggregate preferentially in sulfur-rich domains within the hair fiber, probably due to the affinity of silver ions on the NP’s surface towards sulfur. The additives significantly affected the size and aggregation behavior of the particles. Using HCl, larger, aggregated particles were formed, whereas the application of CA yielded smaller, more uniform particles and a higher penetration depth. Despite different particle sizes, the dye outcome was comparable. In strands treated with HCl, washing brought the particles deeper into the hair cortex and resulted in further aggregation. Thus, HCl promoted the formation of larger particles whereas CA yielded more uniformly sized particles. These findings open a new route for metal nanoparticle-based hair dyes with excellent wash fastness. Full article

Using ultrasound-assisted extraction, we obtained a chlorophyll-rich extract from Opuntia ficus-indica cladodes (OFI) characterized through thin-layer chromatography (TLC), Fourier-transform infrared spectroscopy (FTIR), and spectrophotometric absorption analysis. The dye exhibited a strong fluorescence response in the visible range (400–800 nm) with a pronounced red emission when excited with a UV source. Antioxidant ability was evaluated via DPPH assay, showing an IC₅₀ of 185 µg/mL, highlighting its potential for reactive oxygen species scavenging. The extract was incorporated into polymethyl methacrylate (PMMA), polyvinylpyrrolidone (PVP), and polyvinyl alcohol (PVA), leading to fluorescence intensity enhancements of up to 40 times compared to the dye alone depending on matrix polarity, consistent with aggregation and polarity effects. Stability tests confirmed the dye’s resistance to CO₂ exposure, pH variations, and prolonged storage, positioning it as a viable alternative to synthetic fluorophores. These findings suggest that the OFI extract provides a functionally relevant, bio-derived dye platform promoting the valorization of agricultural by-products in high-value technological applications, highlighting a circular and scalable approach to developing ecofriendly fluorescent materials, aligning with sustainability and green technology goals. Full article