Search Results (53)

Tomato waste (TW) was employed as a sustainable source for the synthesis of fluorescent carbon dots (CDs) via a microwave-assisted hydrothermal carbonization (Mw-HTC) method, aiming at its valorization. Several amines were used as nitrogen additives to enhance the fluorescence quantum yield (QY) of CDs, and a set of reaction conditions, including additive/TW mass ratio (0.04–0.32), dwell time (15–60 min), and temperature (200–230 °C) of the HTC process, were scrutinized. The structural analysis of the tomato waste carbon dots (TWCDs) was undertaken by FTIR and ¹H NMR techniques, revealing their most relevant features. In solid state, transmission electron microscopy (TEM) analysis showed the presence of nearly spherical nanoparticles with an average lateral size of 8.1 nm. Likewise, the topographical assessment by atomic force microscopy (AFM) also indicated particles’ heights between 3 and 10 nm. Their photophysical properties, revealed by UV–Vis, steady-state, and time-resolved fluorescence spectroscopies, are fully discussed. Higher photoluminescent quantum yields (up to 0.08) were attained when the biomass residues were mixed with organic aliphatic amines during the Mw-HTC process. Emission tunability is a characteristic feature of these CDs, which display an intensity average fluorescence lifetime of 8 ns. The new TWCDs demonstrated good antioxidant properties by the ABTS radical cation method (75% inhibition at TWCDs’ concentration of 5 mg/mL), which proved to be related to the dwell time used in the CDs synthesis. Moreover, the synthesized TWCDs suppressed the growth of Escherichia coli and Staphylococcus aureus at concentrations higher than 2000 μg/mL, encouraging future antibacterial applications. Full article

Methylene blue (MB), a widely used industrial dye, is a persistent pollutant with documented toxicity to aquatic organisms and potential health risks to humans, even at ultra-trace levels. Conventional monitoring techniques such as UV–Vis spectroscopy and fluorescence emission suffer from limited sensitivity, typically failing to detect MB below ~10⁻⁷ M. In this study, we introduce a surface-enhanced Raman spectroscopy (SERS) platform based on silver nanowire (AgNW) substrates that enables MB detection over an unprecedented dynamic range—from 1.5 × 10⁻⁴ M down to 1.5 × 10⁻¹⁶ M. Raman mapping confirmed the presence of individual signal hot spots at the lowest concentration, consistent with the theoretical number of analyte molecules in the probed area, thereby demonstrating near-single-molecule detection capability. The calculated enhancement factors reached up to 1.90 × 10¹², among the highest reported for SERS-based detection platforms. A semi-quantitative calibration curve was established spanning twelve orders of magnitude, and this platform was successfully applied to monitor MB degradation during two advanced oxidation processes (AOPs): TiO₂ nanotube-mediated photocatalysis under UV irradiation and atmospheric-pressure dielectric barrier discharge (DBD) plasma treatment. While UV–Vis and fluorescence techniques rapidly lost sensitivity during the degradation process, the SERS platform continued to detect the characteristic MB Raman peak at ~1626 cm⁻¹ throughout the entire treatment duration. These persistent SERS signals revealed the presence of residual MB or partially degraded aromatic intermediates that remained undetectable by conventional optical methods. The results underscore the ability of AgNW-based SERS to provide ultra-sensitive, molecular-level insights into pollutant transformation pathways, enabling time-resolved tracking of degradation kinetics and validating treatment efficiency. This work highlights the importance of integrating SERS with AOPs as a powerful complementary strategy for advanced environmental monitoring and water purification technologies. By delivering an ultra-sensitive, low-cost sensor (<USD 0.16 per test) and promoting reagent-free treatment methods, this study directly advances SDG 6 (Clean Water and Sanitation) and SDG 12 (Responsible Consumption and Production). Full article

Although melanin is viewed as a natural sunscreen that protects pigmented cells against the adverse effects of solar radiation, recent studies have demonstrated that, under certain conditions, the pigment can actually contribute to light-induced oxidative damage of the cells. However, the main issue with such studies is finding natural pigments without photooxidative modifications. Recently, melanin obtained from melanocytes, generated from human induced pluripotent stem cells (hiPSC-Mel), was suggested as a promising source of the pigment without significant photooxidation. Although different studies have demonstrated the feasibility of the above-mentioned technique to obtain melanin-producing cells, no thorough analysis of the physicochemical properties of the pigment has been performed. To address this issue, we examined the key physicochemical parameters, including the aerobic photoreactivity of melanin isolated from hiPSC-Mel and compared them with those of melanin from other known sources of the pigment, such as bovine retinal pigment epithelium (bRPE) and phototype V (PT-V) hair. Electron paramagnetic resonance (EPR) spectroscopy, dynamic light scattering, UV–Vis absorption and HPLC analysis of melanin degradation products were used. The ability of the examined melanins to photogenerate reactive oxygen species was determined by employing EPR oximetry, EPR spin-trapping and time-resolved singlet oxygen phosphorescence. Although the results of such measurements demonstrated that melanin obtained from hiPSC-Mel exhibited the physicochemical properties typical for eumelanin, a contribution from pheomelanin with a substantial presence of benzothiazine subunits, was also evident. Importantly, the hiPSC-Mel pigment had significantly lower photoreactivity compared to bRPE melanin and PT-V hair melanin. Our findings indicate that hiPSC-Mel could be an excellent source of high-quality pigment for photoprotection studies. Full article

In this study, we report the synthesis and characterization of a novel photocatalyst composite composed of functionalized carbon nanotubes (f-CNT) and phenyl-modified graphitic carbon nitride (PhCN). The incorporation of the phenyl group extends the absorption range into the visible spectrum compared to pure g-C₃N₄. Additionally, the formation of the heterostructure in the f-CNT/PhCN composite exhibits improved charge transfer efficiency, facilitating the separation and transfer of photogenerated electron-hole pairs and reducing recombination rates. The photocatalytic performance of this composite was evaluated by the degradation of Rhodamine B (RhB) under visible light irradiation. The f-CNT/PhCN composite exhibits remarkable efficiency in degrading RhB, achieving 60% degradation after 4 h, and 100% after 24 h under low-power white LED excitation. This represents a substantial improvement over the non-functionalized CNT/PhCN composite, which shows much lower performance. In contrast, pure PhCN demonstrates very little activity. Structural and optical properties were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), Raman spectroscopy, and UV–Vis spectroscopy. Time-resolved photoluminescence measurements were used to study the behavior of photoexcited carriers, confirming that the composite improves charge transfer efficiency for photogenerated carriers by approximately 30%. The results indicate that the functionalization of CNTs significantly enhances the photocatalytic properties of the composite, making f-CNT/PhCN a promising candidate for environmental remediation applications, particularly in the degradation of organic pollutants in wastewater. Full article

The abnormal deposition of protein in the brain is the central factor in neurodegenerative disorders (NDs). These detrimental aggregates, stemming from the misfolding and subsequent irregular aggregation of α-synuclein protein, are primarily accountable for conditions such as Parkinson’s disease, Alzheimer’s disease, and dementia. Two-photon-excited (TPE) probes are a promising tool for the early-stage diagnosis of these pathologies as they provide accurate spatial resolution, minimal intrusion, and the ability for prolonged observation. To identify compounds with the potential to function as diagnostic probes using two-photon techniques, we explore three distinct categories of compounds: Hydroxyl azobenzene (AZO-OH); Dicyano-vinyl bithiophene (DCVBT); and Tetra-amino phthalocyanine (PcZnNH₂). The molecules were structurally and optically characterized using a multi-technique approach via UV-vis absorption, Raman spectroscopy, three-dimensional fluorescence mapping (PLE), time-resolved photoluminescence (TRPL), and pump and probe measurements. Furthermore, quantum chemical and molecular docking calculations were performed to provide insights into the photophysical properties of the compounds as well as to assess their affinity with the α-synuclein protein. This innovative approach seeks to enhance the accuracy of in vivo probing, contributing to early Parkinson’s disease (PD) detection and ultimately allowing for targeted intervention strategies. Full article

The one-pot synthesis of N-doped graphene quantum dots (GQDs), capped with a positively charged polyamine (trien), has been realized through a microwave-assisted pyrolysis on solid L-glutamic acid and trien in equimolar amounts. The resulting positively charged nanoparticles are strongly emissive in aqueous solutions and are stable for months. The interaction with the anionic tetrakis(4-sulphonatophenyl)porphyrin (TPPS₄) has been investigated at neutral and mild acidic pH using a combination of UV/vis absorption spectroscopy together with static and time-resolved fluorescence emission. At pH = 7, the experimental evidence points to the formation of a supramolecular adduct mainly stabilized by electrostatic interactions. The fluorescence emission of the porphyrin is substantially quenched while GQDs remain still emissive. On decreasing the pH, protonation of TPPS₄ leads to formation of porphyrin J-aggregates through the intermediacy of the charged quantum dots. Full article

Thin films of carbazole (Cz) derivatives are frequently used in organic electronics, such as organic light-emitting diodes (OLEDs). Because of the proximity of the Cz units, the excited-state relaxation in such films is complicated, as intermolecular pathways, such as singlet–singlet annihilation (SSA), kinetically compete with the emission. Here, we provide an investigation of two benchmark systems employing neat carbazole and 3,6-di-tert-butylcarbazole (t-Bu-Cz) films and also their thin film blends with poly(methyl methacrylate) (PMMA). These are investigated by a combination of atomic force microscopy (AFM), femtosecond and nanosecond transient absorption spectroscopy (fs-TA and ns-TA) and time-resolved fluorescence. Excitonic J-aggregate-type features are observed in the steady-state absorption and emission spectra of the neat films. The S₁ state shows a broad excited-state absorption (ESA) spanning the entire UV–Vis–NIR range. At high S₁ exciton number densities of about 4 × 10¹⁸ cm⁻³, bimolecular diffusive S₁–S₁ annihilation is found to be the dominant SSA process in the neat films with a rate constant in the range of 1–2 × 10⁻⁸ cm³ s⁻¹. SSA produces highly vibrationally excited molecules in the electronic ground state (S₀*), which cool down slowly by heat transfer to the quartz substrate. The results provide relevant photophysical insight for a better microscopic understanding of carbazole relaxation in thin-film environments. Full article

Carbazole-based molecular units are ubiquitous in organic optoelectronic materials; however, the excited-state relaxation of these compounds is still underexplored. Here, we provide a detailed investigation of carbazole (Cz) and 3,6-di-tert-butylcarbazole (t-Bu-Cz) in organic solvents using femtosecond and nanosecond UV–Vis–NIR transient absorption spectroscopy, as well as time-resolved fluorescence experiments upon photoexcitation in the deep-UV range. The initially prepared S_x singlet state has a (sub-)picosecond lifetime and decays to the S₁ state by internal conversion (IC). The S₁ state exhibits absorption peaks at 350, 600 and 1100 nm and has a lifetime of 13–15 ns, which is weakly dependent on the solvent. Energy transfer from vibrationally hot S₁ molecules (S₁*) to the surrounding solvent molecules takes place with a time constant of 8–20 ps. The T₁ triplet state is populated by intersystem crossing (ISC) from S₁ with a typical quantum yield of 51–56% and shows a lifetime which is typically in the few microseconds regime. The S₁ and T₁ states of both carbazole compounds in solution are strongly quenched by O₂. Two-photon excitation leads to the formation of a small amount of the respective radical cation. The influence of the tert-butyl substituents on the photophysics is relatively weak and mainly reflects itself in a small increase in the Stokes shift. The results provide important photophysical information for the interpretation of carbazole relaxation in more complex environments. Full article

The bioavailability of the administered drugs that reach the systemic circulation is the first point in resolving the pathology of patients. Albumin-based nanoparticles represent an increasingly used strategy to deliver cancer drugs into cells that otherwise cannot overcome biological barriers. In this work, rutin (Ru), a flavonoid with anticancer and antioxidant potential, was incorporated into bovine serum albumin nanoparticles (BSA-Ru NPs), developed using the desolvation method, and the entire system was characterized and evaluated by scanning electron microscopy (SEM), atomic force microscopy (AFM), and UV–Vis absorption spectroscopy. The results showed that BSA and BSA–Ru NPs are uniformly distributed, have relatively large sizes, and have a time stability of more than 60%. Furthermore, the effect of these nanohybrids on the thermal stability of liposomal membranes was evaluated by surface plasmon resonance (SPR), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The viability evaluation was assessed by the tetrazolium salt (3-(4,5-dimethylthiazol-2-yl)-5-(3-carboxymethoxyphenyl)-2-(4-sulfophenyl)-2H-tetrazolium) (MTS) protocol in the fibroblast L929 line and a high level of biocompatibility, confirmed by SEM results, was found. Full article

Conventional single-component quantum dots (QDs) suffer from low recombination rates of photogenerated electrons and holes, which hinders their ability to meet the requirements for LED and laser applications. Therefore, it is urgent to design multicomponent heterojunction nanocrystals with these properties. Herein, we used CdSe quantum dot nanocrystals as a typical model, which were synthesized by means of a colloidal chemistry method at high temperatures. Then, CdS with a wide band gap was used to encapsulate the CdSe QDs, forming a CdSe@CdS core@shell heterojunction. Finally, the CdSe@CdS core@shell was modified through the growth of the ZnS shell to obtain CdSe@CdS@ZnS heterojunction nanocrystal hybrids. The morphologies, phases, structures and performance characteristics of CdSe@CdS@ZnS were evaluated using various analytical techniques, including transmission electron microscopy, X-ray diffraction, UV-vis absorption spectroscopy, fluorescence spectroscopy and time-resolved transient photoluminescence spectroscopy. The results show that the energy band structure is transformed from type II to type I after the ZnS growth. The photoluminescence lifetime increases from 41.4 ns to 88.8 ns and the photoluminescence quantum efficiency reaches 17.05% compared with that of pristine CdSe QDs. This paper provides a fundamental study and a new route for studying light-emitting devices and biological imaging based on multicomponent QDs. Full article

Aggregating gold(I) complexes in solution through short aurophilic contacts promotes new photoluminescent deactivation pathways (aggregation-induced emission, AIE). The time dependence of spontaneous AIE is seldom studied. We examine the behavior of complex [Au(N⁹-hypoxanthinate)(PTA)] (1) in an aqueous solution with the aid of variable-temperature NMR, time-resolved UV–Vis and photoluminescence spectroscopy, and PGSE NMR. The studies suggest that partial ligand scrambling in favor of the ionic [Au(PTA)₂][Au(N⁹-hypoxanthinate)₂] pair followed by anion oligomerization takes place. The results are rationalized with the aid of computational calculations at the TD-DFT level of theory and IRI analysis of the electron density. Full article

The template effect of giant polyoxometalates (POM) shows promising results towards the supramolecular design of hybrid materials suitable for photocatalytic reactions. Here, we demonstrate a novel synthetic approach for covalently grafting the xanthene dye eosin Y (EY) to the nanoscale Keplerate POM {Mo₁₃₂} via an organosilicon linker (3-aminopropyltrimethoxysilane, APTMS) in a homogeneous regime. Using a phase transfer agent, tetrabutylammonium bromide, we solubilize the Keplerate POM modified with six {Si(CH₂)₃NH₂} groups, {Mo₁₃₂}@Si₆, in a series of organic solvents—acetonitrile, acetone, tetrahydrofuran, and dichloromethane—to perform post-functionalization by using an NHS-ester of EY. Both IR and Raman spectroscopy affirm the preservation of the POM’s structure and showcase an amide bond formation between POM and EY in the obtained conjugate {Mo₁₃₂}@Si₆@EY@TBA. Grafting’s success is observed through significant downfield shifting of EY’s aromatic protons’ signals on the ¹H NMR spectrum as compared to the spectra of EY and EY-NHS. The current synthetic approach enables us to exercise precise control of the stoichiometry in the POM-dye conjugates—1:1 for the POM-EY system—as confirmed by elemental analysis. Comprehensive photophysical analysis of {Mo₁₃₂}@Si₆@EY@TBA by means of UV-Vis and steady-state and time-resolved fluorescence measurements points to an existing strong interaction between molecular orbitals of EY and {Mo₁₃₂}, leading to a photoinduced electron transfer, partial fluorescence quenching, and elongation of the excited state’s lifetime. These findings demonstrate that using APTMS as an organosilicon linker in tandem with the Keplerate POM as a nanoscale template can be readily applied as a routine synthetic procedure for grafting various organic dyes or other organic molecules bearing a carboxylic group in their structure to the giant POM surface in a variety of aprotic organic solvents. Full article

Single crystals of 2-methylbenzimidazolium perchlorate were prepared for the first time with a slow evaporation method from an aqueous solution of a mixture of 2-methylbenzimidazole (MBI) crystals and perchloric acid HClO₄. The crystal structure was determined by single crystal X-ray diffraction (XRD) and confirmed by XRD of powder. Angle-resolved polarized Raman and Fourier-transform infrared (FTIR) absorption spectra of crystals consist of lines caused by molecular vibrations in MBI molecule and ClO₄⁻ tetrahedron in the region ν = 200–3500 cm⁻¹ and lattice vibrations in the region of 0–200 cm⁻¹. Both XRD and Raman spectroscopy show a protonation of MBI molecule in the crystal. An analysis of ultraviolet-visible (UV-Vis) absorption spectra gives an estimation of an optical gap E_g~3.9 eV in the crystals studied. Photoluminescence spectra of MBI-perchlorate crystals consist of a number of overlapping bands with the main maximum at E_photon ≅ 2.0 eV. Thermogravimetry-differential scanning calorimetry (TG-DSC) revealed the presence of two first-order phase transitions with different temperature hysteresis at temperatures above room temperature. The higher temperature transition corresponds to the melting temperature. Both phase transitions are accompanied by a strong increase in the permittivity and conductivity, especially during melting, which is similar to the effect of an ionic liquid. Full article

Functional metal nanomaterials, especially in the nanocluster (NC) size regime, with strong fluorescence, aqueous colloidal stability, and low toxicity, necessitate their application potential in biology and environmental science. Here, we successfully report a simple cost-effective method for red-/green-color-emitting protein/amino-acid-mediated Cu NCs in an aqueous medium. As-synthesized Cu NCs were characterized through UV-Vis absorption spectroscopy, fluorescence spectroscopy, time-resolved photoluminescence, dynamic light scattering, zeta potential, transmission electron microscopy and X-ray photoelectron spectroscopy. The optical properties of both Cu NCs responded linearly to the variation in pH in the neutral and alkaline ranges, and a robust pH reversible nature (between pH 7 and 11) was observed that could be extended to rapid, localized pH sensor development. However, a contrasting pH response nature between protein–Cu NCs and amino acid–Cu NCs was recorded. The alteration in protein secondary structure and strong binding nature of the surfactants were suggested to explain this behavior. Furthermore, we investigated their use as an efficient optical probe for fluoride ion detection. The limit of detection for protein–Cu NCs is 6.74 µM, whereas the limit of detection for amino acid–Cu NCs is 4.67 µM. Thus, it is anticipated that ultrasmall Cu NCs will exhibit promise in biological and environmental sensing applications. Full article

Long-wave infrared (LWIR) emissions of laser-induced plasma on solid potassium chloride and acetaminophen tablet surfaces were studied using both a one-dimensional (1-D) linear array detection system and, for the first time, a two-dimensional (2-D) focal plane array (FPA) detection system. Both atomic and molecular infrared emitters in the vicinity of the plasma were identified by analyzing the detected spectral signatures in the infrared region. Time- and space-resolved long-wave infrared emissions were also studied to assess the temporal and spatial behaviors of atomic and molecular emitters in the plasma. These pioneer temporal and spatial investigations of infrared emissions from laser-induced plasma would be valuable to the modeling of plasma evolutions and the advances of the novel LWIR laser-induced breakdown spectroscopy (LIBS). When integrated both temporally (≥200 µs) and spatially using a 2-D FPA detector, the observed intensities and signal-to-noise-ratio (SNR) of single-shot LWIR LIBS signature emissions from intact molecules were considerably enhanced (e.g., with enhancement factors up to 16 and 3.76, respectively, for a 6.62 µm band of acetaminophen molecules) and, in general, comparable to those from the atomic emitters. Pairing LWIR LIBS with conventional ultraviolet–visible–near infrared (UV/Vis/NIR) LIBS, a simultaneous UV/Vis/NIR + LWIR LIBS detection system promises unprecedented capability of in situ, real-time, and stand-off investigation of both atomic and molecular target compositions to detect and characterize a range of chemistries. Full article