Publications

Abstract Here we report the near-infrared-upconversion (NIR-UC) luminescence of the organic dye fluorescein, without the need of metal-based NIR-UC materials or the use of high-energy and high-cost two-photon absorption excitation (TPA) systems. Fluorescein upconverts NIR light (lambda = 920 nm) to visible light (lambda = 545 nm) in aqueous solutions, with a pH-dependent light-intensity, by using a low-energy and low-cost nanosecond pulsed laser. The NIR-UC of fluorescein is explained with a triplet-triplet annihilation (TTA) mechanism, assisted by molecular vibrations. This work opens the door for deep-penetration bioimaging and photodynamic therapy, as well for NIR-excited TTA, photocatalysis and photovoltaics, by using solely high quantum yield organic molecules.

Abstract Chemical functionalization of multiwalled carbon nanotubes (MWCNTs) is important from the view point of polymer based composite manufacturing. As pristine MWCNTs has certain disadvantage such as they have lower dispersion, they are hydrophobic and are not readily soluble in a solvent, these characteristics makes them unreliable candidate for most of the industrial applications. By doing chemical functionalization of MWCNTs, these shortcomings can be overcome, and the MWCNTs can be used as a filler in composite manufacturing. This has the advantage of better nanofillers’ dispersion and provide the better interfacial bonding. In this study, MWCNTs are functionalized by the carboxylic group, chemical functionalization of MWCNTs is an optimization problem, governed by parameters like mixture acid concentration, temperature, time of heating and amount of MWCNTs used. Material characterization of MWCNTs is done and test specimens are manufactured according to different concentrations of MWCNTs within a bio-based epoxy resin. Mechanical properties are then compared according to different concentrations. These mechanical and material characterizations increase the understanding of chemical functionalization by carboxylic group and the influence of the concentration of MWCNTs dispersed within the bio-based resin matrix.

Abstract Surface disinfection is of utmost importance in the prevention of bacterial infections. This study aims to assess the ability of ten phytochemicals and related derivatives as potentiators of two commonly used biocides-cetyltrimethylammonium bromide (CTAB) and lactic acid (LA). LA in combination with cinnamic, hydrocinnamic, alpha-methylcinnamic, and alpha-fluorocinnamic acids had a factional inhibitory concentration index (FICI) <= 1 for Escherichia coli and Staphylococcus aureus. Several phytochemicals/derivatives in combination with biocides improved the biocidal efficacy against early sessile bacteria. The most effective combination was LA with allyl cinnamate (2.98 +/- 0.76 log CFUcm(-2) reduction) against E. coli. The combination with CTAB was successful for most phytochemicals/derivatives with a maximum bactericidal efficacy against sessile E. coli when combined with allyl cinnamate (2.20 +/- 0.07 log CFUcm(-2) reduction) and for S. aureus when combined with alpha-methylcinnamic acid (1.68 +/- 0.30 log CFUcm(-2) reduction). This study highlights the potential of phytochemicals and their derivatives to be used in biocide formulations.

Abstract Herein, the synthesis of Ho3+ (2 mmol%)/Yb3+ (18 mmol%) doped NaGdF4 up-conversion (UC) phosphor particles via two different chemical routes namely thermal decomposition (sample 1) and hydrothermal (sample 2) methods is done and then the structural and optical properties were studied. The properties of the samples are characterized via different techniques. The UC emission bands are obtained in the visible range at 488 nm, 543 nm, 645 nm and 754 nm wavelengths corresponding to F-5(3) -> I-5(8), F-5(4)/S-5(2) -> I-5(8), F-5(5) -> I-5(8) and I-5(4) -> I-5(8) transitions, respectively. The change in sample internal temperature due to the 980 nm diode laser excitation is calculated for both the samples. The variation in UC emission intensity as a function of the complete cycle of the applied magnetic field (0-1.1 x 10(4) Oe-0) is confirmed the optical bi-stability behavior of the present sample. Sample 1 has found a colloidal stable in water and hence this sample dispersed in the aqueous medium of polyvinyl alcohol (PVA) and thus utilized in security witting demonstration on a bank-note surface. Sample 2 with high emission intensity is demonstrated for latent fingermark detection.

Abstract Aqueous biphasic systems constituted by ionic liquids (IL-based ABSs) are a target of investigation in the separation of high-value biomolecules. However, identification of the molecular-level mechanisms ruling the two-phase formation and extraction performance of these systems is crucial to the successful design of effective separation processes. In this work, IL-based ABSs formed by K2HPO4 and cholinium carboxylate ILs ([Ch] [CnCO2] with n = 1-7, comprising anions with odd and even alkyl chain lengths) were investigated. The corresponding ternary phase diagrams, including binodal curves, tie-lines, tie-line lengths, and critical points, as well as the Setschenow salting-out coefficients (k(s)), which quantitatively describe the two-phase formation ability, were determined at 298 K. The extraction capability of these systems was then evaluated for four amino acids (L-tryptophan, L-phenylalanine, L-tyrosine, and L-3,4-dihydroxyphenylalanine/L-dopa). It was found that ILs composed of anions with even alkyl chains display slightly higher k(s) values, meaning that these ILs are more easily salted out or more easily phase-separated to form ABSs, whereas ABSs formed by ILs with anions comprising odd alkyl chains lead to slightly higher partition coefficients of amino acids. Beyond the neat IL odd-even effect resulting from their nanostructuration, being this a well-known phenomenon occurring in a series of their thermophysical properties, the existence of an odd-even effect displayed by the IL anion aliphatic moiety in aqueous solution is shown here, visible in both the two-phase formation ability and extraction performance of ABSs. These findings contribute to elucidate of the molecular-level mechanisms governing ABS formation and partitioning of biomolecules, ultimately contributing to the design of proficient separation platforms.

Abstract 6-Bromochromone-2-carboxylic acid (3) was synthesized by a microwave-assisted process. The optimization of the reaction was performed varying parameters, such as type of base/number of reagent equivalents, solvent, temperature and reaction time. The yield of the reaction was improved to 87%. The new synthetic route is versatile as several chromone-2-carboxylic acids (compounds 4B-10B) were obtained with good yields (54-93%). Only in the case of the nitro substituent (compound 11B), an ester was obtained instead of the desired carboxylic acid. Following this synthetic route chromone carboxylic acids can be attained with a high degree of purity, without the need of the tedious and expensive purification processes through column chromatography. The reaction is safe, cost-effective, fast and robust, and can be used in the development of concise and diversity-oriented libraries based on chromone scaffold. The overall study can be looked as a step forward to speed-up the discovery of chromone-based multitarget-directed ligands.

Abstract Carbon dots have attracted great attention from the research community given their very attractive luminescent properties. However, the recent discovery that some of these properties may result from fluorescent impurities originating from the synthesis process, and not from the carbon dots themselves, constitute a significant setback to our knowledge of these materials. Herein, we proceeded to the study of carbon dots generated from citric acid and urea via a microwave-assisted synthesis, focusing on their analysis by AFM, HR-TEM, XPS, FT-IR, ESI-MS, UV-Vis and fluorescence spectroscopy. We have found that this synthesis process does generate molecular fluorophores that can mask the luminescence of the carbon dots. More importantly, our data demonstrates that when present in the same solution, the carbon dots and these fluorophores do not behave as separated species with individual emission. Instead, they interact to produce a hybrid luminescence, which excited state properties and reactivity are different from the properties of the individual species. These results indicate the possibility for the development of hybrid materials composed by carbon dots and related molecular fluorophores with new and improved properties.

Abstract The ring-opening reaction of epoxides is an essential step in CO2 conversion into value-added heterocyclic carbonates. There has been an increasing focus on developing organocatalysts composed by a nucleophile and a hydrogen bond donor (HBD), so that CO2 conversion can occur at ambient conditions, with the rationale that HBD can aid epoxide's ring-opening. Nevertheless, it is not clear what is the real role of HBDs on this reaction. Herein, it was employed a combined spectroscopic and theoretical approach to obtain mechanistic insight into the ring-opening of a model epoxide, when catalyzed by pyridine and different HBDs. While the pyridine-HBD system decreased the activation barrier from (similar to)60 to (similar to)22-23 kcal mol(-1), by itself pyridine decreased it to (similar to)27 kcal mol(-1). This shows that HBDs present a small effect on the activation energy. Furthermore, it was found that water molecules can act as HBD with similar results to other molecules. This helps to explain why catalytic amounts of water have found to be advantageous in CO2 conversion. Further work found that the activation barrier is mainly controlled by steric contributions. Subsequent spectroscopic analysis showed that the obtained rate constants follow the same trend found in the theoretical calculations, while these reactions lead to the formation of the same products in similar ratios. It was also found that one pyridine molecule can catalyze the opening of two epoxides, resulting in a trimeric structure. Finally, the addition of electron-donating groups to pyridine increases the catalytic properties of the system.

Abstract While brown carbon is a strongly-light-absorbing type of organic aerosol that is capable of significant regional radiative forcing, it has been neglected from climate models, which results in differences between model predictions and measured data. This also results from uncertainty regarding the relationship between the chemical composition of brown carbon and its optical properties. Herein, here was utilized a time-dependent density functional theory (TD-DFT) approach to model the "real-world" absorption of thirty polycyclic aromatic hydrocarbons (PAHs) and twenty-five derivatives (ten nitro-PAHs and fifteen oxygenated-PAHs) present in the atmosphere over three Southern European cities (Porto, Florence and Athens). These data were corrected both for "real-world" experimental concentration of these molecules over these cities, and for their theoretical fluorescence yield. These results indicate that the absorption of the molecules more relevant for climate forcing are at similar to 330, similar to 360 and similar to 440 nm. Furthermore, the absorption is explained mainly by PAH and oxygenated-PAH molecules, while nitro-PAHs provide only negligible contributions. Porto should be the city to be most affected by radiative forcing induced by these molecules, while Florence and Athens appear to be similarly affected. Finally, these models also demonstrate that absorption at similar to 330 nm is explained by both PAH and oxygenated-PAH-molecules, while absorption at similar to 360 and similar to 440 nmis only attributed to oxygenated-PAHs. More specifically, from the fifty-five studied molecules, only coronene (a PAH), 1,8-naphthalic anhydride, 6-H-benzo[cd]pyrene-6-one and 7H-benz[de]anthracence-7-one (three oxygenated-PAHs) provide relevant contributions to radiative forcing.

Abstract Cypridina bioluminescence has been increasingly used in bioimaging, bioanalysis, and biomedicine, due to high quantum yield and high signal-to-noise ratio. However, there is still no consensus regarding different aspects of the chemiluminescent mechanism of this system, which impairs the development of new applications. Herein, we have used a theoretical DFT and TD-DFT approach to (i) determine the identity of the dioxetanone species responsible for efficient chemiexcitation and (ii) identify the bioluminescent emitter and determine if light-emission occurs from the fluorescent or chemiluminescent state. Our results demonstrate that upon oxygenation of the imidazopyrazinone scaffold, a dioxetanone with a neutral amide group and a cationic guanidinopropyl group is formed. This species is efficiently chemiexcited (with no obvious charge transfer step) to the corresponding oxyluciferin with a neutral amide and cationic guanidinopropyl groups. After the "dark" chemiluminescent state, this oxyluciferin species is converted into a bright blue-emitting fluorescent state.