Publications

Abstract The impact of structural differentiation between phenylcarbazoles (PhC, mCP, CBP, TCB) and phenylamines (TPA, BDB, TPB, TDAB) on the phase equilibria, optical spectrum, band gap, and thin-film morphology is evaluated and discussed. The carbazolyl units lead to a lower electronic conjugation contributing to a wide band gap when compared with the diphenylamine analogs. The fusion and sublimation equilibria indicate that entropic contribution is the key factor for the distinguished melting behavior and solid-phase volatility between phenylcarbazole derivatives and phenylamine analogs. The molecular differentiation between the two classes of compounds is not reflected in the crystal packing and intermolecular interactions. However, compared with the diphenylamino groups, the incorporation of carbazolyl moieties contributes to a less flexible molecule. Moreover, the results evidence that intermolecular bonding disruption along the fusion transition is more extensive for phenylamine derivatives. Due to the asymmetric nonplanar structure, mCP is characterized by a ratio of {T-g/T-m approximate to 3/4} while the more symmetric CBP and TCB molecules display ratios closer to {T-g/T-m approximate to 2/3}. Vapor-deposited thin films of mCP, CBP, and TCB are amorphous and their morphology is highly dependent on the substrate roughness. The lower flexibility of nonplanar phenylcarbazoles induces the formation of a glassy state due to the harder packing mechanism leading to the lower ability of the crystallization process.

Abstract The authors regret the existence of an error on one of the results reported in the original and published manuscript. The error has been identified and rectified as follows: • In Abstract, page 2469: the half-life period of “23.8 ± 0.6 s” should be read as “47.6 ± 1.1 s”. • In page 2472, section Results and discussion, second paragraph: the half life was “23.8 ± 0.6 s” should be read as “47.6 ± 1.1 s”. • In page 2478, section Conclusions, first paragraph: the half life period of “23.8 ± 0.6 s” should be read as “47.6 ± 1.1 s”. The authors would like to apologise for any inconvenience caused to the editorial staff and the editor of the Journal of Environmental Chemical Engineering, as well as all its valuable readers and followers.

Abstract Carbon dots (CDs) are carbon-based nanoparticles with very attractive luminescence features. Furthermore, their synthesis by bottom-up strategies is quite flexible, as tuning the reaction precursors and synthesis procedures can lead to an endless number of CDs with distinct properties and applications. However, this complex variability has made the characterization of the structural and optical properties of the nanomaterials difficult. Herein, we performed a systematic evaluation of the effect of three representative bottom-up strategies (hydrothermal, microwave-assisted, and calcination) on the properties of CDs prepared from the same precursors (citric acid and urea). Our results revealed that these synthesis routes led to nanoparticles with similar sizes, identical excitation-dependent blue-to-green emission, and similar surface-functionalization. However, we have also found that microwave and calcination strategies are more efficient towards nitrogen-doping than hydrothermal synthesis, and thus, the former routes are able to generate CDs with significantly higher fluorescence quantum yields than the latter. Furthermore, the different synthesis strategies appear to have a role in the origin of the photoluminescence of the CDs, as hydrothermal-based nanoparticles present an emission more dependent on surface states, while microwave- and calcination-based CDs present an emission with more contributions from core states. Furthermore, calcination and microwave routes are more suitable for high-yield synthesis (similar to 27-29%), while hydrothermal synthesis present almost negligible synthesis yields (similar to 2%). Finally, life cycle assessment (LCA) was performed to investigate the sustainability of these processes and indicated microwave synthesis as the best choice for future studies.

Abstract This work presents a new Knudsen effusion apparatus employing continuous monitoring of sample deposition using a quartz-crystal microbalance sensor with internal calibration by gravimetric determination of the sample mass loss. The apparatus was tested with anthracene and 1,3,5-triphenylbenzene and subsequently used for the study of sublimation behavior of several proteinogenic amino acids. Their low volatility and thermal instability strongly limit possibilities of studying their sublimation behavior and available literature data. The results presented in this work are unique in their temperature range and low uncertainty required for benchmarking theoretical studies of sublimation behavior of molecular crystals. The possibility of dimerization in the gas phase that would invalidate the effusion experiments is addressed and disproved by theoretical calculations. The enthalpy of sublimation of each amino acid is analyzed based on the contributions in two hypothetical sublimation paths involving the proton transfer in the solid and in the gas phase.

Abstract Spent coffee grounds (SCGs) are known for containing many organic compounds of interest, including carbohydrates, lipids, phenolic compounds and proteins. Therefore, we investigated them as a potential source to obtain carbon dots (CDs) via a nanotechnology approach. Herein, a comparison was performed between CDs produced by SCGs and classic precursors (e.g., citric acid and urea). The SCG-based CDs were obtained via the one-pot and solvent-free carbonization of solid samples, generating nanosized particles (2.1-3.9 nm). These nanoparticles exhibited a blue fluorescence with moderate quantum yields (2.9-5.8%) and an excitation-dependent emission characteristic of carbon dots. SCG-based CDs showed potential as environmentally relevant fluorescent probes for Fe(3+)in water. More importantly, life cycle assessment studies validated the production of CDs from SCG samples as a more environmentally sustainable route, as compared to those using classic reported precursors, when considering either a weight- or a function-based functional unit.

Abstract Catechol O-methyltransferase (COMT) inhibitors are valuable co-adjuvant drugs in the clinical management of Parkinson's disease (PD), and recent data also suggest therapeutic benefits in other neurological disorders associated with dopamine depletion. However, the relationship between tolcapone administration with fatal cases of drug-induced liver damage gave COMT inhibitors a bad reputation as hepatotoxic drugs. Thus, there is a pressing need to feed the pipeline with safe COMT inhibitors to replace tolcapone, the only currently available COMT inhibitor that effectively reaches the brain. Recent efforts led to promising phenolic and nonphenolic COMT inhibitors, which allow isoform-specific targeting and avoid the toxicological and pharmacokinetic (PK) shortcomings of classic nitrocatechols. Here, we describe advances made in this field over the past 5 years.

Abstract This work aims to apply photonic-crystal-based nanocoatings with unusual aesthetical orientation to wood application. Structural colors are currently a formula to achieve those colorful coatings including nonfading properties. They can be produced from self-assembled colloidal spheres into photonic crystals, which possess particular optical properties. Herein, photonic crystals with iridescent structural colors were prepared from the self-assembly of monodispersed nanospheres. Particle sizes can be adjusted from 308 to 196 nm, and well-ordered structures are arranged through self-assembly process into films, which exhibit brilliant colors over a wide visible spectrum, from red to violet. Color varies with the angle of observation of incidence light. The present study provided an effective and simple approach to prepare structural color films and their practical application to wood coating for an aesthetic appeal.

Abstract In this study, a homogeneous thin film growth of pentacene onto indium tin oxide (ITO) coated glass surfaces is explored using a high-resolution and reproducible vapor deposition methodology. Moreover, vacuum thermal evaporation of ionic liquids (ILs) ([C(2)C(1)im][NTf2] and [C(2)C(1)im][OTF]) onto ITO, gold/palladium (AuPd) and pentacene surfaces were performed. A greater wettability behavior of ILs is observed for surfaces containing AuPd. Sequential and simultaneous depositions of ILs and pentacene were explored. Simultaneous depositions lead to the formation of nanocomposites films, consisting of IL micro- and nanodroplets covered by pentacene layers. Plasma surface treatment was used to induce the ILs droplets coalescence and explore the dynamics and phase separation of the nanocomposites. The [C(2)C(1)im][OTF] droplets were found to be completely covered with pentacene, which suggests a great affinity between cation-anion pairs and the aromatic moiety. Pentacene films and their nanocomposites with ILs exhibit a typical optical band gap ofE(gap)=1.77 eV, indicating that the nanocomposite phase domains are large enough to behavior as the bulk.

Abstract Background: The increasing demand of effective pharmaceutical products directed to fight against malaria lead to the combination of at least two antimalarial drugs. This combination aims to minimize the Plasmodium falciparum resistance which is found when the most frequently used drugs are taken individually. Within this context, proguanil hydrochloride and chloroquine phosphate which have independent modes of action are taken together to prevent malaria. This paper aims to develop a fast and powerful analytical method for the simultaneous determination of proguanil hydrochloride and chloroquine phosphate in the commercial Paludrine/Avloclor dosage forms using a multi-way chromatographic calibration based on high-performance liquid chromatography with diode array detection (HPLC-DAD) and multivariate curve resolution - alternating least-squares (MCR-ALS). Methods: A rapid and powerful analytical method based on HPLC-DAD and MCR-ALS was developed for the simultaneous quantification of proguanil hydrochloride and chloroquine phosphate in the commercial Paludrine/Avloclor antimalarial drugs. An isocratic mobile phase composed by 0.2 M ammonium acetate, acetonitrile, and methanol (40:25:35) and a flow rate of 1.2 mL min(-1) were employed in the chromatographic runs with an elution time about 5 min. Results: This approach demonstrates that chromatographic analysis may become considerably simpler and economical in terms of time, cost, and organic solvent consumption when coupled to multiway calibration models such as MCR-ALS. In fact, this multi-way chromatographic calibration based on second-order HPLC-DAD data matrices (with extremely low chromatographic resolution) and MCR-ALS allows the development of greener analytical methods for complex samples. The proposed analytical method allowed the simultaneous quantification of two antimalarial APIs present in the commercial Paludrine/Avloclor drugs with low REP values below 8% for the simultaneous determination of proguanil hydrochloride and chloroquine phosphate. Conclusion: The proposed multi-way chromatographic strategy can be used for routine control of pharmaceutical dosage forms. It should be highlighted that MCR-ALS allowed to: (a) achieve the second-order advantage and the quantification of analytes in the presence of uncalibrated compounds such as coeluted profile measured in different magnitude of the signal in each successive chromatographic run and significant overlapping profiles and (b) separate the contribution of several components from chromatographic runs with extremely low separation of peaks through the deconvolution of the signal obtained, performing the so-called mathematical chromatography.

Abstract Microorganisms have the ability to multiply, attach to wet surfaces, and produce a matrix of extracellular polymeric substances (EPS), forming biofilms. The development of biofilms occurs on almost all surfaces (inanimate and living) and can cause serious problems in medical field, food industry, and systems. The multiple layers of cells and EPS confer to biofilms a complex and compact structure that hinders penetration of antimicrobial agents, decreasing their capacity to reach internal layers, and rendering them ineffective. Thus, when microorganisms form biofilms, the resistance to conventional antimicrobial agents increases significantly, and the control of those biofilms becomes hard to achieve. Besides, due to the complexity/heterogeneity of sessile communities, the application of a single strategy is considered insufficient. In this context, there is a need for new strategies, new antimicrobials, and biofilm prevention/control techniques. An ideal antibiofilm strategy should involve approaches to prevent biofilm formation, disintegrate biofilm structure, or remove preformed biofilms. Promising approaches can be based on the application of “green” and biological-based products, such as enzymes. Enzymes are applied in many fields of investigation and are known to be capable of degrading key components of the biofilm matrix. Moreover, it is recognized that the combination of enzymes with other biofilm control agents can enhance their activity. However, enzymes are specific, and to degrade the complex matrix that involves the biofilm, a mixture of enzymes is often necessary. In this chapter, the factors that play a crucial role in the resistance of biofilm-associated bacteria will be addressed. In addition, emergent strategies for biofilm control and eradication will be highlighted. As the use of biofilm-disrupting enzymes appears to be a very promising option to effectively control and eradicate microbial biofilms, a literature review for this strategy will be presented.