Cooperativity of ESPT and Aggregation-Induced Emission Effects-An Experimental and Theoretical Analysis of a 1,3,4-Thiadiazole Derivative.

4-[5-(Naphthalen-1-ylmethyl)-1,3,4-thiadiazol-2-yl]benzene-1,3-diol (NTBD) was extensively studied through stationary UV-vis absorption and fluorescence measurements in various solvents and solvent mixtures and by first-principles quantum chemical calculations. It was observed that while in polar solvents (e.g., methanol) only a single emission band emerged; the analyzed 1,3,4-thiadiazole derivative was capable of producing dual fluorescence signals in low polarity solvents (e.g., n-hexane) and certain solvent mixtures (e.g., methanol/water). As clearly follows from the experimental spectroscopic studies and theoretical modeling, the specific emission characteristic of NTBD is triggered by the effect of enol → keto excited-state intramolecular proton transfer (ESIPT) that in the case of solvent mixture is reinforced by aggregation of thiadiazole molecules. Specifically, the restriction of intramolecular rotation (RIR) due to environmental hindrance suppresses the formation of non-emissive twisted intramolecular charge transfer (TICT) excited keto* states. As a result, this particular thiadiazole derivative is capable of simultaneously producing both ESIPT and aggregation-induced emission (AIE).

Powdered plant beverages obtained by spray-drying without carrier addition-physicochemical and chemometric studies.

Plant-based beverages (PBs) are currently gaining interest among consumers who are seeking alternative sustainable options to traditional dairy drinks. The study aimed to obtain powdered plant beverages without the addition of carriers by spray drying method to implement them in the future as an alternative to the liquid form of dairy drinks. Some of the most well-known commercial beverages sources like soy, almond, rice and oat were analyzed in this work. The effect of different treatments (concentration, addition of oat fiber) and two approaches od spray drying (conventional high temperature spray drying-SD, and dehumidified air spray drying at low temperature-DASD) were presented. Moreover, moisture content, water activity, particle morphology and size of obtained powders were analyzed. It was possible to obtain PBs without the addition of carriers, although the drying yield of four basic beverages was low (16.1-37.4%). The treatments and change in spray drying approach enhanced the drying yield, especially for the concentrated beverage dried using DASD (59.2%). Additionally, Fourier Transform Infrared (FTIR) spectroscopy was applied to evaluate the differences in chemical composition of powdered PBs. FTIR analysis revealed differences in the range of the absorption frequency of amide I, amide II (1700-1500 cm-1) and carbohydrate region (1200-900 cm-1). Principal component analysis (PCA) was carried out to study the relationship between spray dried plant beverages samples based on the fingerprint region of FTIR spectra, as well as the physical characteristics. Additionally, hierarchical cluster analysis (HCA) was employed to explore the clustering of the powders.

Evaluation of the Quality of Selected White and Red Wines Produced from Moravia Region of Czech Republic Using Physicochemical Analysis, FTIR Infrared Spectroscopy and Chemometric Techniques.

The FTIR-ATR method coupled with the multivariate analysis of specific spectral areas of samples was developed to characterize two white grape varieties (Sauvignon Blanc and Hibernal) and two blue grape varieties (André and Cabernet Moravia) of wine planted and harvested in the Moravia region, Czech Republic. Principal component analysis and hierarchical cluster analysis were performed using fingerprint regions of FTIR spectra for all wines. The results obtained by principal component analysis in combination with linear discriminant analysis (PCA-LDA) scores yielded clear separation between the four classes of samples and showed very good discrimination between the wine samples, with a 91.7% overall classification rate for the samples. The conducted FTIR spectroscopy studies coupled with chemometrics allowed for the swift analysis of multiple wine components with minimal sample preparation. These methods can be used in research to improve specific properties of these wines, which will undoubtedly enhance the quality of the final wine samples obtained.

The Visibility of Changes in the Antioxidant Compound Profiles of Strawberry and Raspberry Fruits Subjected to Different Storage Conditions Using ATR-FTIR and Chemometrics.

Strawberry cultivars Portola and Enduro, as well as raspberry cultivars Enrosadira and Kwazi, were evaluated for their antioxidant potential after treatment with gaseous ozone and different refrigeration storage conditions. Their antioxidant capacity was investigated with ABTS and DPPH methods, and the chemical composition was determined by measuring the total phenolic (TPC) and flavonoid (TFC) compounds. The classification of different samples of berry puree was influenced significantly by both the cultivars and the refrigeration storage method. Moreover, FTIR spectroscopy coupled with chemometrics was used as an alternative technique to conventional methods to determine the chemical composition of strawberries and raspberries. The chemometric discrimination of samples was achieved using principal component analysis (PCA), hierarchical clustering analysis (HCA) and linear discriminant analysis (LDA) modelling procedures performed on the FTIR preprocessed spectral data for the fingerprint region (1800-500 cm-1). The fingerprint range between 1500 and 500 cm-1, corresponding to deformation vibrations from polysaccharides, pectin and organic acid content, had a significant impact on the grouping of samples. The results obtained by PCA-LDA scores revealed a clear separation between four classes of samples and demonstrated a high overall classification rate of 97.5% in differentiating between the raspberry and strawberry cultivars.

Naturally Occurring Chalcones with Aggregation-Induced Emission Enhancement Characteristics.

In this paper, the natural chalcones: 2'-hydroxy-4,4',6'-trimethoxychalcone (HCH), cardamonin (CA), xanthohumol (XN), isobavachalcone (IBC) and licochalcone A (LIC) are studied using spectroscopic techniques such as UV-vis, fluorescence spectroscopy, scanning electron microscopy (SEM) and single-crystal X-ray diffraction (XRD). For the first time, the spectroscopic and structural features of naturally occurring chalcones with varying numbers and positions of hydroxyl groups in rings A and B were investigated to prove the presence of the aggregation-induced emission enhancement (AIEE) effect. The fluorescence studies were carried out in the aggregate form in a solution and in a solid state. As to the results of spectroscopic analyses conducted in the solvent media, the selected mixtures (CH3OH:H2O and CH3OH:ethylene glycol), as well as the fluorescence quantum yield (ϕF) and SEM, confirmed that two of the tested chalcones (CA and HCH) exhibited effective AIEE behaviour. On the other hand, LIC showed a large fluorescence quantum yield and Stokes shift in the polar solvents and in the solid state. Moreover, all studied compounds were tested for their promising antioxidant activities via the utilisation of 1,1- diphenyl-2-picrylhydrazyl as a free-radical scavenging reagent as well as potential anti-neurodegenerative agents via their ability to act as acetylcholinesterase (AChE) and butyrylcholinesterase (BuChE) inhibitors. Finally, the results demonstrated that licochalcone A, with the most desirable emission properties, showed the most effective antioxidant (DPPH IC50 29%) and neuroprotective properties (AChE IC50 23.41 ± 0.02 µM, BuChE IC50 42.28 ± 0.06 µM). The substitution pattern and the biological assay findings establish some relation between photophysical properties and biological activity that might apply in designing AIEE molecules with the specified characteristics for biological application.

Impact of Metal Nanoparticles on the Phytochemical and Antioxidative Properties of Rapeseed Oil.

The agricultural uses of nanoparticles continue to be considered as innovative methods that require more in-depth research into their impact on product quality. In our study, we investigated the effects of fertilizers containing metal nanoparticles (silver AgNPs and copper CuNPs) during the plant growth stage of winter rape cultivation, and in most experimental variants, with the exception of the (x2) application of AgNPs, we observed a decrease in the mass of one thousand seeds (MTS). The obtained result was 11.55% higher relative to the control sample in 2019, and also increased after the (x1) 4.36% and (x2) 11.11% application of CuNPS in 2020. The analyzed oxidative stability of the oil increased in both experimental years (2019-2020), with the highest values recorded after the (x1) and (x2) application of CuNPS-4.94% and 8.31%, respectively, in the first year of cultivation, and after the (x2) application of CuNPS-12.07% in the subsequent year. It was also observed that the content of polyphenols, flavonoids, squalene, tocopherols α and δ, chlorophylls, and carotenoids increased in the oil. Moreover, spectral FTIR analysis was performed on the oil samples obtained from cultivations sprayed with solutions containing Ag or Cu nanoparticles and revealed changes in several spectral regions with the maxima at ~1740, 1370, 1230, and ~1090 cm-1. Additionally, a FTIR analysis conducted in combination with multivariate analysis allowed us to classify the studied oils into the most similar groups and to study the structure of data variability. The conducted analyses revealed that the use of nanoparticles resulted in decreased size of the produced seeds and improved antioxidative properties of rapeseed oil.

Spectroscopic characterization and assessment of microbiological potential of 1,3,4-thiadiazole derivative showing ESIPT dual fluorescence enhanced by aggregation effects.

In the presented study, advanced experimental techniques, including electronic absorption and fluorescence spectroscopies [with Resonance Light Scattering (RLS)], measurements of fluorescence lifetimes in the frequency domain, calculations of dipole moment fluctuations, quantum yields, and radiative and non-radiative transfer constants, were used to characterize a selected analogue from the group of 1,3,4-thiadiazole, namely: 4-[5-(naphthalen-1-ylmethyl)-1,3,4-thiadiazol-2-yl]benzene-1,3-diol (NTBD), intrinsically capable to demonstrate enol → keto excited-states intramolecular proton transfer (ESIPT) effects. The results of spectroscopic analyses conducted in solvent media as well as selected mixtures were complemented by considering biological properties of the derivative in question, particularly in terms of its potential microbiological activity. The compound demonstrated a dual fluorescence effect in non-polar solvents, e.g. chloroform and DMSO/H2O mixtures, while in polar solvents only a single emission maximum was detected. In the studied systems, ESIPT effects were indeed observed, as was the associated phenomenon of dual fluorescence, and, as demonstrated for the DMSO: H2O mixtures, the same could be relatively easily induced by aggregation effects related to aggregation-induced emission (AIE). Subsequently conducted quantum-chemical (TD-)DFT calculations supported further possibility of ESIPT effects. The following article provides a comprehensive description of the spectroscopic and biological properties of the analyzed 1,3,4-thiadiazole derivatives, highlighting its potential applicability as a very good fluorescence probes as well as a compound capable of high microbiological activity.

Classification of Honey Powder Composition by FTIR Spectroscopy Coupled with Chemometric Analysis.

Fourier transform infrared spectroscopy (FTIR) in connection with chemometric analysis were used as a fast and direct approach to classify spray dried honey powder compositions in terms of honey content, the type of diluent (water or skim milk), and carrier (maltodextrin or skim milk powder) used for the preparation of feed solutions before spray drying. Eleven variants of honey powders containing different amounts of honey, the type of carrier, and the diluent were investigated and compared to pure honey and carrier materials. Chemometric discrimination of samples was achieved by principal component analysis (PCA), hierarchical clustering analysis (HCA), linear discriminant analysis (LDA), and partial least squares-discriminant analysis (PLS-DA) modelling procedures performed on the FTIR preprocessed spectral data for the fingerprint region (1800-750 cm-1) and the extended region (3600-750 cm-1). As a result, it was noticed that the type of carrier is a significant factor during the classification of different samples of powdered multifloral honey. PCA divided the samples based on the type of carrier, and additionally among maltodextrin-honey powders it was possible to distinguish the type of diluent. The result obtained by PCA-LDA and PLS-DA scores yielded a clear separation between four classes of samples and showed a very good discrimination between the different honey powder with a 100.0% correct overall classification rate of the samples.

Insight into dual fluorescence effects induced by molecular aggregation occurring in membrane model systems containing 1,3,4-thiadiazole derivatives.

This work reports on biophysical insights into the excited state intramolecular proton transfer (ESIPT) processes taking place in three 1,3,4-thiadiazole derivatives that served as model compounds, on which electronic absorption, fluorescence, Fourier-transform infrared spectroscopy (FTIR), surface plasmon resonance (SPR) and electrochemical impedance spectroscopy (EIS) studies were performed. The fluorescence spectra recorded in various solvents revealed an interesting dual fluorescence effect. In molecules in their monomeric form, the effect is associated with the ESIPT phenomenon, and may be further enhanced by aggregation-related effects, such as aggregation-induced emissions. Other spectroscopic studies on the selected molecules in a liposomal medium as a model revealed that, in a biomimetic environment, they can exist in both monomeric and aggregated forms. In both cases, however, the effects observed are closely related to the lipid's main phase transition temperature and the structure of the molecule. Introduction of specific substituents to the phenyl moiety either allows or prevents proton transfer from occurring in the excited state. The hydrophobicity changes in a lipid environment may result in an emergence of specific molecular forms and therefore either facilitate or hinder ESIPT processes. SPR and EIS confirmed the significant hydrophobicity changes in the model lipid systems, while FTIR measurements revealed a notable influence of 1,3,4-thiadiazoles on the fluidity of liposomal membranes. The results obtained clearly show that the thiadiazole derivatives are very good model molecules for studying hydrophobic-hydrophilic environments, and particularly with polymers or liposomes used as drug delivery systems.

Physical Properties, Spectroscopic, Microscopic, X-ray, and Chemometric Analysis of Starch Films Enriched with Selected Functional Additives.

Biodegradable materials are used in the manufacture of packaging and compostable films and various types of medical products. They have demonstrated a large number of potential practical applications in medicine and particularly in the treatment of various cardiac, vascular, and orthopedic conditions in adults as well in children. In our research, the extrusion-cooking technique was applied to prepare thermoplastic starch (TPS), which was then utilized to obtain environmentally friendly starch-based films. Potato starch was the basic raw material exploited. Polyvinyl alcohol and keratin were used as functional additives in amounts from 0.5 to 3%, while 20% of glycerol was harnessed as a plasticizer. The processing of the thermoplastic starch employed a single screw extruder-cooker with an L/D ratio of 16. The film blowing process was carried out using a film-blowing laboratory line with L/D = 36. FTIR Spectroscopy was applied for the assignment of the prominent functional groups. The results showed that the processing efficiency of thermoplastic starch with functional additives varied depending on the level of polyvinyl alcohol and keratin addition. Moreover, the FTIR data correlated with the changes in the physical properties of the tested films. The analysis of FTIR spectra revealed several changes in the intensity of bands originating from stretching vibrations characteristic of the -OH substituent. The changes observed depended on the presence/lack of the hydrogen bonding occurring upon interactions between the starch molecules and the various additives used. In addition, notable changes were observed in bands assigned to glycoside bonds in the starch.

Isolation of Chitin from Black Soldier Fly (Hermetia illucens) and Its Usage to Metal Sorption.

Chitin has become a desirable raw material used in various areas of life. The black soldier fly (Hermetia illucens) can be a source of this substance. In the literature, there are many methods of obtaining chitin but there is no one universal method of isolating it. In this publication, we present various procedures for the isolation of chitin from H. illucens pupal exuviae. The obtained chitin variants were characterized using different techniques (optical and confocal microscopy, FTIR, XRD, EDX, thermogravimetric analysis). The tested chitin isolated with an efficiency of 5.69-7.95% was the α form with a crystallinity degree of 60% and maximum degradation temperature of 392 °C. Furthermore, we characterized the nickel ion biosorption process on chitin and proposed the mechanism of this process to be ion exchange and complexation. There have been no such studies thus far on the isolation of chitin from H. illucens exuviae or on the biosorption of nickel ions on this type of biosorbent. The conducted research can be used to develop the application of chitin as a metal biosorbent that can be obtained with relatively high efficiency and good sorption properties.

Synthesis and Characterization of a (-)-Epicatechin and Barbituric Acid Cocrystal: Single-Crystal X-ray Diffraction and Vibrational Spectroscopic Studies.

The paper presents the contribution of the cocrystallization method in the physicochemical modification of catechins that exhibit low oral bioavailability. This was done to obtain cocrystals for two naturally occurring polyphenolic diastereoisomers (+)-catechin and (-)-epicatechin with commonly used coformers. Due to distinct crystallization behavior, only the (-)-epicatechin cocrystal with barbituric acid in a 1:1 stoichiometry was obtained. The cocrystal of (-)-epicatechin (EC) with barbituric acid (BTA) was prepared by the slow solvent-evaporation technique. The structure and intermolecular interactions were determined by X-ray crystallographic techniques. The analysis of packing and interactions in the crystal lattice revealed that molecules in the target cocrystal were packed into tapes, formed by the O-H···O type contacts between the (-)-epicatechin and coformer molecules. The EC molecules interact with the carboxyl group in the BTA coformer mainly by -OH groups from the benzene ring A. The cocrystalline phase constituents were also investigated in terms of Hirshfeld surfaces. The application of Raman spectroscopy confirmed the involvement of the C=O group in the formation of hydrogen bonds between the (-)-epicatechin and barbituric acid molecules. Additionally, the solubility studies of pure EC and the EC-BTA cocrystal exhibited minor enhancement of EC solubility in the buffer solution, and pH measurements confirmed a stable level of solubility for EC and its cocrystal.