On the selective formation of cubic tetrastack crystals from tetravalent patchy particles.

Achieving the formation of target open crystalline lattices from colloidal particles is of paramount importance for their potential application in photonics. Examples of such desired structures are the diamond, tetrastack, and pyrochlore lattices. Here, we demonstrate that the self-assembly of tetravalent patchy particles results in the selective formation of cubic tetrastack crystals, both in the bulk and in the systems subjected to external fields exerted by the solid substrate. It is demonstrated that the presence of an external field allows for the formation of well-defined single crystals with a low density of defects. Moreover, depending on the strength of the applied external field, the mechanism of epitaxial growth changes. For weakly attractive external fields, the crystallization occurs in a similar manner as in the bulk, since the fluid does not wet the substrate. Nonetheless, the formed crystal is considerably better ordered than the crystals formed in bulk, since the surface induces the ordering in the first layer. On the other hand, it is demonstrated that the formation of well-ordered cubic tetrastack crystals is considerably enhanced by the increase in external field strength, and the formation of the thick crystalline film occurs via a series of layering transitions.

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.

Design, Spectroscopy, and Assessment of Cholinesterase Inhibition and Antimicrobial Activities of Novel Coumarin-Thiadiazole Hybrids.

A novel series of coumarin-thiadiazole hybrids, derived from substituted coumarin-3-carboxylic acids was isolated and fully characterized with the use of a number of spectroscopic techniques and XRD crystallography. Several of the novel compounds showed intensive fluorescence in the visible region, comparable to that of known coumarin-based fluorescence standards. Moreover, the new compounds were tested as potential antineurodegenerative agents via their ability to act as acetylcholinesterase (AChE) and butyrylcholinesterase (BuChE) inhibitors. Compared to the commercial standards, only a few compounds demonstrated moderate AChE and BuChE activities. Moreover, the novel derivatives were tested for their antimicrobial activity against a panel of pathogenic bacterial and fungal species. Their lack of activity and toxicity across a broad range of biochemical assays, together with the exceptional emission of some hybrid molecules, highlights the possible use of a number of the novel hybrids as potential fluorescence standards or fluorescence imaging agents.

Novel Coumarin-Thiadiazole Hybrids and Their Cu(II) and Zn(II) Complexes as Potential Antimicrobial Agents and Acetylcholinesterase Inhibitors.

A series of coumarin-thiadiazole hybrids and their corresponding Cu(II) and Zn(II) complexes were synthesized and characterized with the use of spectroscopic techniques. The results obtained indicate that all the coumarin-thiadiazole hybrids act as bidentate chelators of Cu(II) and Zn(II) ions. The complexes isolated differ in their ligand:metal ratio depending on the central metal. In most cases, the Zn(II) complexes are characteristic of a 1:1 ligand:metal ratio, while in the Cu(II) complexes the ligand:metal ratio is 2:1. All compounds were tested as potential antibacterial agents against Gram-positive (Staphylococcus aureus, Staphylococcus epidermidis) and Gram-negative (Escherichia coli, Pseudomonas aeruginosa) bacterial strains demonstrating activities notably lower than commercially available antibiotics. The more promising results were obtained from the assessment of antineurodegenerative potency as all compounds showed moderate acetylcholinesterase (AChE) inhibition activity.

Spectroscopic Study of the Molecular Structure of the New Hybrid with a Potential Two-Way Antibacterial Effect.

Bacterial strains become resistant to almost all classes of antibiotics, which makes it necessary to look for new substitutes. The non-absorbable ciprofloxacin-biguanide bismuth complex, used locally, may be a good alternative to a conventional therapy. The purpose of this study was to study the structure of the proposed ciprofloxacin (CIP) -bismuth(III)-chlorhexidine (CHX) composite (CIP-Bi-CHX). The spectroscopic techniques such as UV-VIS (ultraviolet-visible) spectroscopy, FTIR (Fourier-transform infrared) spectroscopy and NMR (Nuclear Magnetic Resonance) spectroscopy were used for structure characterization of the hybrid compound. The performed analysis confirmed the presence of the two active components-CIP and CHX and revealed the possible coordination sites of the ligands with bismuth ion in the metallo-organic structure. Spectroscopic study showed that the complexation between Bi(III) and CIP occurs through the carboxylate and ketone groups of the quinolone ring, while CHX combines with the central ion via the biguanide moieties.

Structural Features of 1,3,4-Thiadiazole-Derived Ligands and Their Zn(II) and Cu(II) Complexes Which Demonstrate Synergistic Antibacterial Effects with Kanamycin.

Classical synthetic protocols were applied for the isolation of three novel 1,3,4-thiadiazole derivatives which were then complexed with the biologically important Cu(II) and Zn(II) ions. All free ligands and their corresponding complexes were characterized using a number of spectroscopic techniques including Ultraviolet-visible (UV-vis), Fluorescence, Infrared (FT-IR), tandem liquid chromatography-mass (LC-MS), X-ray diffraction (XRD), and Nuclear Magnetic Resonance (NMR) spectroscopy (1H, 13C, HSQC, HMBC). The results obtained are consistent with the formation of dihydrate complexes, in which the chelation of the metal ion occurs via one of the thiadiazole nitrogen atoms and the deprotonated hydroxyl group of the neighboring resorcynyl moiety. The Zn(II) complexes utilize a 1:1 ligand-metal ratio, while in the Cu(II) complexes the ligand-metal ratio is 2:1. Although the antibacterial testing identified moderate activity of the compounds against the tested bacterial strains and additionally modest antioxidant activity, a strong synergistic antibacterial effect against Staphylococcus aureus, using concomitant treatment of thiadiazole derivatives with the commercial antibiotic kanamycin, was observed. The most active thiadiazole derivative demonstrated a minimal inhibitory concentration (MIC) of 500 µg/mL while it was 125 µg/mL in the presence of kanamycin. Moreover, in the presence of few thiadiazole derivatives the MIC value of kanamycin decreased from 0.39 µg/mL to 0.5 µg/mL. The antioxidant activity (IC50) of the most active thiadiazole derivative was determined as 0.13 mM which was nearly three-fold lower compared to that of TROLOX (0.5 mM).

Structure and Physical Properties of Cardamonin: A Spectroscopic and Computational Approach.

This is the first study of the crystal structure of cardamonin (CA) confirmed using single-crystal XRD analysis. In the crystal lattice of CA, two symmetry independent molecules are linked by hydrogen bonds within the layers and by the π···π stacking interactions in the columns which lead to the occurrence of two types of conformations among the CA molecules in the crystal structure. To better understand the stability of these arrangements in both crystals and the gaseous phase, seven different CA dimers were theoretically calculated. The molecular structures were optimized using density functional theory (DFT) at the B3LYP/6-311G+(d,p) level and the spectroscopic results were compared. It was found that the calculated configurations of dimer I and III were almost identical to the ones found in the CA crystal lattice. The calculated UV-Vis spectra for the CA monomer and dimer I were perfectly consistent with the experimental spectroscopic data. Furthermore, enhanced emissions induced by aggregated CA molecules were registered in the aqueous solution with the increase of water fractions. The obtained results will help to further understand the relation between a variety of conformations and the biological properties of CA, and the results are also promising in terms of the applicability of CA as a bioimaging probe to monitor biological processes.

Formation of Prenylated Chalcone Xanthohumol Cocrystals: Single Crystal X-Ray Diffraction, Vibrational Spectroscopic Study Coupled with Multivariate Analysis.

Four novel xanthohumol (XN) cocrystals with pharmaceutically acceptable coformers, such as nicotinamide (NIC), glutarimide (GA), acetamide (AC), and caffeine (CF) in the 1:1 stoichiometry were obtained by the slow evaporation solution growth technique. The structure of the cocrystals was determined by single crystal X-ray diffraction. The analysis of packing and interactions in the crystal lattice revealed that molecules in the target cocrystals were packed into almost flat layers, formed by the O-HO, O-HN, and N-HO-type contacts between the xanthohumol and coformer molecules. The results provided details about synthons responsible for crystal net stabilization and all hydrogen bonds observed in the crystal lattice. The main synthon was formed via the hydrogen bond between the hydroxyl group in the B ring of XN and coformers. The three-dimensional crystal lattice was stabilized by the hydrogen XN-XN interactions whereas the π-π stacking interactions played an additional role in layer binding, with the exception of low quality cocrystals formed with caffeine. Application of FTIR and Raman spectroscopy confirmed that the crystalline phase of obtained cocrystals was not a simple combination of individual components and completely different crystal phases resulted from the effect of intermolecular interactions. The multivariate analysis showed the changes in the spectra, and this technique can be applied in a combination with vibrational spectroscopy for fast screening of new crystal phases. Additionally, the solubility studies of pure XN and its cocrystals exhibited a 2.6-fold enhancement in XN solubility in aqueous solution for XN-AC and, to a lesser extent, for other cocrystals.

Controlling the growth of Bi(110) and Bi(111) films on an insulating substrate.

We demonstrate the controlled growth of Bi(110) and Bi(111) films on an α-Al2O3(0001) substrate by surface x-ray diffraction and x-ray reflectivity using synchrotron radiation. At temperatures as low as 40 K, unanticipated pseudo-cubic Bi(110) films are grown with thicknesses ranging from a few to tens of nanometers. The roughness at the film-vacuum as well as the film-substrate interface, can be reduced by mild heating, where a crystallographic orientation transition of Bi(110) towards Bi(111) is observed at 400 K. From 450 K onwards high quality ultrasmooth Bi(111) films form. Growth around the transition temperature results in the growth of competing Bi(110) and Bi(111) domains.

Acid-Base Properties of Xanthohumol: A Computational and Experimental Investigation.

UV-vis spectrophotometry has been applied to determine acid dissociation constants of the prenylated chalcone xanthohumol. The pKa values were compared with those derived from pH-metric titrations. The order of the deprotonation site in the xanthohumol molecule was estimated by quantum mechanical calculations as 2'-OH, 4'-OH, and 4-OH. Furthermore, the electronic and spectroscopic properties of xanthohumol have been investigated on the basis of the time-dependent density functional theory (TDDFT). The TDDFT method, combined with a hybrid exchange-correlation functional using the B3LYP and CAM-B3LYP levels of theory in conjunction with the SMD solvation model, was used to optimize all geometries and predict the excitation energies of the neutral form and ionized species of the chalcone depending on pH value. The computed results were in good agreement with the experimental data. Consideration of the acid-base profile in conjunction with other molecular properties has a great importance and has the potential to be used to further improve the bioavailability of xanthohumol.

Effect of cholesterol and ergosterol on the antibiotic amphotericin B interactions with dipalmitoylphosphatidylcholine monolayers: X-ray reflectivity study.

Amphotericin B is a Streptomyces nodosus metabolite and one of the oldest polyene antibiotics used in the treatment of invasive systemic fungal infections. Despite its over 50-year existence in clinical practice and the recognition of amphotericin B as the gold standard in the treatment of serious systemic mycosis, it still remains one of the most toxic pharmaceuticals. Understanding of the processes at the molecular levels and the interactions between amphotericin B with lipid membranes containing sterols should elucidate the mechanisms of the action and toxicity of this widely used antibiotic. In this work, we use X-ray reflectivity to study the structural changes on a molecular scale after amphotericin B incorporation. These changes are accompanied by an increase in monolayer surface pressure which is more pronounced for ergosterol - rather than cholesterol-rich membranes. The data indicate that this difference is not due to the higher affinity of amphotericin B towards ergosterol-containing membranes but is rather due to a ~3Angstrom corrugation of the monolayer. Furthermore, the total quantity of amphotericin B incorporated into lipid monolayers containing cholesterol and ergosterol is the same.

Influence of Solvent Polarizability on the Keto-Enol Equilibrium in 4-[5-(naphthalen-1-ylmethyl)-1,3,4-thiadiazol-2-yl]benzene-1,3-diol.

This work presents spectroscopic studies of the keto-enol equilibrium induced by solvent polarizability in 4-[5-(naphthalen-1-ylmethyl)-1,3,4-thiadiazol-2-yl]benzene-1,3-diol a strong antiproliferative and anticancer thiadiazol derivative. Electronic absorption, steady state and time resolved fluorescence, and infrared spectroscopies were applied to investigate the keto and enol forms of this compound in a series of polar and non-polar solvents. The enol form dominates in polar solvents while, surprisingly, the keto form dominates in non-polar solvents with high average electric dipole polarizability e.g. n-alkenes. The electronic absorption spectrum of this derivative is more dependent on spatially averaged electric dipole polarizability of the solvent than on Kirkwood's correlation or on Lorenz-Lorenz electric polarizability. By analogy of n-alkanes to the alkyl parts of lipids, one can expect that the transformation of 1,3,4-thiadiazoles to the keto form may be facilitated in the hydrophobic core of the lipid membrane. Such a transition may be of great practical importance for the design of biologically active pharmaceutics, which are able to interact with the hydrophobic regions of cell membranes in a specific manner.

Spectroscopic Studies of Dual Fluorescence in 2-((4-Fluorophenyl)amino)-5-(2,4-dihydroxybenzeno)-1,3,4-thiadiazole.

The paper presents results of fluorescence analysis of ionic and nonionic 2-((4-fluorophenyl)amino)-5-(2,4-dihydroxybenzeno)-1,3,4-thiadiazole (FABT) in monocrystals and solutions. We found a single fluorescence band in the case of FABT crystals grown in methanol and dual fluorescence for FABT crystals grown in an aqueous environment. The effect of dual fluorescence was preserved for FABT dissolved in aqueous solutions with pH ranging from 7.5 to 1. In contrast, FABT dissolved in methanol exhibited a single fluorescence band. The dual fluorescence effect is associated with conformational changes in the FABT molecule, which can be induced by aggregation effects. On the basis of crystallographic data, two types of FABT crystal molecule conformations were distinguished. In methanol, FABT molecules are in conformation "S" (the -OH group from the resorcyl ring oriented toward the sulfur atom from the 1,3,4-thiadiazole ring), which a gives single fluorescence band. In water, FABT in conformation "N" (the -OH group from the resorcyl ring oriented toward the nitrogen atom from the 1,3,4-thiadiazole ring due to 180° rotation) has two fluorescence bands. This significant finding implies the possibility of performing a rapid analysis of conformational changes in FABT molecules using fluorescence spectroscopy both in solutions and in biological samples.

The molecular organization of prenylated flavonoid xanthohumol in DPPC multibilayers: X-ray diffraction and FTIR spectroscopic studies.

Xanthohumol (XN) is the major prenylated flavonoid found in hop resin. It has attracted considerable attention in recent years due to its wide spectrum of biological activities and the beneficial effect on human health. Since lipid membrane is first target for biologically active compounds, we decided to investigate the influence of XN on the dipalmitoylphosphatidylcholine (DPPC) multibilayers. Interactions of XN with DPPC were investigated as a function of temperature and its concentration by using X-ray diffraction and the ATR-FTIR spectroscopy techniques. The aim of understanding the mechanisms of molecular interactions between XN and DPPC was to indicate the localization of the XN with respect to the membrane and the type of interaction with phospholipids. The results revealed that XN changes the physical properties of the DPPC multibilayers in the form of dry film. A new complex formation between XN and DPPC is reported. The detailed analysis of refraction effect indicates the changes in electron density ratio between hydrophobic and hydrophilic zones of lipid at phase transition. This is in compliance with reported changes in FTIR spectra where at pretransition XN moves from interface region between polar heads to the neighborhood of phosphate groups.

Recent progress in the study of the interactions of amphotericin B with cholesterol and ergosterol in lipid environments.

In the past decade substantial progress has been made in understanding the organization and biological activity of amphotericin B (AmB) in the presence of sterols in lipid environments. This review concentrates mainly on interactions of AmB with lipids and sterols, AmB channel formation in membranes, AmB aggregation, AmB modifications important for understanding its biological activity, and AmB models explaining its mechanism of action. Most of the reviewed studies concern monolayers at the water-gas interface, monolayers deposited on a solid substrate by use of the Langmuir-Blodgett technique, micelles, vesicles, and multi-bilayers. Liposomal AmB formulations and drug delivery are intentionally omitted, because several reviews dedicated to this subject are already available.

The Influence of Processing Using Conventional and Hybrid Methods on the Composition, Polysaccharide Profiles and Selected Properties of Wheat Flour Enriched with Baking Enzymes.

In this study, a developed wheat flour blend (F), consisting of a high content of non-starch polysaccharides, was fortified with cellulase (C) and a cellulase-xylanase complex (CX) and then processed via conventional and hybrid treatment methods. Dry heating (T), hydrothermal treatment (H) and extrusion processing (E) were applied without or with enzyme addition as hybrid treatments. Proximate composition and polysaccharide profiles selected techno-functional and structural properties of modified wheat flours, were analyzed. Conventional and hybrid treatments induced changes in polysaccharide fraction compositions (especially the arabinoxylans) and the rheology of modified flour. Dry heating caused an inconsiderable effect on flour composition but reduced its baking value, mainly by reducing the elasticity of the dough and worsening the strain hardening index, from 49.27% (F) to 44.83% (TF) and from 1.66 (F) to 1.48 (TF), respectively. The enzymes added improved the rheological properties and baking strength, enhancing the quality of gluten proteins. Hydrothermal enzyme-assisted treatment increased flour viscosity by 14-26% and improved the dough stability by 12-21%; however, the use of steam negatively affected the protein structure, weakening dough stretchiness and elasticity. Extrusion, especially enzyme-assisted, significantly increased the hydration properties by 55-67% but lowered dough stability, fat content and initial gelatinization temperature due to the changes in the starch, mostly induced by the hybrid enzymatic-extrusion treatment. The structure of extruded flours was different from that obtained for other treatments where the peak intensity at 20° was the highest, suggesting the presence of amorphous phases of amylose and lipids. The results can be helpful in the selection of processing conditions so as to obtain flour products with specific techno-functional properties.

Effect of 2-(4-fluorophenylamino)-5-(2,4-dihydroxyphenyl)-1,3,4-thiadiazole on the molecular organisation and structural properties of the DPPC lipid multibilayers.

Interactions and complex formation between lipids and biologically active compounds are crucial for better understanding of molecular mechanisms occurring in living cells. In this paper a molecular organisation and complex formation of 2-(4-fluorophenylamino)-5-(2,4-dihydroxybenzeno)-1,3,4-thiadiazole (FABT) in DPPC multibilayers are reported. The simplified pseudo binary phase diagram of this system was created based on the X-ray diffraction study and fourier transform infrared spectroscopic data. The detailed analysis of the refraction effect indicates a much higher concentration of FABT in the polar zones during phase transition. Both the lipid and the complex ripple after cooling. It was found that FABT occupied not only the hydrophilic zones of the lipid membranes but also partly occupied the central part of the non polar zone. The infrared spectroscopy study reveals that FABT strongly interact with hydrophilic (especially PO(2)(-)) and hydrophobic (especially "kink" vibrations of CH(2) group). The interactions of FABT molecules with these groups are responsible for changes of lipid multibilayers observed in X-ray diffraction study.

Pursuing colloidal diamonds.

The endeavor to selectively fabricate a cubic diamond is challenging due to the formation of competing phases such as its hexagonal polymorph or others possessing similar free energy. The necessity to achieve this is of paramount importance since the cubic diamond is the only polymorph exhibiting a complete photonic bandgap, making it a promising candidate in view of photonic applications. Herein, we demonstrate that due to the presence of an external field and delicate manipulation of its strength we can attain selectivity in the formation of a cubic diamond in a one-component system comprised of designer tetrahedral patchy particles. The driving force of such a phenomenon is the structure of the first adlayer which is commensurate with the (110) face of the cubic diamond. Moreover, after a successful nucleation event, once the external field is turned off, the structure remains stable, paving an avenue for further post-synthetic treatment.

The Optical and Spectroscopic Properties of Fuchsite, Spodumene, and Lepidolite from Northern Scandinavia (Kautokeino, Kaustinen, Kolmozero).

Li-Ce-Ta (LCT) pegmatites containing lithium mineralization in the form of spodumene and lepidolite, as well as fuchsite, from the regions of northern Scandinavia (N Norway, N Finland, N Russia) were studied. Detailed analyses of the chemical compositions of these minerals were carried out, involving scanning electron microscopy (SEM) with energy-dispersive spectroscopy (EDS), Fourier transform infrared (FTIR) spectroscopy with attenuated total reflectance (ATR), and X-ray photoelectron spectroscopy (XPS) studies. Their crystal structures were confirmed with the X-ray diffraction technique. Studies involving microscopy were also carried out, indicating the optical features of these minerals. Based on the analyses carried out in the studied rocks, the characteristics of these minerals were determined, as well as the crystallization conditions. This research indicates that the N Scandinavian area is prospective and may lead to further discoveries of this type of pegmatite in the studied region.

Correction: Pursuing colloidal diamonds.

Correction for 'Pursuing colloidal diamonds' by Lukasz Baran et al., Nanoscale, 2023, 15, 10623-10633, https://doi.org/10.1039/D3NR01771K.