Bioactive and biodegradable cotton fabrics produced via synergic effect of plant extracts and essential oils in chitosan coating system.

Functional antibacterial textile materials are in great demand in the medical sector. In this paper, we propose a facile, eco-friendly approach to the design of antibacterial biodegradable cotton fabrics. Cotton fiber fabrics were enhanced with a chitosan coating loaded with plant extracts and essential oils. We employed Fourier-transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS), UV-Vis spectrophotometry, optical microscopy, scanning electron microscopy (SEM), and thermogravimetric analysis (TGA) to characterize the color, structure, and thermal properties of the modified fabrics. The fabrics were found to effectively induce growth inhibition of Gram-positive and Gram-negative bacteria, especially when a synergic system of aloe vera extract and cinnamon essential oil was applied in the coating formulation. Additionally, we observed significant color and weight changes after 5, 10, and 20 days in soil biodegradability tests. Given the straightforward modification process and the use of non-toxic natural materials, these innovative bio-based and biodegradable cotton fabrics show great promise as protective antimicrobial textiles for healthcare applications.

Multi-Analytical Techniques for the Study of Burial Clothes of Polish King Sigismund III Vasa (1566-1633) and His Wife Constance Habsburg (1588-1631).

The subjects of this research are the burial clothes of Polish King Sigismund III Vasa and his wife Constance, which were woven and embroidered with silk and metal threads. Fragments of the textiles underwent spectroscopic, spectrometric, and thermogravimetric analyses. The hydrofluoric acid extraction method was improved to isolate various classes of dyes from the textile samples that had direct contact with human remains. High-performance liquid chromatography, coupled with diode array and tandem mass spectrometry detectors with electrospray ionization (HPLC-DAD-ESI-MS/MS) facilitated the detection and identification of colorants present in the textiles. Cochineal, indigo-, madder-, orchil-, and tannin-producing plants were identified as the sources of dyes used. Scanning electron microscopy with an energy-dispersive X-ray detector (SEM-EDS) was employed to identify and characterize the silk fibers and mordants and the metal threads. The presence of iron, aluminum, sodium, and calcium in the silk threads suggests their potential use as mordants. The analysis of the metal threads revealed that most of them were made from flattened gilded silver wire, with only a few being cut from a sheet of metal. Typical degradation mechanisms of metal threads were shown, resulting from both burial environment and earlier manufacturing process, and the use of the textiles in clothing, i.e., a significant loss of the gold layer was observed in most of silver gilt threads, caused by abrasion and delamination. The results of the thermal analysis confirmed the presence of silk and silver threads in the examined textiles.

Novel amides of mycophenolic acid and some heterocyclic derivatives as immunosuppressive agents.

The group of 18 new amide derivatives of mycophenolic acid (MPA) and selected heterocyclic amines was synthesised as potential immunosuppressive agents functioning as inosine-5'-monophosphate dehydrogenase (IMPDH) uncompetitive inhibitors. The synthesis of 14 of them employed uronium-type activating system (TBTU/HOBt/DIPEA) while 4 of them concerned phosphonic acid anhydride method (T3P/Py) facilitating amides to be obtained in moderate to excellent yields without the need of phenolic group protection. Most of optimised protocols did not require complicated reaction work-ups, including chromatographic, solvent-consuming methods. The biological activity assay was performed on the T-Jurkat cell line and peripheral mononuclear blood cells (PBMCs) which are both dedicated for antiproliferative activity determination. Each of designed derivatives was characterised by reduced cytotoxicity and benzoxazole analogue (A2) revealed the most promising activity. Subsequently, an observed structure-activity relationship was discussed.

Structure and Stability Characterization of Natural Lake Pigments Made from Plant Extracts and Their Potential Application in Polymer Composites for Packaging Materials.

Natural dyes were extracted from various plant sources and converted into lake pigments based on aluminum and tin. Three different plants (weld, Persian berries, and Brazilwood) were chosen as representative sources of natural dyes. High-performance liquid chromatography (HPLC) and triple-quadrupole mass spectrometry (QqQ MS) were used to identify dyestuffs in the raw extracts. The natural dyes and lake pigments were further characterized by optical and scanning electron microscopy (SEM), UV-Vis spectrophotometry, and thermogravimetric analysis (TGA). The stabilization of the studied plant extracts onto aluminum and tin salts led to the formation of natural lake pigments characterized by different color shades. The natural lake pigments showed improved thermal and chemical stability, which was confirmed by their higher degradation temperatures and lower solubility in chemical agents compared to natural dyes extracted from plants. This improvement can be attributed to electrostatic attraction due to the process of chelation. Ethylene-norbornene (EN) composites colored with the lake pigments exhibited uniform color and improved resistance to long-term UV exposure aging. After 300 h of UV exposure, the aging factor of the neat EN copolymer reduced to 0.3, indicating an advanced aging process of polymer compared to colored samples. Prolonged UV exposure deteriorated the mechanical properties of EN by approximately 57%, compared to about 43% with the application of BW/Al lake pigment. Natural lake pigments could be used as effective substitutes for commercial colorants in plastics for packaging applications.

Development of Sulfamoylated 4-(1-Phenyl-1H-1,2,3-triazol-4-yl)phenol Derivatives as Potent Steroid Sulfatase Inhibitors for Efficient Treatment of Breast Cancer.

We present here the advances achieved in the development of new sulfamoylated 4-(1-phenyl-1H-1,2,3-triazol-4-yl)phenol derivatives as potent steroid sulfatase (STS) inhibitors for the treatment of breast cancer. Prompted by promising biological results and in silico analysis, the initial series of similar compounds were extended, appending a variety of m-substituents at the outer phenyl ring. The inhibition profiles of the newly synthesized compounds were evaluated using a radioisotope enzymatic assay and, together with the preceding reported derivatives, using a radioisotope assay in MCF-7 cells. The most active compound, 5l, demonstrated an extraordinary STS inhibitory potency in MCF-7 cells with an IC50 value improved 5-fold compared to that of the reference Irosustat (0.21 vs 1.06 nM). The five most potent compounds were assessed in vivo in a 67NR mouse mammary gland cancer model, with 4b measured to induce up to 51% tumor growth inhibition at 50 mg/kg with no evidence of side effects and toxicity.

The Mechanism of a Retro-Diels-Alder Fragmentation of Luteolin: Theoretical Studies Supported by Electrospray Ionization Tandem Mass Spectrometry Results.

The mechanisms of retro-Diels-Alder fragmentation of luteolin are studied theoretically using the Density Functional Theory method (B3LYP hybrid functional) together with the 6-311++G(d,p) basis set and supported by electrospray ionization tandem mass spectrometry (ESI-MS) results. The reaction paths leading to the formation of 1,3A- and 1,3B- fragment ions observed as the main spectral features in the ESI-MS spectrum are described and discussed, including the structures of the transition states and intermediate products. The heights of the activation energy barriers which have to be overcome along the reaction paths corresponding to 1,3-retrocyclization cleavage of the ionized luteolin are predicted to span the 69-94 kcal/mol range (depending on the initial isomeric structure) for the concerted retrocyclization mechanism and the 60-89 kcal/mol (first barrier) and 24-52 kcal/mol (second barrier) barriers for the stepwise mechanism (also depending on the initial isomeric structure). It is also demonstrated that the final fragmentation products (1,3A- and 1,3B-) are in fact represented by various isomeric systems which are not experimentally distinguishable. In addition, the absence of the spectral feature corresponding to the [M-B]- fragment ion formed by the rupture of the C-C bond connecting luteolin's B and C rings (which does not occur during the ESI-MS experiment) is explained by much larger energy barriers predicted for such a process.

Effects of Basalt and Carbon Fillers on Fire Hazard, Thermal, and Mechanical Properties of EPDM Rubber Composites.

Due to growing restrictions on the use of halogenated flame retardant compounds, there is great research interest in the development of fillers that do not emit toxic compounds during thermal decomposition. Polymeric composite materials with reduced flammability are increasingly in demand. Here, we demonstrate that unmodified graphene and carbon nanotubes as well as basalt fibers or flakes can act as effective flame retardants in polymer composites. We also investigate the effects of mixtures of these carbon and mineral fillers on the thermal, mechanical, and rheological properties of EPDM rubber composites. The thermal properties of the EPDM vulcanizates were analyzed using the thermogravimetric method. Flammability was determined by pyrolysis combustion flow calorimetry (PCFC) and cone calorimetry.

Investigation into the Effect of Spinel Pigments on the Photostability and Combustion Properties of Ethylene-Norbornene Copolymer.

Multicolor ethylene-norbornene (EN) composites filled with three different spinel pigments (Cobalt Green-PG50, Zinc Iron Yellow-PY 119, Praseodym Yellow-PY159) were prepared by melt mixing and characterized in terms of their stability under destructive environmental conditions. The EN films were subjected to accelerated aging by ultraviolet (UV) photooxidation for 300 h, 600 h, or 900 h. The mechanical performance of the EN composites was investigated in static and dynamic mechanical tests. The morphologies of the EN samples and their color changes during the aging process were evaluated by scanning electron microscopy (SEM) and spectrophotometric measurements. Fourier transform infrared (FTIR) spectroscopy was applied to determine the amount of carbonyl groups resulting from surface oxidation at different aging times. The effects of the spinel pigments on the thermal stability and combustion properties of the multicolor polymer composites were also assessed, and compared with a sample containing the organic Pigment Yellow 139 (PY139). The results show that the color changes (ΔE) in the spinel pigments were minor in comparison to those in the organic pigment (PY139) and the reference film. The Zinc Yellow (PY119) pigment was the most effective stabilizer of EN copolymer. Moreover, the spinel pigments had a positive effect on the flame retardancy of the EN composites. Microcombustion tests (MCC) showed that the incorporation of both the spinels and the organic pigment PY139 into the EN matrix reduced the heat release rate (HRR) and total heat release (THR) parameters.

Multi-Technique Investigation of Grave Robes from 17th and 18th Century Crypts Using Combined Spectroscopic, Spectrometric Techniques, and New-Generation Sequencing.

The textile fragments of the funeral clothes found in the 17th and 18th century crypts were subjected to spectroscopic, spectrometric, and microbial investigation. The next-generation sequencing enabled DNA identification of microorganisms at the genus and in five cases to the species level. The soft hydrofluoric acid extraction method was optimized to isolate different classes of dyes from samples that had direct contact with human remains. High-performance liquid chromatography coupled with diode matrix and tandem mass spectrometry detectors with electrospray ionization (HPLC-DAD-ESI-MS/MS) enabled the detection and identification of 34 colourants that are present in historical textiles. Some of them are thus far unknown and uncommon dyes. Indigo, madder, cochineal, turmeric, tannin-producing plant, and young fustic were identified as sources of dyes in textiles. Scanning electron microscopy with energy-dispersive X-ray detector (SEM-EDS) and Fourier transform infrared spectroscopy (FT-IR) were used to identify and characterize fibres and mordants in funeral gowns. Of the 23 textile samples tested, 19 were silk while the remaining four were recognized as wool. The presence of iron, aluminium, sodium, and calcium suggests that they were used as mordants. Traces of copper, silica, and magnesium might originate from the contaminants. The large amount of silver indicated the presence of metal wire in one of the dyed silk textiles. SEM images showed that textile fibres were highly degraded.

The Effect of Posaconazole, Itraconazole and Voriconazole in the Culture Medium on Aspergillus fumigatus Triazole Resistance.

Triazoles are the only compounds used as antibiotics in both medicine and agriculture. The presence of triazoles in the environment can contribute to the acquisition of azole resistance among isolates of Aspergillus fumigatus. The objective of this study was to investigate the effect of A. fumigatus exposure to triazoles on susceptibility to these compounds. Seventeen triazole-resistant and 21 triazole-sensitive A. fumigatus isolates were examined. The isolates were transferred 20 times on the Sabouraud medium supplemented with posaconazole, itraconazole or voriconazole, followed by five times on the medium not supplemented. The minimum inhibitory concentrations of antimycotics were examined according to the EUCAST broth microdilution method after the 20th transfer and also the 25th transfer. In addition, the expression levels of genes mdr1, mdr2, mdr3, atrF, cyp51A and cyp51B were determined. Cultivation of A. fumigatus on media supplemented with posaconazole, itraconazole and voriconazole resulted in the acquisition of resistance to the tested triazoles of all examined isolates. After recultivation on Sabouraud without azoles, most of the isolates lost their acquired resistance. The long-term use of triazole compounds in agriculture may result in the occurrence of triazole resistant A. fumigatus isolates in the environment, not only by induction or selection of mutations in the cyp51A gene, but also by contribution to changes in the gene expression.

Chromatographic and Spectroscopic Identification and Recognition of Natural Dyes, Uncommon Dyestuff Components, and Mordants: Case Study of a 16th Century Carpet with Chintamani Motifs.

A multi-tool analytical practice was used for the characterisation of a 16th century carpet manufactured in Cairo. A mild extraction method with hydrofluoric acid has been evaluated in order to isolate intact flavonoids and their glycosides, anthraquinones, tannins, and indigoids from fibre samples. High-performance liquid chromatography coupled to spectroscopic and mass spectrometric detectors was used for the identification of possible marker compounds with special attention paid to natural dyes present in the historical samples. Weld, young fustic, and soluble redwood dye were identified as the dye sources in yellow thread samples. Based on the developed method, it was possible to establish that red fibres were coloured with lac dye, whereas green fibre shades were obtained with indigo and weld. Tannin-containing plant material in combination with indigo and weld were used to obtain the brown hue of the thread. Hyphenation of high-performance liquid chromatography (HPLC) with quadrupole time-of-flight mass spectrometry (QTOF MS) and triple-quadrupole mass spectrometry (QqQ MS) enabled us to recognise four uncommon and thus-far unknown dye components that were also found in the historical samples. These compounds probably represent a unique fingerprint of dyed threads manufactured in a Turkish workshop. Scanning electron microscopy with energy-dispersive X-ray detector (SEM-EDS) and Fourier transform infrared spectroscopy (FT-IR) were used for the identification and characterisation of substrates and mordants present in the historical carpet. Carbon and oxygen were detected in large quantities as a part of the wool protein. The presence of aluminium, iron, and calcium indicated their usage as mordants. Trace amounts of copper, silica, and magnesium might originate from the contaminants. FT-IR analysis showed bands characteristic for woollen fibres and SEM micrographs defined the structure of the wool.

Phototransformation of amlodipine: degradation kinetics and identification of its photoproducts.

Nowadays, monitoring focuses on the primary compounds and does not include degradation products formed during various biological and chemical processes. Transformation products may have the same effects to human health and the environment or sometimes they can be more toxic than the parent compound. Unfortunately, knowledge about the formation of degradation products is still limited, however, can be very important for the environmental risk assessment. Firstly, the photodegradation kinetic of amlodipine was investigated in two experimental conditions: during the exposure to solar radiation and during the exposure to the light emitted by the xenon lamp. In all cases degradation of amlodipine followed a pseudo-first-order kinetics. In the next step, identification of transformation products of amlodipine formed during the exposure to xenon lamp irradiation was performed using ultra high performance liquid chromatography quadrupole time-of-flight mass spectrometry (UHPLC-QTOF-MS). As a result sixteen photoproducts were identified, their structures were elucidated and ultimately the transformation pathway was proposed. Fifteen compounds (out of 16 photoproducts) were newly identified and reported here for the first time; some of those compounds were formed from the first photoproduct, amlodipine pyridine derivative. Several analytes were formed only in acidic or basic conditions. Furthermore, the occurrence of amlodipine and its identified degradation products was investigated in environmental waters. Only one out of 16 compounds was found in wastewater effluent. The possibility of the sorption of examined analytes to sewage sludge particles was discussed based on QSAR.

Polycyclic aromatic hydrocarbons as test probes to investigate the retention behavior of 1,3-alternate calix[4]arene silica-bonded stationary phases.

A series of polycyclic aromatic hydrocarbons (PAHs) of different size and shape has been used to characterize the chromatographic behavior of five calix[4]arene stationary phases in 1,3-alternate conformation synthesized in our laboratory. The selection of linear, four-ring nonlinear, and five-ring PAHs gave data on selectivity changes across range of the calix[4]arene columns. Retention of the 12 aromatic solutes has been evaluated at various methanol contents in the mobile phase (70-100% v/v) and column temperatures (20-45°C). The thermodynamic parameters underlying the retention mechanisms revealed that each of the five calix[4]arene columns exhibited variation in selectivity and retention of PAHs caused by enthalpy and entropy effects. The calixarene stationary phases substituted with electron-withdrawing groups exhibit enhanced selectivity toward PAHs in comparison to the rest of the investigated columns. The observed divergences are due to differences in solute-stationary phase interactions and originate in π-π and π-electron transfer specific to the analytes and the type of calix[4]arene functionalization at the upper rim, as well as steric and sorption phenomena.

Determination of PAHs, PCBs, minerals, trace elements, and fatty acids in Rapana thomasiana as an indication of pollution.

The aim of this investigation was to introduce several analytical methods for determination of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), minerals, trace elements, and fatty acids in Rapana thomasiana as a marine pollution indicator organism. The chemical differences of the gastropod Ra. thomasiana from polluted and nonpolluted sites of the Black Sea on the Bulgarian coast were investigated. Chromatography and high-resolution inductively coupled plasma/MS analyses were used for evaluation of PAHs, PCBs, fatty acids, minerals, and trace elements. These methods can be applied to other marine products.

Chromatographic behavior of a new hybrid type RP material containing silica bonded 1,3-alternate 25,27-bis-[cyanopropyloxy]-26,28-bis-[3-propyloxy]-calix[4]arene.

A novel 1,3-alternate 25,27-bis-[cyanopropyloxy]-26,28-bis-[3-propyloxy]-calix[4]arene-bonded silica gel stationary phase (CalixPrCN) was prepared and its structure was confirmed by ATR-FTIR spectroscopy and elemental analysis. The CalixPrCN phase was characterized in terms of its surface coverage, hydrophobic selectivity, aromatic selectivity, shape selectivity, hydrogen bonding capacity, residue metal content, and silanol activity based on Tanaka, Lindner, and SMR 870 test protocols. The effect of the acetonitrile content on the retention and selectivity of the selected neutral, basic, and acidic solutes was studied. The neutral and acidic analytes exhibited classical RP behavior, in which retention time decreases with increasing acetonitrile content. In contrast, basic analytes showed an increase in retention at low and high percentages of acetonitrile, forming "U-shaped" retention profiles. The new calixarene phase was compared with previously reported 1,3-alternate 25,27-bis-[propyloxy]-26,28-bis-[3-propyloxy]-calix[4]arene stationary phase and commercial cyanopropyl column. The results indicate that the CalixPrCN stationary phase behaves like RP packing; however, inclusion complex formation, dipole-dipole, and π-π interactions seem to be involved in the separation process. The selectivity of this phase was demonstrated in separation of polynuclear aromatic hydrocarbons, non-steroidal anti-inflammatory drugs, and sulfonamides as analytes.

Characterization of 1,3-alternate calix[4]arene-silica bonded stationary phases and their comparison to selected commercial columns by using principal component analysis.

Twelve calix[4]arene stationary phases in 1,3-alternate conformation, synthesized in the authors' laboratory, were characterized in terms of their surface coverage, hydrophobic selectivity, aromatic selectivity, shape selectivity, hydrogen bonding capacity and ion-exchange capacity. The set of tests commonly used for evaluation of commercially available stationary phases was applied to assess fundamental chromatographic properties of the calixarene phases. The new calixarene phases were compared to each other, to Caltrex and LiChrosorb C-18 columns. Principal component analysis has been used to provide comparison between 1,3-alternate calix[4]arene phases and commercially available phenyl, fluorophenyl and fluoroalkyl columns.

1,3-Alternate calix[4]arene-bonded silica stationary phases. Effect of calixarene skeleton substituents on the retention mechanism and column selectivity.

Four novel 1,3-alternate calix[4]arene-bonded silica gel stationary phases possessing different aromatic and aliphatic substituents at the upper rim (CalixNph, CalixBph, CalixHex, and CalixDdc) were prepared and structurally characterized. The comparison and selectivity of these phases were done by using alkylbenzenes, fatty acid p-bromophenacyl esters, aromatic positional isomers, and polynuclear aromatic hydrocarbons as analytes. Quantum chemistry calculations have also been performed (using an ab initio method) to support the experimental findings. The effect of the type and content of organic modifier on the retention and selectivity of the alkylbenzenes was studied. The retention mechanism is also discussed. The results indicate that the stationary phases behave like RP packings. However, inclusion complex formation and hydrophobic and pi-pi interactions seem to be involved in the separation process.

Partial characterization of three Korean white lotus cultivars.

The nutritional and bioactive values of Korean white lotus cultivars (Muan, Chungyang, and Garam) extracted with methanol, water, and acetone solvents were evaluated by the contents of their bioactive compounds and antioxidant activity determined by ABTS, CUPRAC, FRAP, DPPH, and ß-carotene-linoleic acid assays. HPLC, fluorometry, and FTIR spectroscopy were employed for evaluation of polyphenols and fatty acids. All lotus cultivar extracts possessed high amounts of total phenolics, ascorbic acid, proteins, and fatty acids and exhibited high levels of antioxidant activity, which were higher in water than in organic solvents. The significant highest content of the above-mentioned indices and biological activity were recorded in the Chungyang cultivar. Therefore, all studied Korean white lotus cultivars and in particular Chungyang could be recommended as effective nutritional and bioactive products, however, after investigation on humans.

Preparation and evaluation of 1,3-alternate 25,27-bis-(pentafluorobenzyloxy)-26,28-bis-(3-propyloxy)-calix[4]arene-bonded silica gel high performance liquid chromatography stationary phase.

A 1,3-alternate 25,27-bis-(pentafluorobenzyloxy)-26,28-bis-(3-propyloxy)-calix[4]arene-bonded silica gel stationary phase (CalixBzF(10)) was synthesized, structurally characterized, and used as a selector in liquid chromatography. The selectivity study of this phase was done by using fluorine-containing compounds (fluorobenzenes, fluoro-pyrimidine bases), as well as non-fluorinated analytes (non-steroidal anti-inflammatory drugs, sulfonamides, xanthines and polynuclear aromatic hydrocarbons). The effects of organic modifiers on the retention of various compounds possessing basic, acidic and neutral characteristics were studied. It was shown that only basic analytes exhibit a "U-shaped" retention profile and that retention depends on the mobile phase pH. Selectivity comparisons of the novel phase vs. the 1,3-alternate 25,27-bis-(benzyloxy)-26,28-bis-(3-propyloxy)-calix[4]arene phase (CalixBz) were performed. The retention mechanism is also discussed. The results indicate that the fluorinated calixarene stationary phase behaves like reversed-phase packing material; however, fluorine-fluorine interactions seem to be involved in the separation process of fluorine-containing analytes.

Preparation and HPLC evaluation of a new 1,3-alternate 25,27-bis-[p-chlorobenzyloxy]-26,28-bis-[3-propyloxy]-calix[4]arene silica bonded stationary phase.

The 1,3-alternate 25,27-bis-[p-chlorobenzyloxy]-26,28-bis-[3-propyloxy]-calix[4]arene-bonded silica gel stationary phase was synthesized, structurally characterized, and used as a selector in high performance liquid chromatography. Selectivity studies on that phase used aromatic positional isomers, alkylbenzenes, polynuclear aromatic hydrocarbons, sulfonamides, and non-steroidal anti-inflammatory drugs as analytes. The effects of organic modifier content and pH of the mobile phase on retention and selectivity of selected aromatic positional isomers were studied. Selectivity comparisons of the novel phase vs. 1,3-alternate 25,27-di-[benzyloxy]-26,28-bis-[3-propyloxy]-calix[4]arene phase and commercially available RP-Phenyl phases were performed. The retention mechanism was also discussed. The results indicated that the calixarene stationary phase behaves like a reversed-phase packing; however, other retention mechanisms seem to be involved in the separation process.