The Influence of Two‐Dimensional Organization on Peptide Conformation

Molecular crowding plays a significant role in regulating molecular conformation in cellular environments. It is also likely to be important wherever high molecular densities are required, for example in surface‐phase studies, in which molecular densities generally far exceed those observed in solution. Using on‐surface circular dichroism (CD) spectroscopy, we have investigated the structure of a synthetic peptide assembled into a highly packed monolayer. The immobilized peptide undergoes a structural transition between α‐helical and random coil conformation upon changes in pH and ionic concentration, but critically the threshold for conformational change is altered dramatically by molecular crowding within the peptide monolayer. This study highlights the often overlooked role molecular crowding plays in regulating molecular structure and function in surface‐phase studies of biological molecules.     

Isotope effects on miscibility of 1-butyl-3-methylimidazolium tetrafluoroborate with butanols

The liquid-liquid miscibility temperatures as a function of composition and deuterium substitution have been experimentally determined for the binary mixtures of 1-butyl-3-methylimidazolium tetrafluroborate with 1-butanol, isobutyl alcohol, 2-butanol, and tert-butyl alcohol and their deuterated forms (OH/OD substitution). All systems exhibit upper critical solution temperatures (UCSTs) with a visible effect of branching in alcohols. Deuteration of alcohols in the hydroxyl group results in a decrease of the UCST of the given system and the largest shift is observed for tert-butyl alcohol. These solvent isotope effects nicely correlate with the polarity expressed by dielectric constants or E(T)(30) parameters of alcohols. The effect of the isotope substitution on the miscibility of ILs with butanols can be rationalized by using the statistical-mechanical theory of the isotope effects coupled with a phenomenological g(E) model. Following this procedure one finds that the isotope shift of UCST is associated mainly with the zero-point energy contribution.     

Rosa platyacantha Schrenk from Kazakhstan—Natural Source of Bioactive Compounds with Cosmetic Significance

Plants belonging to the Rosa genus are known for their high content of bioactive molecules and broad spectrum of healing and cosmetic activities. Rosa platyacantha Schrenk is a wild-type species abundant in the mountainous regions of Kazakhstan. The phytochemical composition as well as the bioactivity of R. platyacantha extracts have not been fully investigated to date. In this study, various parts of R. platyacantha plant, collected in Almaty region, Kazakhstan, were used to prepare five hydroalcoholic extracts (R1–R5). The extracts were compared for the content of phytochemicals and selected biological activities, which are important for the potential cosmetic application of R. platyacantha. Extract R3, prepared from flower buds, showed the most significant antioxidant and tyrosinase inhibitory potential, decreasing the monophenolase and diphenolase activities of tyrosinase. Extract R3 showed also collagenase inhibitory activity and cytotoxicity against human melanoma cells A375, being less cytotoxic for noncancerous skin keratinocytes HaCaT. Analysis of fractions E and F, obtained from R3 extracts, revealed that quercetin, kaempferol, rutin, and their derivatives are more likely responsible for the tyrosinase inhibitory properties of R. platyacantha extracts.     

Application of DLLME to Isolation and Concentration of Non-Steroidal Anti-Inflammatory Drugs in Environmental Water Samples

Dispersive liquid–liquid microextraction (DLLME) coupled with liquid chromatography-tandem mass spectrometry detection was applied for determination of selected anti-inflammatory pharmaceuticals: ibuprofen, ketoprofen, naproxen and diclofenac. Development of DLLME procedure included optimisation of several important parameters such as kind and volume of extracting and dispersive solvents as well as sample pH. Under optimised conditions a two-step extraction with sonication was used. Chloroform was applied as the extracting and acetone as dispersing solvent. Calibration curves ranges were 1–500 μg L^?1 for naproxen and ibuprofen and 0.25–500 μg L^?1 for ketoprofen and diclofenac with correlation coefficients at least 0.997. Limits of quantitation were from 0.5 to 10 ng L^?1. The developed analytical method was employed for determination of ibubrofen, ketoprofen, naproxen and diclofenac in river and tap water samples. The results showed that DLLME is a simple, rapid and sensitive analytical technique for the pre-concentration of trace amounts of pharmaceuticals in environmental water samples.     

The Synthesis and Antibacterial Activity of Novel 4‐Pyrrolidin‐3‐cyanopyridine Derivatives

2‐Bromo‐4‐(pyrrolidin‐1‐yl)pyridine‐3‐carbonitrile obtained from 2‐(1,3‐bis(pyrrolidin‐1‐yl)allylidene)malononitrile has been used as a substrate for the synthesis of new cyanopyridine derivatives: 2‐methoxy, 2‐phenoxy, 2‐aminoethylthio, and 2‐thioxo. 4‐(Pyrrolidin‐1‐yl)‐2‐thioxo‐1,2‐dihydropyridine‐3‐carbonitrile 7 in reaction with suitable alkyl and aminoalkyl halides gave respective sulfides. All synthesized compounds were evaluated for their antimicrobial activity against 26 aerobic and anaerobic bacteria. Determined minimal inhibitory concentration values ranged from 6.2 to 100 µg/mL. Derivatives 1 , 3 , 4 , 6 , and 12 were the most active compounds.     

Transparent titanium dioxide/block copolymer modified epoxy-based systems in the long scale microphase separation threshold

Microphase separated epoxy-based materials modified with an amphiphilic poly(styrene-block-ethylene oxide) diblock copolymer (PS-b-PEO) with low amount of PEO-block as well as ternary systems modified with this block copolymer and containing via sol–gel in situ synthesized TiO₂ nanoparticles were prepared and characterized. The obtained results indicate that block copolymer had enough amount of PEO-block in order to achieve microphase separated materials for a high range of PS-b-PEO contents, morphologies changing from spherical micelles to long wormlike micelles passing through vesicles upon increasing copolymer amounts. In the case of 20 wt.% inorganic/organic epoxy-based materials, addition of synthesized TiO₂ nanoparticles into PS-b-PEO-(DGEBA/MCDEA) system led to location of the nanoparticles in PEO-block/epoxy-rich confined between two microphase separated PS-block-rich phases. Designed highly transparent multiphase inorganic/organic epoxy-based materials possess interesting specific properties such as high UV shielding efficiency and high water repellence.     

Preliminary Microbiological Tests of S-Carvone and Geraniol and Selected Derivatives of These Compounds That May Be Formed in the Processes of Isomerization and Oxidation

This work presents a literature review on the biological activity of S-carvone, geraniol and derivatives of these compounds, which are formed in the process of isomerization (during the process of geraniol isomerization, oxidation products of this compound are also obtained). Moreover, this work presents preliminary microbiological tests of creams with the addition of these biologically active compounds: S-carvone, geraniol, carvacrol (an S-carvone isomerization product), nerol (a geraniol isomerization product), linalool (a geraniol isomerization product) and citral (a geraniol oxidation product). Because the post-reaction mixture obtained after the S-carvone isomerization has a relatively simple composition, it was also added to creams and tested without isolating pure compounds. This may be a cheaper alternative to creams prepared with the addition of pure compounds. The mixture obtained after the geraniol isomerization process has a very complex composition; therefore, only compounds with the lowest molecular weight and are easily commercially available were selected for studies. The content of the tested compounds in the creams ranged from 0.5 to 3 wet%. The following microorganisms were selected for microbiological tests: the Gram-negative bacterium Escherichia coli K12, the Gram-positive bacterium Staphylococcus epidermidis, and the fungi Candida albicans, Trichophyton rubrum, Aspergillus niger, and Penicillium chrysogenum. A content of 3% carvacrol, nerol, geraniol and citral inhibited the growth of E. coli, and attenuated the growth of C. albicans and T. rubrum. On the other hand, 3% carvacrol and citral only poorly attenuated the growth of the mould fungi P. chrysogenum and A. niger.     

Altering Oxygen Binding by Redox-Inactive Metal Substitution to Control Catalytic Activity: Oxygen Reduction on Manganese Oxide Nanoparticles as a Model System**

Establishing generic catalyst design principles by identifying structural features of materials that influence their performance will advance the rational engineering of new catalytic materials. In this study, by investigating metal-substituted manganese oxide (spinel) nanoparticles, Mn₃O₄:M (M=Sr, Ca, Mg, Zn, Cu), we rationalize the dependence of the activity of Mn₃O₄:M for the electrocatalytic oxygen reduction reaction (ORR) on the enthalpy of formation of the binary MO oxide, Δ_fH°(MO), and the Lewis acidity of the M²⁺ substituent. Incorporation of elements M with low Δ_fH°(MO) enhances the oxygen binding strength in Mn₃O₄:M, which affects its activity in ORR due to the established correlation between ORR activity and the binding energy of *O/*OH/*OOH species. Our work provides a perspective on the design of new compositions for oxygen electrocatalysis relying on the rational substitution/doping by redox-inactive elements.     

Performance evaluation of a rapid-scanning quadrupole mass spectrometer in the comprehensive two-dimensional gas chromatography analysis of pesticides in water

The performance of a novel rapid-scanning (20,000 amu/s) quadrupole mass spectrometer (qMS) has been evaluated in the comprehensive 2-D gas chromatography (GC×GC) analysis of pesticides contained in water. Analyte extraction was performed by using direct solid-phase microextraction (SPME). The MS system was operated using a rather wide m/z 50-450 mass range and a 33 Hz spectral production rate, a frequency which was found sufficient for reliable quantification. The qMS performance was evaluated considering: (i) number of data points per peak, (ii) mass spectral quality, (iii) extent of peak skewing, and (iv) consistency of retention times. Seven-point calibration curves (external calibration) were constructed for 28 pesticides over the limit of quantification range of 100 μg/L (1, 5, 10, 25, 50, and 100 μg/L). The solid-phase microextraction-GC×GC-qMS method was validated by calculating limits of detection and quantification, intraday peak area precision, accuracy, and intraday retention-time precision. A series of tap water samples were subjected to analysis, fortunately giving negative results.     

Enhanced adsorption of paracetamol on closed carbon nanotubes by formation of nanoaggregates: carbon nanotubes as potential materials in hot-melt drug deposition-experiment and simulation

We present the new results of systematic studies of paracetamol adsorption on closed, commercially available, unmodified carbon nanotubes. The results of thermal analysis, static adsorption measurements and the comparison with phenol adsorption data lead to suggestion that the formation of paracetamol nanoaggregates in the interstitial spaces between nanotubes occurs. This effect is also confirmed by the results of (performed in two ways) independent dynamic measurements and by molecular dynamics simulation technique. Next, we show that the behavior of adsorbed paracetamol during heating leads to the creation of a new drug delivery system. The properties of this system depend on the type of applied nanotubes and the parameters of the process called hot-melt drug deposition. Thus, we conclude that confined nanoaggregate formation, as well as hot-melt deposition should be promising effects in the preparation of highly effective, new drug delivery systems.