Selective Detection of Carbohydrates and Their Peptide Conjugates by ESI-MS Using Synthetic Quaternary Ammonium Salt Derivatives of Phenylboronic Acids

We present new tags based on the derivatives of phenylboronic acid and apply them for the selective detection of sugars and peptide-sugar conjugates in mass spectrometry. We investigated the binding of phenylboronic acid and its quaternary ammonium salt (QAS) derivatives to carbohydrates and peptide-derived Amadori products by HR-MS and MS/MS experiments. The formation of complexes between sugar or sugar-peptide conjugates and synthetic tags was confirmed on the basis of the unique isotopic distribution resulting from the presence of boron atom. Moreover, incorporation of a quaternary ammonium salt dramatically improved the efficiency of ionization in mass spectrometry. It was found that the formation of a complex with phenylboronic acid stabilizes the sugar moiety in glycated peptides, resulting in simplification of the fragmentation pattern of peptide-derived Amadori products. The obtained results suggest that derivatization of phenylboronic acid as QAS is a promising method for sensitive ESI-MS detection of carbohydrates and their conjugates formed by non-enzymatic glycation or glycosylation.

The Identification of Cotton Fibers Dyed with Reactive Dyes for Forensic Purposes

Some of the most common microtraces that are currently collected at crime scenes are fragments of single fibers. The perpetrator leaves them at a crime scene or takes them away, for example, on their clothing or body. In turn, the microscopic dimensions of such traces mean that the perpetrator does not notice them and therefore usually does not take action to remove them. Cotton and polyester fibers dyed by reactive and dispersion dyes, respectively, are very popular within clothing products, and they are hidden among microtraces at the scene of a crime. In our recently published review paper, we summarized the possibilities for the identification of disperse dyes of polyester fibers for forensic purposes. In this review, we are concerned with cotton fibers dyed with reactive dyes. Cotton fibers are natural ones that cannot easily be distinguished on the basis of morphological features. Consequently, their color and consequently the dye composition are often their only characteristics. The presented methods for the identification of reactive dyes could be very interesting not only for forensic laboratories, but also for scientists working in food, cosmetics or pharmaceutical/medical sciences.     

Synthesis,Crystal Structures,and Spectroscopic Properties of Novel Gadolinium and Erbium Triphenylsiloxide Coordination Entities

In alkali metal and lanthanide coordination chemistry, triphenylsiloxides seem to be unduly underappreciated ligands. This is as surprising as that such substituents play a crucial role, among others, in stabilizing rare oxidation states of lanthanide ions, taking a part of intramolecular and molecular interactions stabilizing metal-oxygen cores and many others. This paper reports the synthesis and characterization of new lithium [Li₄(OSiPh₃)₄(THF)₂] (1), and sodium [Na₄(OSiPh₃)₄] (2) species, which were later used in obtaining novel gadolinium [Gd(OSiPh₃)₃(THF)₃]·THF (3), and erbium [Er(OSiPh₃)₃(THF)₃]·THF (4) configuration, it can result in res were determined for all 1–4 compounds, and in addition, IR, Raman, absorption spectroscopy studies were conducted for 3 and 4 lanthanide compounds. Furthermore, direct current (dc) variable-temperature magnetic susceptibility measurements on polycrystalline samples of 3 and 4 were carried out in the temperature range 1.8–300 K. The 3 shows behavior characteristics for the paramagnetism of the Gd³⁺ ion. In contrast, the magnetic properties of 4 are dominated by the crystal field effect on the Er³⁺ ion, masking the magnetic interaction between magnetic centers of neighboring molecules.     

Barrier Dispersion-Based Coatings Containing Natural and Paraffin Waxes

Petroleum, synthetic, and natural waxes have been used as hydrophobic bases for dispersions intended for use as barrier coatings for packaging paper. Oil-in-water dispersions with alkaline pH were prepared by a two-step homogenization procedure containing paraffin wax, with various characteristics, the Fischer–Tropsch synthesis product or beeswax. The size of the dispersed particles determined by dynamic light scattering depended on the type of hydrophobic base used and was in the range of 350–440 nm. The ability of dispersion particles in aggregation driven by electrostatic attraction, evaluated by Zeta potential analysis by electrophoretic light scattering, was from −26 to −50 mV. Static multiply light scattering was used for 30 days of stability assessment and helped to select the dispersion with a Sarawax SX70 wax base as the most stable. Dispersions were further used for coating the backing of kraft paper by the Meyer rod method. Coated paper with an applied coating of 6 g/m² had very good hydrophobic properties (Cobb60 < 4 g/m²), sufficient strength properties, and air permeation, which enabled its application as a packaging material. The dispersions based on Sarawax SX70 wax were evaluated as the best coating for Mondi ProVantage Kraftliner 125 g/m² backing paper. Good hydrophobic properties and strength properties indicate the possibility of using the SX70-based wax dispersion coating as a replacement for PFAS coatings in some applications.     

Micro- and Nanosecond Pulses Used in Doxorubicin Electrochemotherapy in Human Breast and Colon Cancer Cells with Drug Resistance

(1) Background: Pulsed electric field (PEF) techniques are commonly used to support the delivery of various molecules. A PEF seems a promising method for low permeability drugs or when cells demonstrate therapy resistance and the cell membrane becomes an impermeable barrier. (2) Methods: In this study, we have used doxorubicin-resistant and sensitive models of human breast cancer (MCF-7/DX, MCF-7/WT) and colon cancer cells (LoVo, LoVoDX). The study aimed to investigate the susceptibility of the cells to doxorubicin (DOX) and electric fields in the 20–900 ns pulse duration range. The viability assay was utilized to evaluate the PEF protocols’ efficacy. Cell confluency and reduced glutathione were measured after PEF protocols. (3) Results: The obtained results showed that PEFs significantly supported doxorubicin delivery and cytotoxicity after 48 and 72 h. The 60 kV/cm ultrashort pulses × 20 ns × 400 had the most significant cytotoxic anticancer effect. The increase in DOX concentration provokes a decrease in cell viability, affected cell confluency, and reduced GSSH when combined with the ESOPE (European Standard Operating Procedures of Electrochemotherapy) protocol. Additionally, reactive oxygen species after PEF and PEF-DOX were detected. (4) Conclusions: Ultrashort electric pulses with low DOX content or ESOPE with higher DOX content seem the most promising in colon and breast cancer treatment.     

Spin disorder scattering in magnetic metallic alloys

Anomalous behavior of the resistivity at or just below the Néel temperature in antiferromagnetic metals is usually attributed to the formation of superzone gaps. However, we find that RMn12-xFex alloys which have no such gaps exhibit a similarly anomalous resistivity. We show that electron scattering by substitutional spin disorder can account for such behavior of itinerant magnets. This mechanism, which has not been studied before, leads to a relaxation rate that is proportional to x(12-x)m(2), where m is the staggered magnetization. Together with spin fluctuations, phonon, and impurity scattering, it accounts well for the resistivity data we obtain for HoMn12-xFex, for 0< or =x< or =9, in the temperature range of 4 to 400 K.     

Evidence for dimer formation by an amphiphilic heptapeptide that mediates chloride and carboxyfluorescein release from liposomes

Heptapeptides having dioctadecyl, N-terminal hydrocarbon chains insert in phospholipid bilayer membranes and form pores through which at least chloride ions pass. Although amphiphilic, these compounds do not typically form vesicles themselves. They insert in the bilayers of phospholipid vesicles and mediate the release of carboxyfluorescein. Hill analysis indicates that at least two molecules of the amphiphile are involved in pore formation. In CD2Cl2, dimer formation is detected by NMR chemical shift changes. The anion release activity of individual anion transporters is increased by linking them covalently at the C-terminus or, even more, by linking them at the N-terminus. Evidence is presented that either linked molecule releases chloride from liposomes more effectively and rapidly than the individual transporter molecule at a comparable concentration.     

Determination of nonsteroidal antiinflammatory drugs in water samples using liquid chromatography coupled with diode-array detector and mass spectrometry

An analytical method for the determination of trace levels of six different nonsteroidal antiinflammatory drugs (NSAIDs) in water samples has been developed and validated. Environmentally relevant pharmaceuticals were chosen according to human consumption in Poland. Final analysis of the target compounds was performed by RP LC-diode-array detection-MS, whereas sample preparation included an SPE step. For this SPE step, a number of packing materials, such as LiChrolut RP-18, calixarene, Strata-X, BAKERBOND Narc-2, BAKERBOND Polar Plus, BAKERBOND styrene divinylbenzene-1, and Discovery DSC-18, were used, and their respective advantages and disadvantages in this study were discussed. The RP-18 phase was found to be the most retentive for all analytes. The detection limits for compounds in surface waters were varied from 0.005 for diflunisal to 0.095 microg/L for ibuprofen. The average recoveries of NSAIDs from the surface water samples ranged from 80 up to 103%. RSD value is relatively low (from 4% for fenoprofen up to 8% for ibuprofen). The performance of the method was tested with several environmental water samples.     

A fine-tuned molybdenum hexacarbonyl/phenol initiator for alkyne metathesis

A new, highly potent activator for molybdenum hexacarbonyl and 2-fluorophenol is described. An "instant"catalyst formed in situ from molybdenum hexacarbonyl and 2-fluorophenol shows high activity for cross- and ring-closing alkyne metathesis reaction. The use of 2-fluorophenol can be combined with other activation methods to allow alkyne metathesis at relatively low temperature (80 degrees C).     

Chiral polymers containing a carbohydrate moiety: synthesis

This paper reports the preparation of poly(acetal-ethers) by two alternative synthetic pathways (alkaline and acid-catalyzed conditions). Polycondensations of methyl 2,3:4,6-di-O-salicylidene-alpha-D-mannopyranoside (3) (mixtures of endo-H and exo-H dioxolan-2-yl-diastereomers) with 1,4-dibromobutane (4) (method I a and I b) were performed in solvents (DMF, butyl acetate/DMF, DMSO) and were catalyzed by K2CO3/KI or KOH. A similar polymer (6) was formed by the reaction of methyl alpha-D-mannopyranoside (1) and 1,4-bis(2-formylphenoxy)butane (7), catalyzed by p-toluenesulfonic acid (method II). Regardless of conversion or initial comonomer feed ratios, the composition of the polycondensates depended on the reaction conditions, leading to the formation of macrocyclic [1 + 1] (5) and [2 + 2] compounds, which were macromolecules with diverse molecular weights and optical properties. The regioselective polycondensation was examined by 1H NMR spectroscopy of selected polymers. In the case of 5-membered cyclic acetal units, mixtures of the endo-H and exo-H dioxolan-2-yl system, diastereomers were formed in the polymer chain. The macrocycles and linear oligomers were identified by NMR and electrospray mass spectrometry (ESI-MS). Thermodynamically controlled reactions for making macrocycles as well as oligomers in the absence of templates are also discussed.