Perimidine-based synthetic receptors for determination of copper(II) in water solution

Perimidine-based chelators 1 and 2 were prepared, and their structures were confirmed by ¹H and ¹³C NMR, MS spectroscopy and elemental analysis. These compounds were studied as specific synthetic receptors for the recognition of transition metal ions. They exhibited high affinity and selectivity towards Cu(II) ions. The conditional binding constants, linear dynamic range and detection limit were determined by UV–vis spectroscopy. These parameters demonstrated high potential of the prepared synthetic receptors for the recognition and determination of Cu(II) ions. The minimum detectable concentrations of Cu(II) ions for the synthetic receptors 1 and 2 were 270 and 75 nM (R ² = 0.9915 and 0.9964) in aqueous medium (water/DMSO; 99:1 (v/v)), respectively.     

On geodesic mappings of equidistant generalized Riemannian spaces

In this paper geodesic mappings of equidistant generalized Riemannian spaces are discussed. It is proved that each equidistant generalized Riemannian space of basic type admits non-trivial geodesic mapping with preserved equidistant congruence. Especially, there exists non-trivial geodesic mapping of equidistant generalized Riemannian space onto equidistant Riemannian space. An example of geodesic mapping of an equidistant generalized Riemannian spaces is presented.     

Organodiphosphines in cis-Pt(η2-P2L)(η2-S2L) derivatives – structural aspects

Abstract

In this review structural parameters of forty complexes with an inner coordination sphere of Pt(η²-P₂L)(η²-S₂L) are analyzed and classified These complexes crystallize in three crystal systems: orthorhombic (four examples), triclinic (six examples) and monoclinic (thirty examples). The organodiphosphines create four- (PCP), five- (PC₂P), six- (PC₃P) and seven- (PC₄P) membered metallocyclic rings with mean P-Pt-P bite angle values of 72.5° (PCP) < 85.3° (PC₂P) < 93.0° (PC₃P) < 97.4° (PC₄P). The dithiolates create four- (SCS), five- (SC₂S), six- (SC₃S; SCSCS; SPNPS; SPCPS) and seven- (SC₄S) membered metallocyclic rings with mean S-Pt-S bite angle values of 74.5° (SCS) < 85.8° (SCSCS) < 87.0° (SPNPS) < 89.0° (SC₂S) < 92.3° (SC₄S) < 93.5° (SC₃S) < 97.5° (SPCPS). The mean Pt-P and Pt-S bond distances are 2.257 and 2.328?Å, respectively. The data are compared with those found in complexes with inner coordination spheres of Pt(PL)₂(SL)₂, Pt(PL)₂(η²-S₂L) and Pt(η²-P₂L)(SL)₂.     

Mechanistic investigation and DFT calculation of the new reaction between S-methylisothiosemicarbazide and methyl acetoacetate

A study on the synthesis and mechanistical aspects of formation of 3-methyl-5-oxo-3-pyrazolin-1-carboxamide (MOPC) starting from S-methylisothiosemicarbazide hydrogen iodide and methyl acetoacetate was performed. In the alkaline aqueous solution, the intermediate methyl acetoacetate S-methylisothiosemicarbazone undergoes substitution of CH₃S^? anion by hydroxide anion, cyclization, carbanion formation, and elimination of methanol, thus yielding corresponding Na-enolate salt of pyrazol-5-one derivative. The structure of the compound obtained after protonation of the formed enolate salt was determined by means of spectroscopic techniques and single-crystal X-ray diffraction analysis. The mechanism of conversion of methyl acetoacetate S-methylisothiosemicarbazone into MOPC was investigated by means of the B3LYP functional, and it was found that the reaction is thermodynamically controlled.     

Ultrasensitive impedimetric lectin based biosensor for glycoproteins containing sialic acid

We report on an ultrasensitive label-free lectin-based impedimetric biosensor for the determination of the sialylated glycoproteins fetuin and asialofetuin. A sialic acid binding agglutinin from Sambucus nigra I was covalently immobilised on a mixed self-assembled monolayer (SAM) consisting of 11-mercaptoundecanoic acid and 6-mercaptohexanol. Poly(vinyl alcohol) was used as a blocking agent. The sensor layer was characterised by atomic force microscopy, electrochemical impedance spectroscopy and X-ray photoelectron spectroscopy. The biosensor exhibits a linear range that spans 7 orders of magnitude for both glycoproteins, with a detection limit as low as 0.33 fM for fetuin and 0.54 fM for asialofetuin. We also show, by making control experiments with oxidised asialofetuin, that the biosensor is capable of quantitatively detecting changes in the fraction of sialic acid on glycoproteins. We conclude that this work lays a solid foundation for future applications of such a biosensor in terms of the diagnosis of diseases such as chronic inflammatory rheumatoid arthritis, genetic disorders and cancer, all of which are associated with aberrant glycosylation of protein biomarkers.

The unambiguous synthesis and NMR assignment of 4-alkoxy and 3-alkylquinazolines

Contrary to a number of reports, alkylations of the privileged 3,4-dihydroquinazoline scaffold provide N3-alkylated products, and not 4-alkoxyquinazolines. To correctly assign the structure, ¹³C NMR shifts of the –Z–CH_n– (Z=O, N) fragment are necessary; resonances in the 45–55 ppm range are indicative of N3-alkylation. Treatment of 3,4-dihydroquinazoline-4-one with p-TsCl afforded the N3-tosylated compound, whose reaction with an amine yielded the corresponding N3-alkyl derivative. A mechanism corroborated by ¹⁵N-labeling involving pyrimidine ring opening and recyclisation is proposed. Finally, the unambiguous preparation of 4-alkoxyquinazolines is described via treatment of 3,4-dihydroquinazoline-4-ones with PCl₅ followed by an alkoxide.     

CZE study on adsorption processes of aliphatic and aromatic amines on PMMA chip

Adsorption processes on a PMMA chip linked with CZE separations of a group of 13 aliphatic and aromatic mono‐ and di‐amines were studied. Due to the lack of chromophores within aliphatic amines, contact conductivity detection implemented directly onto the chip was used for monitoring of cationic CZE separations. To prevent an adsorption of studied amines to the chip channels, the surface of PMMA chip was modified by dynamic coating. Different surface modifiers, such as aliphatic oligoamines (diethylenetriamine and triethylenetetramine), were added to the BGE solutions filling the chip channels. The effect of various concentrations of surface modifiers on peak profiles and separation parameters of amines was monitored. Of these, mainly, aliphatic di‐amines and aromatic mono‐amines adversely affected the CZE resolution of a whole group of analytes by their strong adsorption to the chip channels. A propionate BGE with pH 3.2 containing 100 μM triethylenetetramine and 25 mM 18‐crown‐6‐ether was found suitable for CZE resolution of 12 from a total of 13 amines studied. Simple dynamic modification of the surface of PMMA chip enabled fast (analysis time lasted 9 min), sensitive (sub‐μM LODs reached) and reproducible (1–3% RSD of the peak areas) CZE analysis of the aliphatic and aromatic amines.