Synthesis,physicochemical, and biological activities of novel N‐acyl tyrosine monomeric and Gemini surfactants in single and SDS/CTAB–mixed micellar system

A series of single‐chained N‐acyl tyrosine surfactants with varying chain lengths (C₁₀‐C₁₈) and degree of unsaturation, as well as an N‐acyl Gemini tyrosine surfactant with chain length C₁₂, were synthesized, and the structures were confirmed using spectral analysis. The effect of chain length and level of unsaturation on the physicochemical and antibacterial properties of the N‐acyl tyrosine surfactants was evaluated. The C₁₂ derivative displayed the optimum antibacterial activity among the single chain surfactants, and the presence of double bond in the oleoyl derivative enhanced the antibacterial activity over its saturated analogue. The N‐acyl Gemini surfactant displayed the highest antibacterial activity among the series and also showed greater micelle forming ability than its single chain analogue. Mixed micellar behavior of the N‐acyl Gemini surfactant with conventional cationic (CTAB) and anionic (SDS) surfactants in aqueous solution was studied. The negative value of the interaction parameter β₁₂ observed for the N‐acyl Gemini in binary mixture with CTAB surfactant indicated a synergistic interaction within the mixed micellar system. However, the binary mixture with SDS displayed antagonistic behavior. The binary mixture of N‐acyl Gemini surfactant with CTAB displayed better antibacterial activity and foaming properties than with SDS mixtures. Optimum antibacterial activity was observed for N‐acyl Gemini surfactant with mole ratio 0.4 to 0.6 in the CTAB binary mixture, at which the lowest ocular irritation index was observed. Overall, the study showed that the Gemini surfactant in combination with the conventional surfactant CTAB can be used as potential ingredients in detergent and pharmaceutical formulations.     

An application of the maximum principle to describe the layer behavior of large solutions and related problems

This work is devoted to the analysis of the asymptotic behavior of positive solutions to some problems of variable exponent reaction-diffusion equations, when the boundary condition goes to infinity (large solutions). Specifically, we deal with the equations ??u = u ^p(x), ??u = ?m(x)u?+?a(x)u ^p(x) where a(x)??? a ₀ >?0, p(x)??? 1 in ??, and ??u = e ^p(x) where p(x)??? 0 in ??. In the first two cases p is allowed to take the value 1 in a whole subdomain ${\Omega_c\subset \Omega}$ , while in the last case p can vanish in a whole subdomain ${\Omega_c\subset \Omega}$ . Special emphasis is put in the layer behavior of solutions on the interphase ?? _i :?= ??? _c ???. A similar study of the development of singularities in the solutions of several logistic equations is also performed. For example, we consider ???u = ?? m(x)u?a(x) u ^p(x) in ??, u = 0 on ???, being a(x) and p(x) as in the first problem. Positive solutions are shown to exist only when the parameter ?? lies in certain intervals: bifurcation from zero and from infinity arises when ?? approaches the boundary of those intervals. Such bifurcations together with the associated limit profiles are analyzed in detail. For the study of the layer behavior of solutions the introduction of a suitable variant of the well-known maximum principle is crucial.     

Multiplicity of solutions to a nonlinear elliptic problem with nonlinear boundary conditions

We study the problem $$\left\{\begin{array}{ll}\Delta_p u = |u|^{q-2}u, & \quad x \in \Omega ,\\ |\nabla u|^{p-2} \frac{\partial u}{\partial \nu}= \lambda |u|^{p-2}u, &\quad x \in \partial \Omega, \end{array}\right.$$ where \({\Omega \subset \mathbb{R}^N}\) is a bounded smooth domain, \({\nu}\) is the outward unit normal at \({\partial \Omega}\) and \({\lambda > 0}\) is regarded as a bifurcation parameter. When p = 2 and in the superlinear regime q > 2, we show existence of n nontrivial solutions for all \({\lambda > \lambda_n}\) , \({\lambda_n}\) being the n-th Steklov eigenvalue. It is proved in addition that bifurcation from the trivial solution takes place at all \({\lambda_n}\) ’s. Similar results are obtained in the sublinear case 1 < q < 2. In this case, bifurcation from infinity takes place in those \({\lambda_n}\) with odd multiplicity. Partial extensions of these features are shown in the nonlinear diffusion case \({p \neq 2}\) and related problems under spatially heterogeneous reactions are also addressed.     

Preparation of substituted pyrimido[4,5-b]-1,4-benzoxazepines, thiazepines, and diazepines via a Pictet-Spengler cyclization

[Reaction: see text]. A synthesis of the title compounds, which have found use as inhibitors of certain receptor tyrosine kinases, was achieved using a Pictet-Spengler cyclization as a key step.     

A comparison among different instrumental approaches for bromide analysis in foodstuffs digested by a suitably modified microwave procedure

Cathodic stripping voltammetry (CSV), ion-chromatography (IC) and spectrophotometry (SP) have been tested as instrumental approaches alternative to inductively coupled plasma mass spectrometry (ICP-MS) for the determination of inorganic bromide residues in foodstuffs fumigated with brominated pesticides and digested by a suitably improved microwave procedure proposed previously. They were chosen in view of the fact that the relevant instrumentation is less expensive than that required for ICP-MS and more frequently available in analytical laboratories designed for routine food control. These approaches were compared with one another, as well as with the ICP-MS method previously adopted, not only with regard to their performance, but also in terms of the interferences caused by the composition of final samples coming from the microwave digestion procedure. The results found pointed out unambiguously that IC turns out to be well suited for replacing ICP-MS, thanks to its consistency with the composition of digested samples and its good sensitivity which allows a quite low detection limit for bromides (0.2 mg kg⁻¹) to be achieved. Conversely, CSV and SP performance appears to be significantly affected by interferences caused by the presence in digested samples of chlorides and ammonium ions, respectively.     

Antibacterial,Antioxidant and Binding Studies of Some Novel Diaryl Sulphide Derivatives

Abstract

A series of novel acyclic and cyclic diaryl sulphides was synthesized from 2,2′-dithiobenzoic acid. The various diaryl sulphides were characterized by use of spectral (IR, ¹H and ¹³C NMR, ESI/MS) and elemental analyses. The antimicrobial activities of the compounds were evaluated in terms of their minimum inhibition concentration (MIC) against a panel of clinical isolates bacteria and were found to possess only moderate antimicrobial activities. N,N′-Bis(2-hydroxyphenyl)-2,2′-thiodibenzamide (13), exhibiting a hydroxy group at the phenyl ring, was the most active antimicrobial agent within the series, with MIC values of 0.05 mg mL^–1 and 10 mg mL^–1 against Staphylococcus aureus and Bacillus cereus, respectively. The antioxidant efficiency of the diaryl sulphides was determined by 2,2-diphenyl-1-picrylhydrazyl (DPPH) scavenging activity with 13 being the most active compound. The interaction of 2,2′-thiodibenzanilide, N,N′-bis(2-methylphenyl)-2,2′-thiodibenzamide, and N,N′-bis(2-hydroxyphenyl)-2,2′-thiobenzamide with guanine, glutamic acid, and urea were studied quantitatively with binding constants ranging from 1 × 10³ M^?1 to 2.7 × 10⁴ M^?1.     

A modified electrode for the electrochemical detection of biogenic amines and their amino acid precursors separated by microchip capillary electrophoresis

The use of a mixed-valent ruthenium oxide/hexacyanoruthenate polymeric film electrochemically deposited onto glassy carbon electrodes is proposed here for the detection of biogenic amines and their amino acid precursors, following their separation by microchip capillary electrophoresis. The ability of this ruthenium coating to electrocatalyze the oxidation of aliphatic and heterocyclic amines, as well as their amino acid precursors, was checked by using ethanolamine, tryptamine and tryptophane as prototype compounds and adopting a 25 mM sulphuric acid as the electrolyte in the detection cell, where a constant potential of 1.05 V versus Ag/AgCl, 3 M KCl was applied to the modified working electrode. Optimization of parameters affecting both detection and separation steps led to satisfactory separations when performed by using a 20 mM phosphate running buffer (pH 2.5) and applying a high voltage of 2.5 kV both in the separation and in the electrokinetic injection (duration 4 s). The recorded peaks were characterized by good repeatability (RSD ≤ 3.6%), high sensitivity and a wide linear range. Detection limits of 23 μM (1.4 mg/L), 27 μM (4.3 mg/L) and 34 μM (6.8 mg/L) were inferred for ethanolamine, tryptamine and tryptophane, respectively. The approach proposed here was also applied for the analysis of some double malt dark beers spiked with a controlled amount of the analytes considered.     

Experimental determination and prediction of bilitranslocase transport activity

The transport activity of a membrane protein, bilitranslocase (T.C. # 2.A.65.1.1), which acts as a transporter of bilirubin from blood to liver cells, was experimentally determined for a large set of various endogenous compounds, drugs, purine and pyrimidine derivatives. On these grounds, the structure-activity models were developed following the OECD principles of QSAR models and their predictive ability for new chemicals was evaluated. The applicability domain of the models was estimated by Euclidean distances criteria according to the applied modeling method. The selection of the most influential structural variables was an important stage in the adopted modeling methodology. The interpretation of selected variables was performed in order to get an insight into the mechanism of transport through the cell membrane via bilitranslocase. Validation of the optimized models was performed by a previously determined validation set. The classification model was build to separate active from inactive compounds. The resulting accuracy, sensitivity, and specificity were 0.73, 0.89, and 0.64, respectively. Only active compounds were used to develop a predictive model for bilitranslocase inhibition constants. The model showed good predictive ability; Root Mean Squared error of the validation set, RMS(V)=0.29 log units.