Reaction of substituted furan-2-carboxaldehydes and furo[b]pyrrole type aldehydes with hippuric acid

4-Heteroarylidene-2-phenyl-1,3-oxazol-5(4H)-ones were prepared by reactions of hippuric acid with substituted furan-2-carboxaldehydes or furo[b]pyrrole type aldehydes. The reactivity of various furan-2-carboxaldehyde derivatives in this reaction is discussed. The effect of microwave irradiation on some condensation reactions was compared with "classical" conditions. The results show that microwave irradiation shortens the reaction times while affording comparable yields. Elementary analysis, UV, IR and 1D NMR proved the structure of new synthesised compounds. 2D NMR spectroscopic measurements confirmed that the configuration at the carbon-carbon double bond corresponds to the pure E isomers of the products.     

Superoxide dismutase mimicking Cu(II)–mixed amino acid complexes covalently grafted onto silica gel—an FT-IR study

Our recent work concerning the synthesis, characterisation and testing of bioinspired electron transfer catalysts is described in this contribution. The catalysts were various Cu(II) complexes having mixed C- or N-protected amino acids (l-histidine and l-tyrosine) as ligands covalently grafted onto surface-modified silica gel. The resulting materials were structurally characterised by FT-IR spectroscopy, and their superoxide dismutase activities were tested. The covalently anchored Cu(II) complexes displayed appreciable activities in the test reaction; thus, they may be considered as promising candidates as durable electron transfer catalysts approaching the efficiency of the enzyme mimicked.     

The invariance of the arithmetic mean with respect to generalized quasi-arithmetic means

The aim of this paper is to find those pairs of generalized quasi-arithmetic means on an open real interval I for which the arithmetic mean is invariant, i.e., to characterize those continuous strictly monotone functions φ,ψ:I→R and Borel probability measures μ,ν on the interval [0,1] such that

     

Electron ionization mass spectra of phosphorus-containing heterocycles. I. 1,4,4a,5,6,7,8,8a-octahydro-2H-3,1,2-benzoxazaphosphinine 2-oxides

The electron ionization mass spectra of 27 cis- and trans-annelated 1,4,4a,5,6,7,8,8a-octahydro-2H-3,1,2-benzoxazaphosphinine 2-oxides were recorded to clarify the effects of the ring heteroatom (O or N), ring annelation, the P configuration and the substituents attached to the ring or to the N and P atoms. For compounds 1-12 different alkyl radical and alkene losses and the cleavage of the P-heteroatom bonds, instead of the P-C bonds, were representative and dependent mainly on the substitution on the N and P atoms. The replacement of Ph and OPh by N(CH2CH2Cl)2 on the P atom had a dramatic influence on the fragmentation process: new fragment ions were obtained and very little M+ (1-3%) was formed. Only slight differences were found between some of the corresponding isomers, but interestingly the compounds formed clear groups on the basis of the differences in their fragmentation, depending on the ring-N and ring-P substituents.     

On the Lipschitz perturbation of monotonic functions

Summary A real valued function <InlineEquation ID=IE"5"><EquationSource Format="TEX"><![CDATA[<InlineEquation ID=IE"6"><EquationSource Format="TEX"><![CDATA[<InlineEquation ID=IE"7"><EquationSource Format="TEX"><![CDATA[<InlineEquation ID=IE"8"><EquationSource Format="TEX"><![CDATA[<InlineEquation ID=IE"9"><EquationSource Format="TEX"><![CDATA[<InlineEquation ID=IE"10"><EquationSource Format="TEX"><![CDATA[<InlineEquation ID=IE"11"><EquationSource Format="TEX"><![CDATA[<InlineEquation ID=IE"12"><EquationSource Format="TEX"><![CDATA[<InlineEquation ID=IE"13"><EquationSource Format="TEX"><![CDATA[<InlineEquation ID=IE"14"><EquationSource Format="TEX"><![CDATA[<InlineEquation ID=IE"15"><EquationSource Format="TEX"><![CDATA[<InlineEquation ID=IE"16"><EquationSource Format="TEX"><![CDATA[<InlineEquation ID=IE"17"><EquationSource Format="TEX"><![CDATA[<InlineEquation ID=IE"18"><EquationSource Format="TEX"><![CDATA[<InlineEquation ID=IE"19"><EquationSource Format="TEX"><![CDATA[<InlineEquation ID=IE"20"><EquationSource Format="TEX"><![CDATA[<InlineEquation ID=IE"21"><EquationSource Format="TEX"><![CDATA[<InlineEquation ID=IE"22"><EquationSource Format="TEX"><![CDATA[<InlineEquation ID=IE"23"><EquationSource Format="TEX"><![CDATA[<InlineEquation ID=IE"24"><EquationSource Format="TEX"><![CDATA[<InlineEquation ID=IE"25"><EquationSource Format="TEX"><![CDATA[<InlineEquation ID=IE"26"><EquationSource Format="TEX"><![CDATA[<InlineEquation ID=IE"27"><EquationSource Format="TEX"><![CDATA[<InlineEquation ID=IE"28"><EquationSource Format="TEX"><![CDATA[<InlineEquation ID=IE"29"><EquationSource Format="TEX"><![CDATA[<InlineEquation ID=IE"30"><EquationSource Format="TEX"><![CDATA[<InlineEquation ID=IE"31"><EquationSource Format="TEX"><![CDATA[<InlineEquation ID=IE"32"><EquationSource Format="TEX"><![CDATA[<InlineEquation ID=IE"33"><EquationSource Format="TEX"><![CDATA[<InlineEquation ID=IE"34"><EquationSource Format="TEX"><![CDATA[$]]></EquationSource></InlineEquation>]]></EquationSource></InlineEquation>]]></EquationSource></InlineEquation>]]></EquationSource></InlineEquation>]]></EquationSource></InlineEquation>]]></EquationSource></InlineEquation>]]></EquationSource></InlineEquation>]]></EquationSource></InlineEquation>]]></EquationSource></InlineEquation>]]></EquationSource></InlineEquation>]]></EquationSource></InlineEquation>]]></EquationSource></InlineEquation>]]></EquationSource></InlineEquation>]]></EquationSource></InlineEquation>]]></EquationSource></InlineEquation>]]></EquationSource></InlineEquation>]]></EquationSource></InlineEquation>]]></EquationSource></InlineEquation>]]></EquationSource></InlineEquation>]]></EquationSource></InlineEquation>]]></EquationSource></InlineEquation>]]></EquationSource></InlineEquation>]]></EquationSource></InlineEquation>]]></EquationSource></InlineEquation>]]></EquationSource></InlineEquation>]]></EquationSource></InlineEquation>]]></EquationSource></InlineEquation>]]></EquationSource></InlineEquation>]]></EquationSource></InlineEquation>]]></EquationSource></InlineEquation>f$ defined on a real interval $I$ is called \emph{$d$-Lipschitz} if it satisfies $|\ell(x)- \ell(y)| \le d(x,y)$ for $x,y\in I$. In this paper, we investigate when a function $p\: I \to \bR$ can be decomposed in the form $p=q+ \ell$, where $q$ is increasing and $\ell$ is $d$-Lipschitz. In the general case when $d\: I^{2} \to \bR$ is an arbitrary semimetric, a function $p\: I \to \bR$ can be written in the form $p=q+ \ell$ if and only if \vspace{-4pt} <InlineEquation ID=IE"1"><EquationSource Format="TEX"><![CDATA[<InlineEquation ID=IE"2"><EquationSource Format="TEX"><![CDATA[<InlineEquation ID=IE"3"><EquationSource Format="TEX"><![CDATA[<InlineEquation ID=IE"4"><EquationSource Format="TEX"><![CDATA[$$]]></EquationSource></InlineEquation>]]></EquationSource></InlineEquation>]]></EquationSource></InlineEquation>]]></EquationSource></InlineEquation> \sum_{i=1}^{n}{\big(p(s_{i})-p(t_{i})-d(t_{i},s_{i}) \big)^{+}} \le \sum_{j=1}^{m}{\big(p(v_{j})-p(u_{j})+d(u_{j},v_{j}) \big)} \vspace{-4pt} $$ is fulfilled for all real numbers $t_{1}<s_{1}, \dots, t_{n}<s_{n}$ and $u_{1}<v_{1}, \dots, u_{m}<v_{m}$ in $I$ satisfying the condition \vspace{-4pt} $$ \sum_{i=1}^{n} 1_{\left]t_i,s_i\right]}= \sum_{j=1}^{m} 1_{\left]u_j,v_j\right]}, \vspace{-4pt} $$ where $1_{\left]a,b\right]}$ denotes the characteristic function of the interval $\left]a,b\right]$. In the particular case when $d\: I^{2} \to R$ is a so-called concave semimetric, a function $p\: I \to \bR$ is of the form $p=q+ \ell$ if and only if \vspace{-4pt} $$ 0 \le \sum_{k=1}^{n}{d(x_{2k-1},x_{2k})} + d(x_0,x_{2n+1}) + \sum_{k=0}^{n}{\big(p(x_{2k+1})-p(x_{2k})\big)} \vspace{-4pt} $$ holds for all $x_0\le x_1\ki \cdots\ki x_{2n}\le x_{2n+1}$ in $I$.     

Substituent-dependent negative hyperconjugation in 2-aryl-1,3-N,N-heterocycles. fine-tuned anomeric effect?

The epimerization reactions of conformationally inflexible 2-aryl-1,3-N,N-heterocycles were used as model systems to study the role of the nitrogen lone pair-C2 associated antibonding orbital hyperconjugative interactions in the experimentally observed substituent-dependent generalized anomeric effect. The measured reaction free enthalpies were found to correlate well with the sum of the hyperconjugative stabilization energies of all the vicinal donor-acceptor orbital overlaps around C2, obtained from ab initio NBO analysis, and both quantities correlated linearly with the Hammett-Brown substituent constant. The individual stereoelectronic interactions (n(N)-sigma(C2)(-)(N), n(N)-sigma(C2)(-)(Ar), n(N)-sigma(C2)(-)(H)) were also observed to exhibit a substituent dependence, despite their distance from the 2-aryl substituent and their nonperiplanar arrangement. The higher the electron-withdrawing effect of the 2-aryl substituent, the larger was the stabilization for n(N)-sigma(C2)(-)(Ar), while the overlaps n(N)-sigma(C2)(-)(N) and n(N)-sigma(C2)(-)(H) changed in the opposite sense. The different polarization of the acceptor sigma orbitals, caused by the 2-aryl substituent, accounted for the observed propagation of the substituent effect. These results promote a detailed explanation of the useful tautomeric behavior of the 2-aryl-1,3-X,N-heterocycles, and reveal the nature of the connection between the anomeric effect and the Hammett-type linear free energy relationship.     

A facile synthesis of α-substituted thiophenes from a functionalized 2-aminothiophene by homo- and cross-coupling reactions

A series of new α-substituted thiophenes with elongated π-conjugation are prepared by homo- and cross-coupling reactions. An efficient one-step synthesis of a key intermediate, a substituted 2-iodothiophene, via aprotic diazotization of a Gewald-like 2-aminothiophene is reported.     

Thermal decomposition of maltitol spreads

The purpose of this study is to research the thermal properties of spreads with maltitol. Thermal characteristics of spreads depend on process parameters (temperature, mixer speed rotation). Spreads are produced at different temperatures (30, 35, and 40 °C) and mixer speed rotation (1, 1.33, and 1.67 Hz). The thermogravimetric method shows the peak position and determinate the spread composition. The temperature decomposition of sucrose and maltitol is two stages (two peaks), and palm fat has a single stage decomposition (one peak). Maltitol peak is dominant for spreads containing 100 and 70 % maltitol as a sweetener. This peak is sharper than sucrose peak and the inflection point is more expressed. Shape and the position of these peaks in spreads are modified. Peaks of maltitol, palm fat, and sucrose in spreads are lower and wider because of the grinding process and the interaction between spread ingredients. Increasing the process parameters (temperature, mixer speed rotation), temperatures of these peaks are higher (closer to temperature peak of pure ingredients). The dominant parameter is mixer speed rotation. The most thermally stable spreads with any amount of maltitol are produced at a temperature of 40 °C and high mixer speed rotation (1.33 and 1.67 Hz), while the least stable maltitol spreads are produced at minimum process parameters (30 °C, 1 Hz).     

A validated method for measurement of serum total,serum free,and salivary cortisol,using high-performance liquid chromatography coupled with high-resolutionESI-TOF mass spectrometry

Blood cortisol level is routinely analysed in laboratory medicine, but the immunoassays in widespread use have the disadvantage of cross-reactivity with some commonly used steroid drugs. Mass spectrometry has become a method of increasing importance for cortisol estimation. However, current methods do not offer the option of accurate mass identification. Our objective was to develop a mass spectrometry method to analyse salivary, serum total, and serum free cortisol via accurate mass identification. The analysis was performed on a Bruker micrOTOF high-resolution mass spectrometer. Sample preparation involved protein precipitation, serum ultrafiltration, and solid-phase extraction. Limit of quantification was 12.5 nmol L^?1 for total cortisol, 440 pmol L^?1 for serum ultrafiltrate, and 600 pmol L^?1 for saliva. Average intra-assay variation was 4.7 %, and inter-assay variation was 6.6 %. Mass accuracy was <2.5 ppm. Serum total cortisol levels were in the range 35.6–1088 nmol L^?1, and serum free cortisol levels were in the range 0.5–12.4 nmol L^?1. Salivary cortisol levels were in the range 0.7–10.4 nmol L^?1. Mass accuracy was equal to or below 2.5 ppm, resulting in a mass error less than 1 mDa and thus providing high specificity. We did not observe any interference with routinely used steroidal drugs. The method is capable of specific cortisol quantification in different matrices on the basis of accurate mass identification.