Microwave-assisted and conventional synthesis and stereogenic properties of monospirocyclotriphosphazene derivatives

The reactions of hexachlorocyclotriphosphazene, N₃P₃Cl₆, with N/O donor type N-alkyl or (aryl)-o-hydroxybenzylamines HO(C₆H₄)CH₂NHR(Ar), [R(Ar) = C(CH₃)₃ (1), Ph (2)] produce monospirocyclic tetrachlorocyclotriphosphazenes (1a and 2a). The geminal substituted cyclotriphosphazenes (1b, 1d, 2b and 2d) are obtained from the reactions of 1 equiv. of 1a and 2a with 2 equiv. of pyrrolidine or morpholine in THF, while the fully substituted phosphazenes (1c, 1e, 2c and 2e) are formed from the reactions of 1a and 2a with the excess pyrrolidine or morpholine in toluene, between 24 and 48 h. The microwave-assisted reactions of 1a and 2a with excess pyrrolidine or morpholine in toluene afford the fully substituted products with higher yields than those which were obtained by conventional methods. The structural investigations of the compounds have been verified by elemental analyses, ESI-MS, FTIR, ¹H, ¹³C, ³¹P NMR and HETCOR techniques. The crystal structure of 2a is determined by X-ray crystallography and the phosphazene ring is in the flattened boat form. Compounds 1b, 1d, 2b and 2d in which the spiro aryloxy moiety provides the one centre of chirality exist as racemates and the chirality has been confirmed by ³¹P NMR spectroscopy on addition of a chiral solvating agent (CSA), (S)-(+)-2,2,2-trifluoro-1-(9′-anthryl)ethanol.     

Asymptotic properties of a new Sturm–Liouville problem with retarded argument

In this work, we study the asymptotic properties of a new Sturm–Liouville problem with retarded argument. Contrary to previous works, differential equation includes eigenparameter as a quadratic function. In the considered problem arise new difficulties. Copyright © 2013 John Wiley & Sons, Ltd.     

High density cationic polymer brushes from combined “click chemistry” and RAFT‐mediated polymerization

A simple method for preparing cationic poly[(ar‐vinylbenzyl)trimethylammonium chloride)] [poly(VBTAC)] brushes was used by combined technology of “click chemistry” and reversible addition‐fragmentation chain transfer (RAFT) polymerization. Initially, silicon surfaces were modified with RAFT chain transfer agent by using a click reaction involving an azide‐modified silicon wafer and alkyne‐terminated 4‐cyanopentanoic acid dithiobenzoate (CPAD). A series of poly(VBTAC) brushes on silicon surface with different molecular weights, thicknesses, and grafting densities were then synthesized by RAFT‐mediated polymerization from the surface immobilized CPAD. The immobilization of CPAD on the silicon wafer and the subsequent polymer formation were characterized by X‐ray photoelectron spectroscopy, water contact angle measurements, grazing angle‐Fourier transform infrared spectroscopy, atomic force microscopy, and ellipsometry analysis. The addition of free CPAD was required for the formation of well‐defined polymer brushes, which subsequently resulted in the presence of free polymer chains in solution. The free polymer chains were isolated and used to estimate the molecular weights and polydispersity index of chains attached to the surface. In addition, by varying the polymerization time, we were able to obtain poly(VBTAC) brushes with grafting density up to 0.78 chains/nm² with homogeneous distributions of apparent needle‐like structures. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Paramagnetic contribution of serum iron to the spin-spin relaxation rate (1/T 2) measured by MRI

Spin-spin relaxation timeT ₂ values of serum with and without iron were measured by magnetic resonance imaging (MRI) to find the proton relaxivity of Fe(III) in serum.T ₂ values in serum containing definite amounts of added iron were also measured before and after addition of ascorbic acid. The difference in the 1/T ₂ of serum with and without ascorbic acid was used for recalculation of the added iron values. Recalculated iron values confirm that the difference in healthy serum is caused by iron only. In addition, in order to find the paramagnetic contribution of serum iron,T ₂ values of iron-deficient, healthy and iron-overloaded serum were measured before and after addition of ascorbic acid. The difference in the 1/T ₂ values was then applied to the calculation of the serum iron values. The consistency of iron values determined from the difference to those by autoanalyzer suggests that the differences in diseased serum also represent the paramagnetic contribution of serum iron. The data imply that serum iron content in healthy, iron-deficient and iron-overloaded serum may be assessed by MRI.     

In vitro evaluation of apoptosis detection by 99mTc-tetrofosmin in MCF-7 breast cancer cell line

Radiolabeled molecules have an important role to evaluate tumor characteristics such as aggressiveness, and to identify the effectiveness of cancer treatments such as chemotherapy and radiotherapy. Various radionuclide (¹⁸F, ^99mTc, ¹²⁴I) labeled molecules can be used apoptosis detection by estimating decrescendos cell viability after therapy. ^99mTc-tetrofosmin which is used as a myocardial perfusion imaging agent in routine and at the same time is known to accumulate in various tumors including breast tumor. The aim of this study was to assess the utility of ^99mTc-tetrofosmin for monitoring the early response of MCF-7 breast cancer to chemotherapy. To evaluate the role of ^99mTc-tetrofosmin in vitro chemotherapy, the uptake ratio was determined using MCF-7 breast cancer line after the cells had been treated with cisplatin. When we examined the apoptotic ratios which induced with different dose of cisplatin in MCF-7 breast cancer cells by using Annexin V and TUNEL methods, it was observed that the rate of apoptosis increased with soaring dose. The uptake rates of ^99mTc-tetrofosmin in MCF-7 cell line in the chemotherapeutic groups were lower than it is in the control group (p < 0.01). The negative correlation between uptake ratios and apoptotic rates shows that ^99mTc-tetrofosmin may be used a radiopharmaceutical for evaluating chemotherapy response. ^99mTc-tetrofosmin might be probably useful as an imaging agent for estimation of early chemotherapy response in breast cancer.     

The maximum surplus in a finite‐time interval for a discrete‐time risk model with exchangeable,dependent claim occurrences

This paper investigates a discrete‐time risk model that involves exchangeable dependent loss generating claim occurrences and compound binomially distributed aggregate loss amounts. First, a general framework is presented to derive the distribution of a surplus sequence using the model. This framework is then applied to obtain the distribution of any function of a surplus sequence in a finite‐time interval. Specifically, the distribution of the maximum surplus is obtained under nonruin conditions. Based on this distribution, the computation of the minimum surplus distribution is given. Asset and risk management–oriented implications are discussed for the obtained distributions based on numerical evaluations. In addition, comparisons are made involving the corresponding results of the classical discrete‐time compound binomial risk model, for which claim occurrences are independent and identically distributed.     

${[\ell_p]}_{e.r}$ Euler-Riesz Difference Sequence Spaces

Başar and Braha [1], introduced the sequence spaces $\breve{\ell}_\infty$, $\breve{c}$ and $\breve{c}_0$ of Euler-Cesáro bounded, convergent and null difference sequences and studied their some properties. Then, in [2], we introduced the sequence spaces ${[\ell_\infty]}_{e.r}, {[c]}_{e.r}$ and ${[c_0]}_{e.r}$ of Euler-Riesz bounded, convergent and null difference sequences by using the composition of the Euler mean $E_1$ and Riesz mean $R_q$ with backward difference operator $\Delta$. The main purpose of this study is to introduce the sequence space ${[\ell_p]}_{e.r}$ of Euler-Riesz $p-$absolutely convergent series, where $1 \leq p <\infty$, difference sequences by using the composition of the Euler mean $E_1$ and Riesz mean $R_q$ with backward difference operator $\Delta$. Furthermore, the inclusion $\ell_p\subset{[\ell_p]}_{e.r}$ hold, the basis of the sequence space ${[\ell_p]}_{e.r}$ is constructed and $\alpha-$, $\beta-$ and $\gamma-$duals of the space are determined. Finally, the classes of matrix transformations from the ${[\ell_p]}_{e.r}$ Euler-Riesz difference sequence space to the spaces $\ell_\infty, c$ and $c_0$ are characterized. We devote the final section of the paper to examine some geometric properties of the space ${[\ell_p]}_{e.r}$.     

Assessing the Impact of Bridging Analogies in Mechanics

The effects of bridging analogies teaching strategy and gender on Turkish high school students' misconceptions in mechanics were investigated. After a pilot study with 67 students in a nearby high school, the researchers administered the revised Mechanics Misconception Test to 119 high school students as a pretest. Students in the experimental group were instructed by using bridging analogies teaching strategy. At the end of a 3‐week treatment period, the same test was administered to all students as a posttest. The data were analyzed by using analysis of covariance (ANCOVA). The statistical results showed that bridging analogies teaching strategy was an effective means of reducing the number of misconceptions students held about normal forces, frictional forces, tension, gravity, inertia, and Newton's third law.     

Photoinduced magnetism caused by charge-transfer excitations in tetracyanoethylene-based organic magnets

The photoinduced magnetism in Mn-tetracyanoethylene (TCNE) molecule-based magnets is ascribed to charge-transfer excitations from manganese to TCNE. Charge-transfer energies are calculated using density functional theory; photoinduced magnetization is described using a model Hamiltonian based on a double-exchange mechanism. Photoexciting electrons from the manganese core spins into the lowest unoccupied orbital of TCNE with photon energies around 3 eV increase the magnetization through a reduction of the canting angle of the manganese core spins for an average electron density on TCNE less than one. When photoexciting with a smaller energy, divalent TCNE molecules are formed. The delocalization of the excited electron causes a local spin flip of a manganese core spin.