On equilibrium intensive thermodynamic properties of composed p‐particles in many‐body systems

Equilibrium intensive thermodynamic properties of p‐particles (p‐ons), i.e., composed particles formed by few particles of the same nature such as fermion or boson pairs (p=2), trios (p=3), etc., are investigated. The relation of the p‐particle correlation functions to its p‐hole counterparts and an existing covariant structure in the hierarchy of the p‐particle correlation functions allow these generalized intensive properties to be properly defined and characterized. The connection between these generalized properties of the composed objects and those of the components is also derived. An explicit derivation of the chemical potential for pairs and its generalization to p‐particles is performed. Such results are further extended to any intensive property. Finally, the present development allows some previous results to be clearly interpreted thus yielding an important support for our theory. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem 85: 63–71, 2001     

Geminal approach to vibronic models of superconductivity in crystals. I. The Jahn–Teller effect

Electronic geminals constructed as linear combinations of binary products of site functions are used to formulate a vibronic model of superconductivity in crystals that is based upon the approximation of independent correlated electron pairs obtained variationally from an electron‐pair Hamiltonian and the Jahn–Teller effect. The cyclic symmetry of the system is taken into account and the geminals are sorted into doubly degenerate pairs. The Herzberg–Teller expansion of the pair Hamiltonian in terms of vibrational modes leads directly to the Jahn–Teller effect. A contact transformation of the vibronic Hamiltonian containing only linear terms lowers the energy of the system by a second‐order term associated with the Jahn–Teller stabilization energy. A possible model for superconductivity in solids is proposed on the basis of the Jahn–Teller effect. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2003     

Nematic–isotropic phase behaviors of polydisperse polymer/liquid‐crystal systems: Chain‐length‐dependent interaction parameter

Phase behaviors of polydisperse polystyrene (PS)/nematic liquid‐crystal systems [P‐ethoxy ‐ benzylidene ‐ p ‐ n‐butylaniline (EBBA)] are investigated with a thermo‐optical analysis technique. We also develop a thermodynamic framework to describe the phase behaviors of polydisperse PS/EBBA systems. The proposed model is based on a modified double‐lattice model to describe isotropic mixing and Maier–Saupe theory for anisotropic ordering. To correlate the polymer chain length and energy parameters in a nematic–isotropic biphasic region and to apply the primary interaction parameter in an isotropic–isotropic phase‐transition behaviors of polydisperse PS/EBBA systems. The proposed model shows remarkable agreement with experimental data for the model systems in comparison with an existing model. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1031–1039, 2006     

Preparation of new π‐conjugated polypyrroles by organometallic polycondensations. Synthesis of N‐BOC (t‐butoxycarbonyl) and N‐phenylethynyl polymers,thermal deprotection of the BOC Group,and packing structure of the N‐phenylethynyl polymer

New π–conjugated polypyrroles such as poly(3‐heptyl‐N‐(t‐butoxycarbonyl)pyrrole‐2,5‐diyl), PPr(3‐Hep; N‐BOC) , and poly(N‐(phenylethynyl)pyrrole‐2,5‐diyl‐alt‐thiophene‐2,5‐diyl), Copoly‐2 , were prepared by organometallic polycondensations using the corresponding 2.5‐dihalopyrroles as the starting materials. Deprotection of the BOC group of PPr(3‐Hep; N‐BOC) proceeded at 185 °C to give poly(3‐heptylpyrrole). XRD (X‐ray diffraction) data of Copoly‐2 indicated that Copoly‐2 assumed a stacked structure in the solid. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 6223–6232, 2005     

Erratum: On equilibrium intensive thermodynamic properties of composed p‐particles in many‐body systems*

Equilibrium intensive thermodynamic properties of p‐particles (p‐ons), i.e., composed particles formed by few particles of the same nature such as fermion or boson pairs (p=2), trios (p=3), etc., are investigated. The relation of the p‐particle correlation functions to its p‐hole counterparts and an existing covariant structure in the hierarchy of the p‐particle correlation functions allow these generalized intensive properties to be properly defined and characterized. The connection between these generalized properties of the composed objects and those of the components is also derived. An explicit derivation of the chemical potential for pairs and its generalization to p‐particles is performed. Such results are further extended to any intensive property. Finally, the present development allows some previous results to be clearly interpreted thus yielding an important support for our theory. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001     

Periodic organic–organometallic microdomain structures in poly(styrene‐block‐ferrocenyldimethylsilane) copolymers and blends with corresponding homopolymers

A series of poly(styrene‐block‐ferrocenyldimethylsilane) copolymers (SF) with different relative molar masses of the blocks were prepared by sequential anionic polymerization. The bulk morphology of these polymers, studied by TEM and SAXS, showed well‐ordered lamellar and cylindrical domains as well as disordered micellar structures. Temperature‐dependent rheological measurements exhibited an order–disorder transition for SF 17/8 (the numbers refer to the relative molar masses in 10³ g/mol) between 170 and 180°C, and an order–order transition for SF 9/19 between 190 and 200°C. The morphologies of binary blends of the diblocks with homopolymer were also investigated. In the blends the molar mass of the homopolymer was always less than the molar mass of the matching block. Ordered spheres on a bcc lattice and double‐gyroid morphology were observed for the blends. The double‐gyroid morphology was found only in F‐rich diblock/homopolymer systems. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1009–1021, 1999     

Relation between BCS Hamiltonian and Ginzburg–Landau equation

It is intended to derive the Ginzburg–Landau (GL) equation directly from the Bardeen–Cooper–Schrieffer (BCS) Hamiltonian. By the use of the Hubbard–Stratonovitch transformation, the electron–electron interaction composed of four fermion operators is eliminated to yield an auxiliary boson field. This is an effective field in which electrons behave as if they were free. In applying the path integral method, the electron field is integrated out to remain the Lagrangian for this boson field. The symmetry breaking and the phase transition of the system described by this field are discussed, and it is shown that this boson field turns out to be the GL order parameter. © 1998 John Wiley & Sons, Inc. Int J Quant Chem 69: 693–703, 1998     

Branching by reactive end groups. III. Synthesis,branching, and analysis of m‐ethynylphenol/p‐t‐butylphenol‐coterminated bisphenol a polycarbonates

The use of m‐ethynylphenol (m‐EP) and p‐t‐butylphenol (PTBP) as coterminators for bisphenol A polycarbonates (BA PCs) provided long‐chain‐branched PCs, partially crosslinked PCs, or both after the thermal reaction of the terminal m‐EP groups, depending on the molar ratio of the chain terminators. Linear m‐EP/PTBP PCs were prepared by solution phosgenation of BA and the two coterminators. Differential scanning calorimetry showed the onset of the m‐EP‐end‐group reaction at about 250 °C by the appearance of a reaction exotherm. The enthalpy (ΔH) of this reaction was roughly proportional to the amount of m‐EP in the PC and to an extent could be used to monitor the progress of the reaction and estimate its kinetics. A complete m‐EP‐end‐group reaction was evident from gel permeation chromatography analysis upon heating under N₂ to 380 °C for 10 min or 360 °C for 60 min. The amount, if any, of gel formed after the m‐EP‐end‐group reaction depended on X_EP; those PCs with a X_EP value less than or equal to 0.33 had little or no gel. The maximum X_EP that precluded the formation of gels after branching was estimated to be about 0.45–0.48. The molecular weight of m‐EP/PTBP PCs increased after branching, as evidenced by gel permeation chromatography analysis. Assuming that the terminal m‐EP groups had a statistical distribution on the polymer chain ends and that they underwent only homopolymerization, the average reacted m‐EP‐group functionality according to estimated gel‐point composition was about 2.8–3.0. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2352–2358, 2000     

Examining the kinetics of the thermal polymerization of commercial aromatic bis‐benzoxazines

Three commercial bis‐benzoxazine monomers based on the aniline derivatives of bisphenol A (BA‐a), bisphenol F (BF‐a), and 3,3′‐thiodiphenol (BT‐a) are examined using a variety of spectroscopic, chromatographic, and thermomechanical techniques. The kinetics of the polymerization of BA‐a were found to be well described using an autocatalytic model for which values of n = 1.39 and m = 2.49 were obtained for the early and later stages of reaction respectively (activation energy = 81–88 kJ/mol.). Following recrystallization the same monomer yielded values of n = 1.80, m = 0.92, and E_a = 94–97 kJ/mol. BF‐a and BT‐a were also found to be well described using an autocatalytic model for which values of n = m = 2.11 (BF‐a) and n = 2.10, m = 1.47 (BT‐a) were obtained for the early and later stages of reaction (activation energy = 80–84 kJ/mol. for BF‐a and 88–95 kJ/mol. for BT‐a). The kinetic data are compared with parallel studies involving chemically initiated benzoxazine monomers. Molecular simulation is used to examine the rotational freedom of the central bridging units and this is related to the degree of conversion achieved. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2068–2081     

Decomposition of model alkoxyamines in simple and polymerizing systems. II. Diastereomeric N‐(2‐methylpropyl)‐N‐(1‐diethyl‐phosphono‐2,2‐dimethyl‐propyl)‐aminoxyl‐based compounds

Thermal reactions of the alkoxyamine diastereomers DEPN‐R′ [DEPN: N‐(2‐methylpropyl)‐N‐(1‐diethylphosphophono‐2,2‐dimethyl‐propyl)‐aminoxyl; R′: methoxy‐carbonylethyl and phenylethyl] with (R,R) + (S,S) and (R,S) + (S,R) configurations have been investigated by ¹H NMR at 100 °C. During the overall decay the diastereomers interconvert, and an analytical treatment of the combined processes is presented. Rate constants are obtained for the cleavage and reformation of DEPN‐R′ from NMR, electron spin resonance, and chemically induced dynamic nuclear polarization experiments also using 2,2,6,6‐tetramethylpiperidinyl‐1‐oxyl (TEMPO) as a radical scavenger. The rate constants depend on the diastereomer configuration and the residues R′. Simulations of the kinetics observed with styrene and methyl methacrylate containing solutions yielded rate constants for unimeric and polymeric alkoxyamines DEPN‐(M)_n‐R′. The results were compatible with the known DEPN mediation of living styrene and acrylate polymerizations. For methyl methacrylate the equilibrium constant of the reversible cleavage of the dormant chains DEPN‐(M)_n‐R′ is very large and renders successful living polymerizations unlikely. Mechanistic and kinetic differences of DEPN‐ and TEMPO‐mediated polymerizations are discussed. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3264–3283, 2002     

Hydrogen Peroxide Enhances the Antibacterial Effect of Methylene Blue‐based Photodynamic Therapy on Biofilm‐forming Bacteria

Recently, increased attention has been focused on endoscopic disinfection after outbreaks of drug‐resistant infections associated with gastrointestinal endoscopy. The aims of this study were to investigate the bactericidal efficacy of methylene blue (MB)‐based photodynamic therapy (PDT) on Pseudomonas aeruginosa (P. aeruginosa), which is the major cause of drug‐resistant postendoscopy outbreak, and to assess the synergistic effects of hydrogen peroxide addition to MB‐based PDT on biofilms. In planktonic state of P. aeruginosa, the maximum decrease was 3 log₁₀ and 5.5 log₁₀ at 20 and 30 J cm^?2, respectively, following MB‐based PDT. However, the maximum reduction of colony forming unit (CFU) was decreased by 2.5 log₁₀ and 3 log₁₀ irradiation on biofilms. The biofilm formation was significantly inhibited upon irradiation with MB‐based PDT. When the biofilm state of P. aeruginosa was treated with MB‐based PDT with hydrogen peroxide, the CFU was significantly decreased by 6 log₁₀ after 20 J cm^?2, by 7 log₁₀ after 30 J cm^?2 irradiation, suggesting significantly higher efficacy than MB‐based PDT alone. The implementation of the combination of hydrogen peroxide with MB‐based PDT through working channels might be appropriate for preventing early colonization and biofilm formation in the endoscope and postendoscopy outbreak.     

Enhanced interfacial interaction by grafting carboxylated‐macromolecular chains on nanodiamond surfaces for epoxy‐based thermosets

A novel core‐shell‐structured carboxylated‐styrene butadiene rubber (XSBR)‐functionalized nanodiamond (ND‐XSBR) was synthesized and characterized. Epoxy (EP) nanocomposites toughened by pristine ND and ND‐XSBR were investigated and compared. The ND‐XSBR‐reinforced nanocomposite exhibited mechanical properties superior to those of the one filled by pristine ND. At a low‐filler loading, the ND‐XSBR exhibited an impressive toughening effect. The maximum flexural strength was shown when the filler loading was as low as 0.1 wt % for the EP/ND‐XSBR nanocomposite. Furthermore, enhanced fracture toughness and fracture energy were shown by surface functionalization, representing enhanced compatibility between the ND‐XSBR and EP matrix. The glass transition temperature (T_g) and storage modulus of the nanocomposites were studied, and the EP/ND‐XSBR0.1 nanocomposite exhibited the highest T_g owing to the stronger interfacial interaction. The EP/ND‐XSBR0.2 exhibited higher storage modulus and T_g than the EP/ND0.2, because the higher interfacial interaction can restrict the molecular mobility of the EP by the functionalized ND‐XSBR. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1890–1898     

Active‐center equilibrium in Ziegler–Natta butadiene polymerization

The Ziegler–Natta‐catalyzed polymerization of 1,3‐butadiene was investigated at a low aluminum alkyl/cobalt (Al/Co) ratio using two different soluble catalyst systems: cobalt(II) octanoate/diethylaluminum chloride/water and cobalt(II) octanoate/methylaluminoxane/tert‐butyl chloride. When the active‐center concentration was determined by the number‐average molecular weight technique, it was found that the percentage of active cobalt depended on the Al/Co ratio. Subsequently, an equilibrium reaction was proposed to be Co + 2Al ? CoAl₂, where Co is cobalt(II) octanoate, Al is either of the aluminum alkyl‐activator species, and CoAl₂ is the active catalyst. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2256–2261, 2001     

Decomposition of model alkoxyamines in simple and polymerizing systems. I. 2,2,6,6‐tetramethylpiperidinyl‐ N‐oxyl‐based compounds

The thermal decomposition of five alkoxyamines labeled TEMPO–R, where TEMPO was 2,2,6,6‐tetramethylpiperidinyl‐N‐oxyl and R was cumyl (Cum), 2‐tert‐butoxy‐carbonyl‐2‐propyl (PEst), phenylethyl (PhEt), 1‐tert‐butoxy‐carbonylethyl (EEst), or 1‐methoxycarbonyl‐3‐methyl‐3‐phenylbutyl (Acrylate‐Cum), was studied with ¹H NMR in the absence and presence of styrene and methyl methacrylate. The major products were alkenes and the hydroxylamine 1‐hydroxy‐2,2,6,6‐tetramethyl‐ piperidine (TEMPOH), and in monomer‐containing solutions, unimeric and polymeric alkoxyamines and alkenes were also found. Furthermore, the reactions between TEMPO and the radicals EEst and PEst were studied with chemically induced dynamic nuclear polarization. In comparison with coupling, TEMPO reacted with the radicals Cum, PEst, PhEt, and EEst and their unimeric styrene adducts by disproportionation to alkenes and TEMPOH only to a minor extent (0.6–3%) but with the radical adducts to methyl methacrylate to a considerable degree (≥20%). Parallel to the radical cleavage, TEMPO–EEst (but not the other alkoxyamines or TEMPO–Acrylate‐Cum) underwent substantial nonradical decay. The consequences for TEMPO‐mediated living radical polymerizations are discussed. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3604–3621, 2001     

Assessment of errors in the determination of Mark–Houwink–Sakurada and Stockmayer–Fixman constants using size‐exclusion chromatography with on‐line viscometric detection: Analyses of poly(p‐substituted styrenes) in tetrahydrofuran

In this work, we present values for the Mark–Houwink–Sakurada (MHS) and Stockmayer–Fixman (SF) constants for a series of homopolymers of para‐substituted styrenes (4‐X‐styrene; X = OCH₃, OCH₂CH₃, CH₃, F, Cl, and Br) in THF at room temperature. The respective values of K (in 10⁻⁵ dL/g) and α were: 0.685 and 13.2; 0.662 and 14.1; 0.740 and 8.41; 0.781 and 5.24; 0.726 and 8.95; 0.700 and 7.79. The respective values for K_θ (in 10⁻⁴ dL/g) and K' (in 10⁻⁷ dL/g) were: 6.01 and 16.1; 6.22 and 9.07; 7.64 and 17.4; 5.59 and 23.7; 6.29 and 17.3; 4.44 and 10.3. These constants were measured using size‐exclusion chromatography with on‐line viscometry. As part of this work, we investigate the applicability of common model fitting procedures to this method of measuring MHS/SF constants and the effect of uncertainties in their estimated values on the accuracy of molecular weight analysis. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2557–2570, 1999     

Highly stereo‐efficient synthesis and luminescence properties of novel trans‐regular vinylene– silylene–thiophene polymers

The novel trans‐stereo‐regular silylene–thiophene derivatives ( 4 , 5 ) with perfect consecutive silylene–arylene–silylene–vinylene linkage were synthesized via silylative coupling polycondensation of 2,5‐bis(vinyldimethylsilyl)thiophene ( 2 ) or 5,5′‐bis(vinyldimethylsilyl)‐2,2′‐bithiophene ( 3 ) catalyzed by ruthenium‐hydride complex [RuHCl(CO)(PCy₃)₂] ( 1 ). Their spectroscopic, absorption, and luminescence properties were characterized and compared with those of model compounds containing thiophene or bithiophene chromophores. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 127–137, 2008     

Predicting the accuracy of protein–ligand docking on homology models

Ligand–protein docking is increasingly used in Drug Discovery. The initial limitations imposed by a reduced availability of target protein structures have been overcome by the use of theoretical models, especially those derived by homology modeling techniques. While this greatly extended the use of docking simulations, it also introduced the need for general and robust criteria to estimate the reliability of docking results given the model quality. To this end, a large‐scale experiment was performed on a diverse set including experimental structures and homology models for a group of representative ligand–protein complexes. A wide spectrum of model quality was sampled using templates at different evolutionary distances and different strategies for target–template alignment and modeling. The obtained models were scored by a selection of the most used model quality indices. The binding geometries were generated using AutoDock, one of the most common docking programs. An important result of this study is that indeed quantitative and robust correlations exist between the accuracy of docking results and the model quality, especially in the binding site. Moreover, state‐of‐the‐art indices for model quality assessment are already an effective tool for an a priori prediction of the accuracy of docking experiments in the context of groups of proteins with conserved structural characteristics. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2010     

Preparation of Organometallic Ruthenium–Arene–Diaminotriazine Complexes as Binding Agents to DNA

The reactions of two diaminotriazine ligands 2,4‐diamino‐6‐(2‐pyridyl)‐1,3,5‐triazine (2‐pydaT) and 6‐phenyl‐2,4‐diamino‐1,3,5‐triazine (PhdaT) with ruthenium–arene precursors led to a new family of ruthenium(II) compounds that were spectroscopically characterized. Four of the complexes were cationic, with the general formula [(η⁶‐arene)Ru(κ²‐N,N‐2‐pydaT)Cl]X (X=BF₄, TsO; arene=p‐cymene: 1.BF4 , 1.TsO arene=benzene: 2.BF4 , 2.TsO ). The neutral cyclometalated complex [(η⁶‐p‐cymene)Ru(κ²‐C,N‐PhdaT*)Cl] ( 3 ) was also isolated. The structures of complexes 2.BF4 and 3.H2O were determined by X‐ray diffraction. Complex 1.BF4 underwent a partial reversible‐aquation process in water. UV/Vis and NMR spectroscopic measurements showed that the reaction was hindered by the addition of NaCl and was pH‐controlled in acidic solution. At pH 7.0 (sodium cacodylate) Ru–Cl complex 1.BF4 was the only species present in solution, even at low ionic strength. However, in alkaline medium (KOH), complex 1.BF4 underwent basic hydrolysis to afford a Ru–OH complex ( 5 ). Fluorimetric studies revealed that the interaction of complex 1.BF4 with DNA was not straightforward; instead, its main features were closely linked to ionic strength and to the [DNA]/complex ratio. The bifunctional complex 1.BF4 was capable of interacting concurrently through both its p‐cymene and 2‐pydaT groups. Cytotoxicity and genotoxicity studies showed that, contrary to the expected behavior, the complex species was biologically inactive; the formation of a Ru–OH complex could be responsible for such behavior.     

Synthesis and antiproliferative activity of (Z + E)‐1‐[4‐(2‐(cyclopentadienyltricarbonylmanganese)‐2‐oxo‐ethoxy)phenyl]‐1,2‐di(p‐hydroxyphenyl)‐but‐1‐ene against breast cancer cells

This paper describes the synthesis of (Z + E)‐1‐[4‐(2‐(cyclopentadienyltricarbonylmanganese)‐2‐oxo‐ethoxy)phenyl]‐1,2‐di(p‐hydroxyphenyl)‐but‐1‐ene. Two synthetic pathways were explored. The best pathway consisted of the alkylation of 1,2‐bis‐[4‐(tert‐butyl‐dimethylsilyloxy)phenyl]‐1‐(4‐hydroxyphenyl)but‐1‐ene with BrCH₂COOEt. The ester obtained was transformed into the Weinreb amide by reaction with HN(OMe)Me–HCl. The reaction of lithium manganese tricarbonylcyclopentadienide with the Weinreb amide produced 1‐[4‐(2‐(cyclopentadienyltricarbonylmanganese)‐2‐oxo‐ethoxy)phenyl]‐1,2‐di(p‐tert‐butyldimethylsiloxyphenyl)‐but‐1‐ene. The deprotection of phenolic functions of the latter compound led to the formation of the final compound. The Z and E isomers could be separated but the isomerization of these isomers from one to another is an easy process. The Z + E compound 2 was tested against the hormone‐dependent MCF‐7 and hormone‐independent MDA‐MB‐231 breast cancer cell lines. The IC₅₀ values of compound 2 were 4.80 ± 2.00 µm and 4.79 ± 0.70 µm for MCF‐7 cells and MDA‐MB‐231 cells, respectively, which was three times better than the ferrocenyl analogue. Copyright © 2012 John Wiley & Sons, Ltd.     

4‐Methoxyanilinium tetrafluoroborate–dibenzo‐18‐crown‐6 (1/1)

In the structure of the complex of dibenzo‐18‐crown‐6 [systematic name: 2,5,8,15,18,21‐hexaoxatricyclo[20.4.0.0^9,14]hexacosa‐1(26),9,11,13,22,24‐hexaene] with 4‐methoxyanilinium tetrafluoroborate, C₇H₁₀NO⁺·BF₄⁻·C₂₀H₂₄O₆, the protonated 4‐methoxyanilinium (MB‐NH₃⁺) cation forms a 1:1 supramolecular rotator–stator complex with the dibenzo‐18‐crown‐6 molecule via N—H...O hydrogen bonds. The MB‐NH₃⁺ group is attached from the convex side of the bowl‐shaped crown, in contrast with similar ammonium cations that nest in the curvature of the bowl. The cations are associated via C—H...π interactions, while the cations and anions are linked by weak C—H...F hydrogen bonds, forming cation–crown–anion chains parallel to [011].