Charge transfer complexes as dual thermal/photo initiators for free-radical frontal polymerization

Frontal polymerization is a process in which a localized reaction zone propagates from the coupling of thermal transport and the Arrhenius rate dependence of an exothermic polymerization; monomer is converted into polymer as the front passes through an unstirred medium. Herein we report the first study of charge transfer complexes (CTCs) as photo/thermal initiators for free-radical frontal polymerization. Front velocity was studied as a function of mole ratio between an aromatic amine, such as dimethyl-p-toluidine or dimethylaniline, and an iodonium salt. It was found that the front velocity reached a maximum at a certain mole ratio of amine to iodonium salt. The velocity remained constant upon increasing the ratio of amine to iodonium salt past this critical ratio. Fronts were also studied using N-phenyl glycine as an electron donor, but its utility was limited by low solubility. Lastly, the steric and electronic effects of the iodonium salt and counter anion were explored. It was found that CTCs using iodonium salts with less nucleophilic anions gave higher front velocities. In terms of intrinsic reactivity, the CTC composed of N,N-dimethyl-p-toluidine and bis[4-(tert-butyl)phenyl]iodonium tetra(nonafluoro-tert-butoxy)aluminate gave the highest front velocity per molal of iodonium salt.     

Charge transfer complexes of N-ethylcarbazole and poly-N-vinylcarbazole

Poly-N-vinylcarbazole and its monomeric analog, i.e., N-ethylcarbazole, act as donors in charge transfer complexes with such electron acceptors as iodine, tetracyanoethylene, and tetracyanoquinodimethane. Poly-N-vinylcarbazole and N-ethylcarbazole are also capable of accepting electrons from an alkali metal such as sodium. A study of the spectral properties of both types of complexes showed that the monomer can both accept and donate electrons to a greater extent than the corresponding unit segment of the polymer chain. Equilibrium constants are presented for both cases, and estimates of the ionization potential of N-ethylcarbazole and related compounds are made from the characteristic charge transfer frequencies. Good agreement between these values and those calculated from molecular orbital theory is outlined.     

Charge transfer complexes and salts of ionenes

A review of the synthesis and properties of ionenes is presented. Particular attention is paid to the electrical and related properties of conductive teteracyano-p-quinodimethane (TCNQ) complex salts of ionenes containing ammonium or sulfonium groups in the main chain and to their chemical stability. The recent work on preparation of such ionenes with inorganic and organic counterions which show interesting linear and nonlinear optical properties is also discussed. It is shown that in the solid state ionenes act as a kind of a matrix fixing, in a chemically controlled way, positions and distribution of different kinds of counterions. Because the reaction of counterion exchange is easy in the case of ionenes it provides a convenient way to prepare a broad class of polyelectrolytes with many different properties.     

电荷转移褪色光度法测定头孢哌酮钠的含量

利用荷移反应测定药物的含量，近年来已有广泛的应用。本文研究了头孢哌酮钠和苯基荧光酮在甲醇介质中的电荷转移反应，该反应为褪色反应，确定了最佳反应条件，与文献方法相比，具有方便、快捷、重复性好等优点。     

Charge transfer complexes and cation radical salts of azino-diselenadiazafulvalene

The synthesis and the redox behaviour of electroactive donor molecules incorporating an azino spacer group between a benzoselenazole core and another heterocyclic moiety, either a benzoselenazole one or a thiazole one, are reported. Neutral complexes were obtained with TCNQ and, for the first time with dithiadiazafulvalene or diselenadiazafulvalene derivatives, cation radical salts by electrocrystallization. Crystal structures data of these complexes are presented and their geometries compared with those deduced from theoretical calculations.     

Charge transfer complexes of picolines with sigma- and pi-acceptors

In the present study CT complexes of 2-, 3- and 4-Picolines with (DDQ) 2, 3-dichloro-5, 6-dicyano parabenzoquinone (pi-acceptor) and (I(2)) Iodine (sigma-acceptor) have been investigated spectrophotometrically in three different solvents (CCl(4), CHCl(3) and CH(2)Cl(2)) at six different temperatures. The formation constants of the CT complexes were determined by the Benesi-Hildebrand equation. The thermodynamic parameters were calculated by Van(')t Hoff equation. The DeltaH degrees , DeltaG degrees and DeltaS degrees values are all negative implying that the formation of studied complexes is exothermic in nature.     

Spectroscopic method for the determination of crystallinity of hematite

The thermal transformation of goethite to hematite and the temperature dependence of the degree of crystallinity have been investigated using transmission and diffraction electron microscopy and infrared spectroscopy. The electron microscopy results reveal that the treatment of natural goethite by NaOH or citrate dithionite-bicarbonate (CDB) has no effect on its structure but leads to increase in the crystallinity of the ore. On the other hand, heat treatment of the untreated or treated sample is found to convert goethite ore to hematite with increase in its crystallinity. An infrared spectroscopic technique is applied for quantitative calculation of the crystallinity changes.     

Selective liquid chromatographic method for determination of fluoxetine in plasma.

A selective and sensitive liquid chromatographic method was developed for the determination of fluoxetine (FLU) in plasma. FLU was isolated from plasma by liquid-liquid extraction. The chromatographic separation was performed on an analytical 250 x 3.9 mm id Novapak C18 column (4 microm particle size) with an isocratic mobile phase consisting of phosphate buffer-acetonitrile-methanol -triethylamine (58 + 30 + 10 + 2, v/v) adjusted to pH 7. Using UV detection at 226 nm, the detection limit for FLU in plasma was 3 ng/mL. No interferences were found with tricyclic antidepressant drugs, which allows this method to be used in clinical studies. The calibration curve was linear over the concentration range of 10-200 ng/mL. The average recovery was about 80% for plasma. The inter- and intraday assay coefficients of variation were <8%.     

Spectrophotometric microdetermination of anti-Parkinsonian and antiviral drug amantadine HCl in pure and in dosage forms

Two simple, rapid, sensitive, low-cost, and accurate methods (A and B) for the microdetermination of amantadine HCl (AMD) in pure form and in pharmaceutical formulations are developed. Method A is based on the formation of tris (o-phenanthroline)-iron(II) complex (ferroin) upon reaction of amantadine HCl with an iron (III)-o-phenanthroline mixture in sodium acetate-acetic acid buffer media. The ferroin complex is spectrophotometrically measured at λ_max 509 nm against reagent blank. Method B is based on the reduction of Fe (III) by the drug which forms colored complex (λ_max 521 nm) with 2,2′-bipyridyl. Optimizations of the experimental conditions are described. Beer’s law is obeyed in the concentration ranges 0.4–10 and 0.6–22 μg mL^?1 using 1,10-phenanthroline and 2,2′-bipyridyl, respectively. The developed methods have been successfully applied for the determination of AMD in bulk drugs and in pharmaceutical formulations. The common excipients and additives did not interfere in their determinations.     

Spectroscopic analysis of charge transfer complexes between morpholine and iodine.

It has been demonstrated spectroscopically that many nitrogen-containing heterocyclic compounds can form charge transfer complexes with iodine. The complexes of morpholine with iodine were shown to be of the n-sigma type with a 1:1 stoichiometry. A strong donor-acceptor interaction was found (Kc = 1261 +/- 12 mol-1 at 20 degrees C in CCl4), considerably higher than those of complexes of aromatic compounds with iodine. The high value of the formation constant for this complex indicated that morpholine could serve as a starting point for the synthesis of novel anti-thyroid drugs.     

Spectroscopic studies of charge transfer complexes between colchicine and some pi acceptors

Charge transfer complexes between colchicine as donor and pi acceptors such as tetracyanoethylene (TCNE), 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ), p-chloranil (p-CHL) have been studied spectrophotometrically in dichloromethane at 21 degrees C. The stoichiometry of the complexes was found to be 1:1 ratio by the Job method between donor and acceptors with the maximum absorption band at a wavelength of 535, 585 and 515 nm. The equilibrium constant and thermodynamic parameters of the complexes were determined by Benesi-Hildebrand and van't Hoff equations. Colchicine in pure form and in dosage form was applied in this study. The formation constants for the complexes were shown to be dependent on the structure of the electron acceptors used.     

Charge transfer across a polymer gel/liquid interface: determination of ionophores

An electrochemical method for the determination of the ionophores monensin and lasalocid was developed, based on the polarization of an agar gel/nitrobenzene electrolyte interface. The measured current corresponding to the facilitated ion transfer across this interface is directly proportional to the concentration of an ionophore dissolved in the organic phase. Using cyclic voltammetry in a three-electrode system the detection limit for both ionophores is about 3 × 10^?5 M.     

Charge transfer spectra of organometallic complexes V : complexes of dialkyltindiiodides and alkyltintriiodides with I2 in CCl4 solution

Thermodynamic and spectrophotometric data collected for [R₂SnI₂:I₂] and [RSnI₃:I₂] molecular complexes with R = Me, Et, n.Prop and n.Bu are discussed in terms of Mulliken Second Order Perturbation Theory.     

Charge transfer in porphyrin-calixarene complexes: ultrafast kinetics, cyclic voltammetry, and DFT calculations

Transient absorption spectroscopy, cyclic voltammetry, and DFT calculations were used to describe charge transfer processes in a series of 5,10,15,20-tetrakis(N-methylpyridinium-n-yl) porphyrins (TMPyPn, n = 4,3,2) and TMPyPn/p-sulfonatocalix[m]arene (clxm, m = 4,6,8) complexes. Excitation of TMPyPn is accompanied by an increasing electron density at the methylpyridinium substituents in the order TMPyP2 < TMPyP3 < TMPyP4. The quenching of the excited singlet states of the complexes increases with the number of ionized phenolic groups of clxm and can be correlated with the partial transfer of the electron density from O(-) to the peripheral methylpyridinium substituents rather than to the porphyrin ring.     

Charge transfer complexes between 4,4′-disubstituted diphenyldiacetylenes: experimental and theoretical study

Novel charge transfer (CT) complexes containing donor and acceptor derivatives of diphenyldiacetylene have been synthesised and characterised. The structure of CT complexes was modelled at the B3LYP/6-31G(d)//B3LYP/6-31G(d) level of theory. It was found that the complex formation is mainly due to dipole–dipole interaction between side groups of diacetylene molecules and there was no significant charge transfer between donor and acceptor in the ground state. On the other hand, optical excitation of CT complexes leads to strong charge transfer from donor to acceptor molecule as followed from the modelling using time-dependent density functional theory (DFT) method. Diacetylene molecules adopt strongly bent configuration in CT complexes which is prohibitive for solid-state topochemical polymerisation of diacetylenes     

Spectroscopic and thermal characterization of biologically and anticancer active novel Schiff base metal complexes

The novel Schiff base ligand 2,2′-((1Z,1′Z)-(1,3-phenylenebis(azanylylidene))-bis(phenylmethanylylidene))dibenzoic acid (H₂L) was obtained by the condensation of m-phenylenediamine with o-benzoylbenzoic acid. The molecular and electronic structure of Schiff base ligand (H₂L) was optimized theoretically, and the quantum chemical parameters are calculated. Molecular docking was used to predict the binding between Schiff base ligand (H₂L) and the receptors of breast cancer mutant 3hb5-oxidoreductase, crystal structure E. coli (3t88) and crystal structure of S. aureus (3q8u). The newly synthesized Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), and Cd(II) complexes were characterized by elemental microanalysis, molar conductance, spectroscopic techniques (IR, ¹H NMR, ESI-mass, ESR, UV–Vis), magnetic susceptibility, thermal (TG/DTG) and powder X-ray diffraction data to explicate their structures. The data showed that the complexes had composition of MH₂L type. The IR results confirmed the bidentate binding of the ligand involving two azomethine nitrogens. ¹H NMR spectral data of the ligand (H₂L) and its Zn(II) and Cd(II) complexes agreed well with the proposed structures. On the basis of electronic spectra and the magnetic measurements, octahedral geometry of the complexes was proposed. Thermogravimetric data (TG and DTG) were also studied. The kinetic and thermodynamic parameters for thermal decomposition of the complexes were calculated using the Coats–Redfern and Horowitz–Metzger methods. In order to appraise the effect of antimicrobial activity of metal ions upon chelation, the newly synthesized ligand and its metal complexes were screened against a number of bacteria organisms as Bacillus subtilis, Staphylococcus aureus, Escherichia coli, and Neisseria gonorrhoeae and against one fungus, Candida albicans, to assess their inhibiting potential by using the disc diffusion method. The results showed that in some cases the antimicrobial activity of complexes was more biologically active than the Schiff base ligand. Anticancer activity of the ligand and its metal complexes were evaluated in human cancer (MCF-7 cells viability). It was found that [Cd(H₂L)(H₂O)₂Cl₂]2H₂O complex showed lowest IC₅₀ than the others, and hence was the more active. The activity index was calculated.     

Charge transfer and van der Waals states of jet-cooled dialkylaniline complexes with anthracene

We report here a study of the influence of a physical parameter (i.e. the ionization energy of different donor aromatic molecules) on the spectroscopic and dynamic properties of a series of molecular complexes A-D (A acceptor, D donor) where A is the anthracene molecule and D is one of the following dialkylanilines: dimethyl, diethyl, dipropyl or dibutyl. All complexes exhibit the same spectroscopic behavior already observed for dimethylaniline and diethylaniline cases and tentatively explained by the existence of two isomeric forms for each complex. Decay times and the broad band maximum frequency shifts for the exciplex-like emission type are experiencing a continuous variation in agreement with the change of the ionization energy of the donors. This is confirmed by calculations done using a very simple model based on the interactions between the diabatic A*D and A⁻D⁺ states of the complexes. This agreement is in favor of the initial assumption, that most physical parameters (complexation geometry, coupling between the diabatic states) are only weakly perturbed when changing the donor molecule and this despite an expected increased steric hindrance.