Antiturbulent Powers of Higher Polyolefins and Olefin Terpolymers

Terpolymers of ethylene with propylene and higher -olefins with various compositions and molecular weights were synthesized, as well as copolymers with higher poly--olefins with various molecular weights. The possibility of laboratory assessment of the antiturbulent power of polymers and turborheometric determination of the volumes and molecular weights of poly--olefin macromolecules was examined.     

New approaches to characterize polymeric oil additives in solution based on pyrene excimer fluorescence

Maleated polyolefins (MaPOs) such as maleated ethylene propylene copolymers or polyisobutylene terminated at one end with a succininic anhydride can be used as polymeric dispersants in engine oils after reaction with polyamines while unmodified EP copolymers improve the viscosity index of oils. MaPOs can also be labeled with pyrene derivatives to generate pyrene‐labeled polyolefins (PyLPOs) as fluorescent mimics of oil additives and pyrene excimer fluorescence (PEF) can be applied to probe their behavior in solution. This review describes new methodology that was recently implemented to characterize the complex fluorescence signal emitted by PyLPOs by using steady‐state and time‐resolved fluorescence. This methodology enables one to gain quantitative information about the level of clustering of the succinic pendants along a maleated polyolefins and intra‐ and intermolecular aggregation of polyolefins in solution. Such information is relevant to scientists aiming to characterize polymeric oil additives used in engine oil. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 7–18     

Studies of thermally stimulated current in polypropylene/calcium carbonate/surfactant systems

Thermally stimulated polarization (TSP) and depolarization (TSD) experiments have been performed with two grades of polypropylene and some respective CaCO₃-filled composites containing small amounts of nonionic surfactant (0–2 wt%). The effects of electrode blocking, electrode materials on the thermally stimulated currents, and reproducibility of the measurements have been studied. The effect of water vapor adsorbed from the ambient air on the AC dielectric properties and on the thermally stimulated polarization behavior has been determined.The addition of either CaCO₃ or surfactant to PP decreases the intensity of the _c depolarization current peak in the pre-melting region, while the presence of both components increases the current. Partial discharges are present in poly propylene/CaCO₃ composites under high voltages if neither water vapor nor a coherent surfactant layer is present at the matrix/filler interface.A short literature survey is presented on the TSC studies of polyolefins and their composites, and various mechanisms responsible for the observed changes are discussed, including interfacial polarization, trap redistribution through nucleation, and oriented adsorption.     

Determination of the half-lives of transactinium isotopes by relative activity method

Relative activity method offers the potentiality of providing half-life values over a wide range in a short time for different -emitting transactinium isotopes. The method involves the preparation of a synthetic mixture using another isotope of the same element followed by the determination of atom ratio and -activity ratio by thermal ionization mass spectrometry and -spectrometry, respectively. A double dilution technique is described which helps in maintaining the atom ratios as well as -activity ratios close to unity so that these could be determined with high precision and accuracy. Results obtained on the half-lives of²³²U,²³⁸Pu,²⁴²Pu and²⁴³Am using double dilution technique in relative activity method are summarized. Requirements, advantages and applications of this technique for determining the half-lives of other transactinium isotopes are presented.     

Effect of Radiation on the Supermolecular Structure of Siloxane Block Copolymers with Different Compositions and Block Sizes

-Radiation-induced changes in the supermolecular structure of dimethylphenylsilsesquioxane block copolymers were studied with the use of electron microscopy. It was found that the supermolecular structure of the block copolymers was altered by irradiation. The character of changes depends on the size of a soft, dimethylsiloxane block, as well as on the total amount of the blocks in the copolymer molecule. A variation in the properties of block copolymers upon -irradiation was also detected by the technique of differential scanning calorimetry.     

New anionites from copolymers of styrene with some N,N′-arylenedimethacrylamides

Conclusions Various anion-exchatige polymers were obtained from the copolymers of styrene and N,N-arylenedimethacrylamides, with subsequent chloromethylation and amination.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 972–974, April, 1972.     

Structural Studies on Host + Guest Recognition Sensory Systems

Rhodamine B-ethylenediamine--cyclodextrins (RhB--CDen) and rhodamine B--cyclodextrins (RhB--CD) can form inclusive complexes with many guest molecules, a reaction which can be used as a nucleic acid probe. In this paper, the most stable conformations of RhB--CDen and RhB--CD have been determined by fluorescence experiments and analyzed by molecular modeling simulation. The interaction between RhB--CDen and two guest molecules, 1-borneol and cyclohexanol, has also been investigated. The results showed that RhB--CDen has a stronger interaction with 1-borneol than with cyclohexanol. Borneol could push the three aromatic-rings of rhodamine B out of the CD cavity, while the cyclohexanol could not. The interactive sites of host and guest are also presented.     

Study of the oxygen distribution in YBa2Cu3O7−x ceramics by (n, α) radiography technique

A technique to determine the oxygen distribution in high T_c superconducting YBa₂Cu₃O_7–x ceramics has been developed which is based on the (n, ) radiography method. The technique enables the non-destructive study of superconducting ceramics as well as monocrystal samples with spatial resolution not worse than 1 m at a relative standard deviation of 1.5%. This technique is used to study the influence of radiation-stimulated diffussion of oxygen on the formation of the superconducting phase in an yttrium ceramic. The oxygen distribution in the samples with a narrow transition (T1 K) and with a transition widened (T10 K) by thermal and thermo-radiative treatment is compared in the experiment. The oxygen distribution radiographs of irradiated and unirradiated samples provide strong evidence for the influence of irradiation on the ordering of superconducting ceramics structure.     

The effectivity of solvents as electron pair donors

The effectivity of solvents as electron pair donors, their donicity as expressed by their donor numbers DN, is reexamined. The linear dependence of the enthalpy and the Gibbs free energy for the reaction of donor solvents with antimony pentachloride is affirmed. Extension of the DN scale by other measured quantities, via their linear correlations for sets of solvents where both kinds of data are known is applied to Drago's E-C scale, Kamlet's scale, and Koppel's B scale. This extension, added to previous extensions employing Selbin's D_{I, II} and Popov's ²³Na, produces a DN scale for 170 solvents. The relation of DN measured for isolated solvent molecules in 1,2-dichloroethane to DN values measured for bulk solvents is examined by means of the scaled particle theory and solute-solvent interaction terms. A scale of normalized donor numbers DN ^N is presented. These values are practically the same as the scale, and for those solvents for which DN values are presented here and values are lacking, they can serve in their place for those preferring to use the scale for donor solvents.     

Solubilization by polysoaps

The aqueous solubilization power of several series of micellar homopolymers and copolymers (polysoaps) is investigated. Using five insoluble or poorly water-soluble dyes, comparisons of the capacities are made with respect ot the influence of structural variables such as the polymer backbone, the polymer geometry, the comonomer content, and the charge of the hydrophilic group. Some guidelines for polysoap structures suited for efficient solubilization are established. Noteworthy is that the solubilization capacities of the polysoaps are neither linked to the ability to reduce the surface tension of water, nor to the polarity of the solubilization sites deduced from spectroscopic probes.     

Unrestricted Hartree-Fock instabilities in nuclear spin-spin coupling calculations. The MNDO method

The MNDO wavefunction is used to calculate the Fermi contact term of nuclear spin-spin coupling constants. Owing to the presence of non-singlet unrestricted Hartree-Fock instabilities of the wavefunction, convergence problems arise in a rather large set of molecules, especially those containing molecular orbitals. A special technique to cope with this situation is presented. The MNDO and transmitted components of the coupling constants in the ethylene molecule are also calculated and compared with those previously obtained with the INDO and INDO/S methods.Part of a Ph.D. thesis (G.E.S.) to be presented to the University of Buenos Aires.Commission of Scientific Research (CIC, Pcia. Bs. As.) fellow.Argentine National Research Council (CONICET) fellow.Member of the Argentine National Research Council (CONICET).     

Improvement of Solubility and Dissolution of 19-Norprogesterone via Inclusion Complexation

In an effort to modify the solubility and dissolution rate of the contraceptive steroid, 19-norprogesterone in order to improve its bioavailability, the cyclodextrin complexation approach was chosen. In solution, the complex formation with -cyclodextrin (-CD), hydroxyethyl -cyclodextrin (HE--CD) and hydroxypropyl -cyclodextrin (HP--CD) was confirmed by using solubility, UV, IR and ¹H-NMR spectrophotometric techniques. The phase solubility diagrams were categorized as A_L-type. The complexing affinity of the CDs investigated were ranked as follows: -CD > HP--CD > HE--CD. The complexation thermodynamic parameters were obtained from the temperature dependence of the dissociation constants. In the solid state, differential scanning calorimetery (DSC) and optical microscopy methods were utilized to characterize the complexes. Dissolution studies showed that such molecularly encapsulated forms offered a marked improvement in the dissolution rate compared to the parent drug.     

Enhancement of Oral Bioavailability of Rofecoxib Using β-Cyclodextrin

The purpose of the present work was to investigate the effect ofcomplexation of rofecoxib with -cyclodextrin on its dissolutioncharacteristics and bioavailability. Inclusion complexes of rofecoxibwith -cyclodextrin were made by freeze-drying technique. Phasesolubility studies were conducted as suggested by Higuchi and Connors.The samples were characterized by performing dissolution studies, X-rayDiffraction studies and Differential Scanning Calorimetry. The complexeswere compressed into tablets and compared in-vitro with various marketedformulations. A single dose study on healthy human volunteers was performedin comparison with a marketed formulation of rofecoxib (without-cyclodextrin) to investigate the relative bioavailability.Phase solubility studies confirmed the formation of a 1 : 1complex in solution of rofecoxib with -cyclodextrin. Tablets ofsolid inclusion complexes of rofecoxib with -cyclodextrin preparedby freeze drying technique showed enhanced dissolution rate in distilledwater in comparison with all the marketed formulations analyzed. This isattributed to the increased solubility and wettability along with decreasedcrystallinity caused by complex formation, which is confirmed, by XRD and DSCstudies. The bioequivalence studies performed showed statistically significantenhancement in bioavailability as compared to the marketed formulation.Apparently, tablets containing complexes of rofecoxib with -cyclodextrinshows faster onset of action due to improved solubility, enhanced dissolutionand faster absorption of the molecule. The results of this investigation withrofecoxib in -cyclodextrin lend ample credence to its better oralbioavailability on complexation.     

Spin conversion of positronium in paramagnetic solutions studied by age-momentum-correlation method

Correlated measurement of the lifetime and of the lineshape of the 511 keV annihilation radiation of positrons (age-momentum correlation, AMOC) has become a powerful tool for investigating reactions of positron or positronium in condensed matter as a function of time. The beam-based ⁺ AMOC method installed at the Stuttgart relativistic positron beam facility (E _kin ^e+ 4MeV) offers substantial advantages over the conventional E coincidence technique resulting in a fast data taking due to the unity detection efficiency of the ⁺ scintillator which provides the start signal for the lifetime measurement. In this paper the application of AMOC to positronium chemistry is illustrated by the study of spin conversion of positronium in the system methanol/HTEMPO as a function of HTEMPO (4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, a paramagnetic solute) concentration. The same technique can be applied to other systems and other reactions in positronium chemistry, e. g., oxidation or complex formation.     

Capillary electrochromatography — Some important considerations in the preparation of packed capillaries and the choice of mobile phase buffers

Summary Capillary electrochromatography is an emerging technique utilising small diameter capillaries (typically 50 m) packed with HPLC-type stationary phases. Using electrically driven flow, higher efficiencies can be obtained than with pumped flow. This paper discusses some important points to enable more efficient, reliable capillaries to be prepared and also offers some suggestions regarding more suitable choices of mobile phase buffer which suffer less depletion problems than those buffers used to date. Separations of some drug candidates are shown and the future development of this technique is briefly discussed.     

Synthesis of Superabsorbent Copolymers by Pulsed Corona Discharges in Water

Pulsed corona discharges have been utilized for plasma polymerization in aqueous solution for the first time. Superabsorbent copolymers, i.e., poly(acrylamide-co-acrylic acid) hydrogels, were synthesized by aqueous solution polymerization using free radicals produced by pulsed corona discharges as initiator and N,N-methylene-bis-acrylamide as cross-linking agent. Acrylic acid contents in the monomers varied from 0% to 50%. The copolymers thus formed adsorbed 30–1100 g H₂O/g of copolymer. The FTIR spectra of the copolymers are comparable with the published FTIR spectra of the corresponding copolymers synthesized by a conventional chemical method and by -ray technique.     

Reaction of diazoalkanes with unsaturated compounds. 10. 1,3-Dipolar cycloaddition of diazocyclopropane to strained cycloalkenes

The reaction of diazocyclopropane, generated in situ by alkaline hydrolysis of N-nitroso-N-cyclopropylurea at –20 to –40C, with the double bond of norbornene hydrocarbons or 3,3-dimethylcyclopropene is a 1,3-dipolar cycloaddition and affords 45–70% yields of thermally stable 1-pyrazolines possessing a spiro-joined cyclopropane fragment. Methylenecyclopropane under the same conditions is a less effective and selective interceptor of diazocyclopropane, forming in 10% yields not only isomeric 1-pyrazolines but the corresponding product of cyclopropylization, dispiro[2.0.2.1]heptane.For previous communication, see [1].Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1057–1062, May, 1991.     

Synthesis and study of properties of linear permethylpoly(silane-siloxanes)

Heterofunctional polycondensation of ,-dichloropermethyloligosilanes Cl(Me₂Si) _m Cl (m = 2—6) with 1,5-dihydroxyhexamethyltrisiloxane was used to synthesize linear permethylpoly(silane-siloxanes) with the regular structure —[(SiMe₂) _m O(SiMe₂O)₃] _n —, which are soluble, unlike polydimethylsilane, in common organic solvents. The use of Py instead of Et₃N as an acceptor of HNl results in an increase in the yield, molecular weight, and characteristic viscosity of the copolymers. The molecular weight and viscosity characteristics, oxidative and thermal stabilities, and spectral properties of the synthesized copolymers were studied. The dependence of the oxidative and thermal stabilities of the synthesized copolymers on the number of the SiMe₂ units in the oligosilane fragment of the main chain was established.     

Modification of Various Functions for Description of Periodic Dependences

The properties of coordination compounds are known to change with the metal or ligand nature. These changes are often recurred, discontinued, or exhibit jumps. Such dialectical dependences can be described by any appropriate function presented as periodic by omitting the integral part in the basic function dependent variable. This approach is illustrated with equations for enthalpies of formation (in the gas phase), ionization energies, absolute electronegativities and hardnesses in a spin-coupled state, and electronic effect constants of complexing metals, as well as for IR spectroscopic constants for metal carbonyl compounds. These equations were used to calculate the above parameters, which were previously unknown, and thus extended the possibilities of describing and predicting the chemical and spectroscopic properties of coordination compounds. Examples are given for various transition metals with H, CH₃, Hal, -Cp, CO, NO, PR₃, and other ligands.