Dynamics of branched polymer molecules in dilute solution

Theoretical formulas for the intrinsic viscosity and viscoelastic properties of some model branched molecules in dilute solution are calculated by means of the normal coordinate method of Rouse modified to include hydrodynamic interactions. The calculations are exact except for the usual approximation of the hydrodynamic interactions by the Kirkwood-Riseman formula. The ratio of the intrinsic viscosity of a branched molecule to that of a linear molecule of the same weight is found to vary almost as the square root of the ratio of the mean square radii, instead of as the latter ratio to three-halves power, as has been postulated before. It is proposed that this square root relation is applicable in general to branched molecules of all types. Several sets of experimental data in the literature are shown to agree well with this hypothesis.     

Electron attachment to molecules in a cluster environment

Low-energy dissociative electron attachment (DEA) to the CF(2)Cl(2) and CF(3)Cl molecules in a water cluster environment is investigated theoretically. Calculations are performed for the water trimer and water hexamer. It is shown that the DEA cross section is strongly enhanced when the attaching molecule is embedded in a water cluster, and that this cross section grows as the number of water molecules in the cluster increases. This growth is explained by a trapping effect that is due to multiple scattering by water molecules while the electron is trapped in the cluster environment. The trapping increases the resonance lifetime and the negative ion survival probability. This confirms qualitatively existing experiments on electron attachment to the CF(2)Cl(2) molecule placed on the surface of H(2)O ice. The DEA cross sections are shown to be very sensitive to the position of the attaching molecule within the cluster and the orientation of the electron beam relative to the cluster.     

Band shape in vibrational spectra and interactions of polar molecules in liquids

The structure and shape of bands in the Raman vibrational spectra of polar molecules in liquids are analyzed. The possibility of using these data to examine interactions of molecules as well as their vibrational and orientational dynamics is shown. Translated from Zhumal Struktumoi Khimii, Vol. 38, No. 2, pp. 270–281, March–April, 1997.     

Hydrodynamic and conformational properties of cellulose valerate molecules in dilute solution

Using the methods of molecular hydrodynamics, structural-conformational studies have been performed for a number of cellulose valerate and acetovalerate samples in the molecular-mass range M = (58.1–464.3) × 10³ and with a mean degree of substitution of 182.4 with respect to valeric acid isomers. The conformations of valerate-substituted cellulose molecules are characterized by an increased local packing density of monomer units. The molecular conformations are quantitatively described in terms of the helix formed by the succession of vectors connecting glycoside oxygens of a chain. The molecular-hydrodynamic and conformational characteristics of cellulose valerate are compared with the corresponding characteristics of cellulose myristate.     

Critical number density in polar liquids: orientational polarizability of polar molecules in n-decanol/n-heptanol and n-heptanol/heptane systems

The orientational polarizability of polar molecules in n-decanol/n-heptanol and n-heptanol/heptane systems has been determined. Experimental permittivities show that both systems (together with the family of aliphatic normal alcohols) are described by a unique function of the number density ϱ and the absolute temperature T. The experimental data show that the polarizability increases rapidly as a function of ϱ from a critical number densityϱ_c.     

Fluorescence study for the electrostatic interaction and aggregation in dilute polar solution of polyelectrolytes

Fluorescence decay and quenching of pyrene labels on copolymers of 2-acrylamido-2-methylpropanesulphonic acid (AMPS) and N,N-dimethylacryl-amide (DMAA) were observed in dilute salt-free aqueous solutions as a function of the mole fraction F_AMPS of AMPS from 0 to 0.896. Monoexponential and biexponential decays were found for the samples of F_AMPS < 0.35 and samples of FAMPS > 0.35, respectively. The fast decay component is 80% and the averaged lifetime <τ> and lifetime τ₁ of the fast decay decreased with increasing F_AMPS. Quenching efficiency of Cu²⁺, CH₃NO₂, and dinitrobenzene to the pyrene label was investigated in the framework of Stern-Volmer plot. The quenching effects of Cu²⁺ included both of dynamic and static ones, the latter was due to the condensed Cu²⁺. For the neutral quenchers, the quenching rate constant k_q increased when F_AMPS < 0.449 then decreased, showing a decline of accessibility to the pyrene label. I₁/I₃ value in salt-free dilute aqueous solution and in DMSO solution decreased obviously with an increase in F_AMPS, indicating that the labeled fluorophore experienced a decrease in polarity of its microenvironment with increasing charge density of the polymer. This I₁/I₃ decrease was enhanced with increasing the polymer concentration and adding salt NaCl up to 0.75 mol/L showed no effect on the appearance of this decrease. These results were interpreted consistently with the counterion condensation concept, where condensed counterions induced the “temporal” aggregation of less-polar in the polyelectrolyte solutions surrounding the pyrene labels.     

Transient Radicals Formed by Electron Transfer between inorganic ions and excited aromatic molecules in polar solvents

Fluorescence quenching of aromatic molecules by inorganic anions has been the subject of many investigations, yet the nature of the quenching mechanism is not fully understood. The fluorescence-quenching rate constants correlate with electrochemical data, but the radicals expected to form upon transfer of an electron to the excited aromatic molecules have escaped observation. We report the first observation of radical-ion species formed by electron-transfer quenching with inorganic anions in acetonitrile. A decisive step leading to formation of separated radical ions is the trapping of the primary charge-transfer complex by a second inorganic ion.     

Model predictions of mean librational frequencies for rigid molecules in dilute decalin solution

The product of the reduced inertia J_r of a dipolar molecule and the square of the far infrared absorption maximum wave-number $\text{ν}$_max that it displays in dilute solution is shown, using a three-parameter Mori/itinerant oscillator model, to be related to the mean-square action on the molecule and hence by a simple argument to the solute volume of rotation V. Estimates of V have been made for seventeen rigid molecules (mainly substituted phenyls) and their $\text{ν}$_max values have been measured in decalin solution at 293 and 110 K. Provided allowance is made for translation—rotation coupling in four cases, the derived relation I_r$\text{ν}$²_max = (8a_a²c²kT)^?1V²P(0) is found to be approximately obeyed at both temperatures with P(0) (the solute-independent mean-square torque acting on a molecule of unit V) having a value of 4.0 × 10¹⁷ (N m^?2)² at both temperatures. It should now be possible to predict $\text{μ}$_max for other solutes in decalin if their structures are known.     

The interaction of polar aromatic molecules with neutral (polar) polymers and polyanions in aqueous solution

The interaction of aniline, pyridine and its homologues, phenol and benzamide with a series of neutral polar polymers and polyanions in aqueous solution has been studied by the equilibrium dialysis method. The interaction isotherms were generally sigmoidal. Significant association between polymer and organic molecule was only observed beyond some specific free organic molecule-polymer concentration ratio; i. e., after inter-chain attractive forces and solvation have been partially weakened by preliminary absorption of a surface layer of organic molecules. Benzamide, in fact, shows practically no interaction with neutral ‘coiled’ polymers. Maximum interaction is reached at up to thirty percent utilisation of ‘polar’ sites on the polymer chain. Klotz's method was modified to correct for these weak interactions at low organic molecule concentration. Equilibrium constants and free energies for the main association were then determined. Equilibrium constants are low;K=5–50 (g. moles per l.)^?1 for interaction with neutral polymers andK=20–120 (g. moles per l.)^?1 for interaction with polyions. The free energies are (?δG)=1–3RT and 3–5RT calories per g. mole respectively. Complexing is due to dipole-dipole and/or ion-dipole type interaction and is greatest for aniline, pyridine and phenol with fully extended polyion chains. Van der Waals' interaction between the aromatic ring and the organic section of the polymer backbone augments the dipole-dipole or ion-dipole binding with pyridine homologues, especially with acridine.     

Statistical thermodynamics of mixtures of polar liquids in the model of hindered rotation of molecules

The model of hindered rotation of molecules was used to calculate the internal energy of mixtures of dipolar hard spheres. A comparison of the analytic equations obtained with the data of Monte Carlo simulations and hypernetted chain theory calculations showed the importance of various correlation effects caused by electrostatic and steric forces.     

Electron trapping in polar-solvated zeolites

Of current interest in our laboratory is the nature of photoinduced processes in the cavities of zeolites completely submerged in polar solvents, or polar-solvated zeolites (PSZ). The present study addresses the nature of electron trapping in PSZ with emphasis on the zeolites NaX and NaY. Free electrons were generated by two-photon, pulsed-laser excitation of either pyrene or naphthalene included in zeolite cavities. Trapped electrons were monitored by diffuse transmittance, transient absorption spectroscopy at visible wavelengths. In anhydrous alcohols, electron trapping by Na(4)(4+) ion clusters was observed in both NaX and NaY. The resulting trapped electrons decayed over the course of tens of milliseconds. No evidence for alcohol-solvated electrons was found. More varied results were observed in solvents containing water. In NaX submerged in CH(3)OH containing 5% or higher water, species having microsecond lifetimes characteristic of solvated electrons were observed. By contrast, a 2 h exposure of NaY to 95/5 CH(3)OH/H(2)O had no effect on electron trapping relative to anhydrous CH(3)OH. The difference between NaX and NaY was explained by how fast water migrates into the sodalite cage. Prolonged exposure to water at room temperature or exposure to water at elevated temperatures was necessary to place water in the sodalite cages of NaY and deactivate Na(4)(4+) as an electron trap. Additional studies in NaY revealed that solvent clusters eventually become lower energy traps than Na(4)(4+) as the water content in methanol increases. In acetonitrile-water mixtures, electron trapping by Na(4)(4+) was eliminated and no equivalent species characteristic of solvated electrons in methanol-water mixtures was observed. This result was explained by the formation of low energy solvated electrons which cannot be observed in the visible region of the spectrum. Measurements of the rate of O(2) quenching in anhydrous solvents revealed rate constants for the quenching of ion cluster trapped electrons that were 2-4 times higher than that for pyrene triplets. In NaX, the rate constant in methanol was 10(4) times smaller than that in cyclohexane, showing greater inhibition of O(2) reactivity in the medium of PSZ. The results of this study point out the conditions under which Na(4)(4+) is active as an electron trap in PSZ and that water must be present in the sodalite cage to produce solvated electrons in the supercage.     

Electron enhanced Raman scattering and its applications in solution chemistry.

The present review describes a new enhancement technique for Raman scattering in aqueous solutions. Raman scattering spectroscopy has an inherent ability to distinguish between molecules with great similarity and provides useful information on local physical and chemical environments at their functional groups' level. Since the Raman scattering signals from water molecules are quite weak, Raman spectroscopy has great advantage for detection or discrimination of a trace amount of analytes in aqueous environments. However, Raman scattering cross-sections are inherently small and it generally requires high power excitation and long acquisition times to obtain high-quality Raman spectra. These conditions create disadvantages for the analyses for living cells and real-time monitoring for environmental analyses. Here, I describe a new Raman enhancement technique, namely "electron enhanced Raman scattering (EERS)", where artificially generated electrons additionally affect the polarizability of target molecular systems and enhance their inherent Raman cross-section. Principles of the EERS and its applications to aqueous solutions are presented.     

Electron trapping in low-density polyethylene

Thermoluminescence (TL) emission from low-density polyethylene has been investigated. The glow curves of gas-free samples x-irradiated at ?190°C and heated to room temperature were found to contain three peaks numbered I, II, and III in order of increasing temperature, in agreement with earlier results. The sites of all traps are accessible to absorbed gases; in the presence of air, O₂, N₂ or Ar, “gas” traps are formed, resulting in the appearance of an additional peak IV in the glow curve at a temperature between peaks I and II, large reductions in the intensities of peaks II and III, and various changes in peak I. The peak I, II, and III traps are formed from particular chain configurations occurring in the chain-fold regions of the samples, these configurations being broken up by different forms of molecular motion within the chains. It is unlikely that the peak IV traps are just the gas molecules themselves; they are probably formed from new chain configurations occurring in the amorphous regions of the samples in the presence of the gas, the properties of the gas influencing the associated TL intensity and emission temperature. These traps are also broken up by molecular motion. The samples can be divided into two main types, differing mainly in the height of peak I relative to peak II, which is of nearly constant intensity in all samples. We suggest that two types of trap which are not interconvertible are associated with peak I, and that the dominant type in a given sample depends on the fine details of the sample fabrication process.     

The non-coincidence effect in polar liquids

The experimental non-coincidence splitting of the C=O stretching Raman band of acetone in dichloromethane, chloroform and carbontetrachloride solvents has been compared with the theoretical values predicted by dipolar resonant transfer model of Mirone and coworkers and that by mean spherical approximation model of Logan. It is observed that Logan's theory better reflects the origin of the non-coincidence effect in these binary mixtures.     

On electron solvation in polar liquids

Experimental and theoretical evidence for the dominance of first solvation shell orientation on the spectral changes observed during electron solvation is evaluated.