Fourier transform IR spectroscopic study on phase transitions of copolymers of <Emphasis Type="Italic">N</Emphasis>-isopropylacrylamide and alkyl acrylates in water

Copolymers of N-isopropylacrylamide (IPA) and alkyl acrylates [methyl acrylate (MA), ethyl acrylate, and butyl acrylate] or vinyl acetate have been prepared and their phase transitions in water have been observed by means of IR spectroscopy. The incorporation of these alkyl acrylates into a poly(IPA) (PIPA) chain induces a decrease in the phase-transition temperatures, T_p, and the magnitude increases with increasing size of the alkyl chains. The profiles of the C=O stretching absorption bands of the ester groups [9(C=O)_ester] and the IR bands due to IPA units exhibit critical changes at the T_p of these copolymers. The 9(C=O)_ester bands shift slightly toward higher wavenumbers (blueshift) upon phase transition, while the amide I and amide II bands of the IPA units undergo a blueshift and a redshift, respectively. Analysis of the 9(C=O)_ester band of PIPA-MA by using a curve-fitting method shows that it consists of three components, at 1,703, 1,720, and 1,738 cm^-1. The relative peak area of the largest component (1,720 cm^-1) is almost constant, and those of the 1,703-cm^-1 and 1,738-cm^-1 components increase and decrease with increasing temperature during the phase transition, respectively. However, the changes are rather small, suggesting that changes in hydrogen bonding of the C=O groups of MA units upon phase transition are not significant. The 9(C=O)_ester bands of other comonomers examined here also exhibit similar changes. The situation is consistent with the change in the hydration states of the amide groups of IPA units, most of which associate with water molecules through hydrogen bonds even after the phase separation.     

Langmuir films of naphthenic acids at different pH and electrolyte concentrations

Langmuir films of naphthenic acids at different pH and electrolyte concentrations are reported. The polydisperse naphthenic acids were commercially available, while two single-component naphthenic acids [5#(H)-cholanoic acid and 1-naphthalenepentanoic acid, decahydro- (9CI)] were synthesized. 1-naphthalenepentanoic acid, decahydro- is too water-soluble to form stable monolayers. 5#(H)-Cholanoic acid and Fluka naphthenic acid form stable films when cations are present in the aqueous subphase. At lower pH the cations are less influential since the naphthenic acids are not protolysed and metal naphthenates cannot be formed. pK_a^s for 5#(H)-cholanoic acid is determined to 5.65. The micellisation of the naphthenates at high pH is described.     

Effect of electrolytes on the physicochemical behaviour of sodium dodecyl sulphate micelles

The values of the critical micelle concentration (cmc) and the degree of electrolytic micelle dissociation, a, for sodium dodecyl sulphate (SDS) as a function of the concentrations of the electrolytes added, NaCl, KCl, NaF, NaClO₄, NH₄ClO₄, and Mg(ClO₄)₂, have been determined. The values of the SDS cmc have been shown to depend on the kind and concentration of the electrolyte cations. The electrolyte cations cause a decrease of the cmc in the following order: Na⁺4⁺+2+. Moreover, a depends on the kind and concentration of the electrolyte added. The electrolyte anions have a much smaller effect on the values of a than the cations. The anions enhance a in the following order: F^->ClO₄^->Cl^-. The effect of different electrolyte cations on a is observed; moreover the values of a either increase or decrease with the electrolyte concentration. Other micellization parameters of SDS versus the concentration of the electrolytes added have been calculated.     

Aggregational behavior of N-butyloxycarbonyl-L-glutamic acid oligomeric benzyl esters (exact residue numbers 4, 6 and 8) in benzene. SAXS studies

N-Butyloxycarbonyl(BOC)-L-glutamic acid oligomeric benzyl esters with exact residue numbers (BOCN_pZ, N_p=4, 6 and 8) have been synthesized by a stepwise procedure in a liquid phase. The SAXS intensity spectra of the BOCN_pZ-benzene systems have been analyzed on the basis of the rod-like aggregate model, in which the #-sheet monomers are one-dimensionally stacked antiparallel to each other. The extracted parameters (the number-averaged aggregation number, the monomer-monomer bond energies corresponding to hydrogen bonding energies, and the number-averaged molecular weights) for these aggregates have been compared with those for the aggregates formed by N-acetyl-L-glutamic acid oligomeric benzyl esters (AN_pZ, N_p=4, 6 and 8) in benzene (PCCP, 2001, 3, 3140-3149). The results indicate that it is more difficult to form aggregates in the BOCN_pZ systems than in the AN_pZ systems. This difference is due to the bulky BOC group, which hinders the formation of aggregates.     

Fluorescence study of chromophore labeled strong polyelectrolyte bound with oppositely charged surfactant

Four strong polyelectrolyte samples of 2-(acrylamido)-2-methylpropanesulfonic acid (AMPS) and N,N-dimethylacrylamide (DMAA) were radically copolymerized with a single label of naphthalene or pyrene, with both labels and without label, containing about 40 mol % AMPS. Fluorescence nonradiative energy transfer (NRET) I_Py/I_Np, anisotropy r, I₁/I₃ and excimer emission I_E/I_M of pyrene labels were observed in dilute aqueous solutions with and without cationic surfactant of cetyltrimethylammonium bromide (CTAB). The overlap concentration was determined as 3 g/L from the appearance of intermolecular excimer. The variation of intra- and intermolecular NRET with total polyelectrolyte concentration showed that the charged chains preferentially interpenetrated each other rather than reduce their coil volume as their concentration beyond the overlap threshold. By binding with CTAB, the polyelectrolyte chain became more coiled as known from the reduced viscosity. The intramolecular NRET was dominant when [CTAB]Д᎒^-5 M and then the intermolecular NRET occurred at higher CTAB concentrations with hydrophobic aggregation between CTAB tails bound on different polyelectrolyte chains. The CTAB concentration corresponding to the maxima of I_Py/I_Np just is equal to the AMPS monomer concentration, indicating the formation of 1:1 binding between surfactant and polyelectrolyte in very dilute solutions. Added salt of NaCl up to 0.1 M hardly affected the intramolecular NRET but affected the I_Py/I_Np value for the intermolecular NRET.     

Calculation of the photo-electrons angular distribution asymmetry parameter β2p near the (3s3p)1 P resonance of He*

Near the (3s3p)¹ P resonance of He, we have calculated the photoelectrons angular distribution asymmetry parameter β_2p in the diagonalization approximation. Using the measured value of β _n=2 near the (3s3p)¹ P level obtained by Lindle et al. in the resonance photo-ionization of He to He^?(n=2), we have estimated the ratioR=σ_2p /σ_2s of the partial 2p photo-ionization cross section to the partial 2s photo-ionization cross section. Our calculation supports the result that in the resonance region, the formation of ions in the 2p level dominates over the 2s level. This is in good agreement with the experimental and most of the theoretical results reported to date.     

Synthesis and solution properties of comblike polymers from octadecyl methacrylate and acrylic acid

Amphiphilic polymers consisting of a statistical distribution of octadecyl methacrylate (ODMA) and acrylic acid in respective molar ratios of 83-22 and 17-78 mol% and in a molecular-weight range of 2.35-4.70᎒⁴ gmol^-1 have been synthesized. The series of polymers consisting of various mole fractions of ODMA and acrylic acid are expected to exhibit unique characteristics resembling ionomer to hydrophobically modified polyelectrolytes. The changes in the I₃/I₁ emission intensity ratios of pyrene, occurring in the presence of tetrahydrofuran (THF) solutions of the polymers have been taken as the main basis for inferring solution structures. The polymers are found to form random-coil to collapsed-coil/aggregated structures in THF solvent depending on the copolymer compositions. The polymer consisting of 83 mol% ODMA and 17 mol% acrylic acid behaves as an ionomer, capable of forming collapsed-coil structures at concentrations of 0.02 gml^-1 and above as shown by a very high I₃/I₁ of 1.20 (I₃/I₁ of pyrene in THF is 0.85). In contrast, the poly(octadecyl methacrylate) homopolymer and the sets of copolymers consisting of a very high proportion of acrylic acid to an extent of 73 mol% and above contribute to almost negligible or very small changes in I₃/I₁ similar to the homopolymer, poly(octadecyl methacrylate), suggesting the formation of random-coil structures.     

Critical composition of ionic–nonionic mixed micelles for counterion condensation

In the mixed micelles of an ionic surfactant (sodium dodecyl sulfate) with a nonionic surfactant (N-decanoyl-N-methylglucamide, hexaoxyethylene glycol-mono-n-decylether, and hexaoxyethylene glycol-mono-n-dodecylether), the critical mole fraction, X_ic, of the ionic surfactant has been determined, below which the counterion is completely released from the micelles. The values of X_ic are 0.074, 0.11, and 0.11, for the respective nonionic surfactants. The valences, i.e., the aggregation numbers of the ionic surfactant, of the mixed micelles at X_ic are almost close to each other, around 6. At X_ic, the critical surface charge density (about 0.03 Cm^-2) for counterion condensation was tentatively calculated. In the present study, a differential conductivity method was applied.     

MONTE CARLO STUDY ON THE CRITICAL ADSORPTION POINT OF BOND-FLUCTUATED POLYMER CHAINS TETHERED ON ADSORBING SURFACES

 The behavior of three-dimensional bond fluctuation model chains tethered on an adsorbing flat surface was simulated by the Monte Carlo method. The dependence of the number of surface contacts M on the interaction strength e and the chain length N was investigated by a finite-size scaling law M = N[a₀ + a₁N^1/v_k + O((N ^1/v_k)²)] for e near the critical adsorption point e_c, i.e., k ≡(e-e_c)/e_c closes to 0. The critical adsorption point was estimated to be e_c = 0.93, and the exponents &#61542; = 0.49 and 1/v= 0.57.     

Synthesis and characterization of copolymers based on benzothiadizole-thiophene-phenylenevinylene

<正>Two novel copolymers based on benzothiadizole-thiophene-phenylenevinylene have been synthesized through palladium catalyzed triple-bond polycondensation method.The copolymers exhibit good solubility in common organic solvents such as CHCl_3,CH_2Cl_2 and THF.The structures and properties of the two copolymers are characterized by FT-IR, ~1H-NMR,UV-Vis absorbance(Abs),gel permeation chromatography(GPC),thermal gravimetric analysis and cyclic voltammetry(CV).The copolymers of P_1 and P_2 show absorption spectra with maximum peak at 532 nm and 573 nm in solution,respectively.Compare to their monomers M_1 and M_2,the absorption peaks of P_1 and P_2 were red-shifted by 34 nm and 54 nm respectively.Thermal gravimetric analysis demonstrated that the polymers were stable and little weight loss was observed below 300℃.Cyclic voltammetry experiments showed that the band gaps of the copolymers were 1.81 eV and 1.62 eV,respectively,suggesting their potential for applications as organic solar cell materials.     

Nanosecond laser measurements of optical absorption coefficients of electrons in polar fluids

Direct measurements of the optical absorption coefficients of the short-lived electrons in polar fluids have been made. Laser-induced photoionization of pyrene in alcohols at 293 K generated equal numbers of electrons (e_s^?) and pyrene positive ions (P⁺). The ?_max(e_s^?) were derived by measuring the relative absorption intensities of e_s^? and P⁺, which had been independently characterised. The ?_max values for e_s^? in methanol to 1-decanol fell within the range (1.0–2.0) × 10⁴ M^?1 cm^?1, the implications of which are discussed.     

The effect of poly(N,N-dimethylacrylamide) on the lamellar phase of Aerosol OT/water

The effect of a water-soluble uncharged polymer on the stability of the lamellar phase of the Aerosol OT (AOT)/water system is studied. The lamellar phase still exists when water is replaced by an aqueous solution of poly(N,N- dimethylacrylamide) (R_gƼ᎒² Å). Since the coil dimensions are (much) larger than the thickness of the water layers (d_wᅣ Å), the polymer molecules do not enter the lamellar phase. Instead segregation in small domains occurs, and in equilibrium with the AOT-rich phase another separate phase containing the polymer is formed. The polymer-rich phase exerts an osmotic pressure that reduces the water content in the AOT-rich phase, and by compression the repeat distance is reduced.     

Influence of flocculant charge on the dewaterability of flocculated clay suspensions

The influence of charged components of cationic polyelectrolytes on the dewatering of clay-containing suspensions was investigated with a view to better predicting the efficiency of flocculating agents. In flocculation and dewatering experiments on suspensions of harbour sediment and gravel washings, flocculating agents of the polyacrylamide-co-(trimethylammoniumpropyl chloride) (PTCA) type exhibited different dewatering efficiencies depending on the degree of cationicity, F. For harbour sediment, a dewatering index, I_D, of 80 was achieved with the highly charged PTCA 3 (F=40%) at 30% lower flocculant dose than with the weakly cationic PTCA 1 (F=3%). However, for gravel washings PTCA 1 proved to be more effective: for comparable degrees of dewatering (I_D=80) approximately 40% less flocculant was required than for PTCA 3. In shear experiments on gravel washings and model suspensions with particles of differing size (d₅₀=0.5 und 5.7 µm) weakly cationic PTCA 1 exhibited an increased floc stability at lower concentrations than is necessary to achieve maximum I_D values. For harbour sediments and model suspensions with unimodal particle size distributions this stability did not occur until the doses used were higher than the concentrations needed to achieve maximum I_D values.     

Calculations of D‐wave bound states and resonance states of the screened helium atom using correlated exponential wave functions

We have investigated the effects of screened Coulomb (Yukawa) potentials on the bound ^1,3D states and the doubly excited ^1,3 D^e resonance states of helium atom using highly correlated exponential basis functions. The Density of resonance states are calculated using stabilization method. Highly correlated exponential basis functions are used to consider the correlation effect between the charged particles. A total of 18 resonances (nine each for ¹ D^e and ³ D^e states) below the n = 2 He ⁺ threshold has been calculated. For each spin states, this includes four members in the 2pnp series, three members in the 2snd series, and two members in 2pnf series. The resonance energies and widths for various screening parameters ranging from infinity to a small value for these ^1,3 D^e resonance states are reported along with the bound‐excited 1s3d ^1,3 D state energies. Overall behavior of the spectral profile of 1s3d ¹D state of helium atom due to electron‐electron and electron‐nucleus screening are also presented. Accurate resonance energies and widths are also reported for He in vacuum. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010     

Inter- and intramolecular N-terminal methyl–side chain interactions in N-acetyl-L-glutamic acid oligomeric benzyl ester solutions. 1H NMR study

Oligomeric N-acetyl-L-glutamic acid benzyl esters with exact residue number (2, 3 or 4) have been synthesized by a stepwise procedure. The aggregational behavior of these oligomeric molecules in dioxane and benzene has been investigated by use of ¹H NMR. In particular, the concentration dependence of the ¹H signals for the N-terminal CH₃ protons has provided evidence that an intermolecular CH₃···? interaction plays a critical role in the formation of aggregates and that an intramolecular CH₃···? interaction occurs in the monomolecular state.     

The counterion releasing effect and the partition coefficient of branched alkanols in ionic micellar solution

In the micellar solution of SDS, the partition coefficient (K_x) of following branched alkanols at infinite dilution was determined by applying a differential conductivity method: the alkanols used were i-C_mH_2m+1OH (m=4-9, i=1-5) in which the position of OH group (i) shifts from an end to the center of a hydrocarbon chain. The method provides two significant quantities, d!/dX_am and dC_sf/dC_af in addition to K_x. The following results have been obtained. (1) The dependence of K_x on i indicates that the hydrophobicity of alkanol is weakened with increasing i, whereas the increase in m strengthens the hydrophobicity. (2) The degree of counterion disossiation of micelles (!) is accelerated by the solubilized alkanols in micelles (mole fraction: X_am) and the acceleration rate, d!/dX_am (=0.17), depends on neither m nor i. (3) In the bulk water, the monomerically dissolved alkanols (concentration: C_af) depresses the concentration of free monomer surfactant (C_sf), and the depressing rate, dC_sf/dC_af, in micellar solution is identical with the corresponding quantity, ((CMC/(C_a)_o at CMC.     

Femtosecond induced transparency and absorption in the extreme ultraviolet by coherent coupling of the He 2s2p (P) and 2p (S) double excitation states with 800 nm light

Femtosecond high-order harmonic transient absorption spectroscopy is used to observe electromagnetically induced transparency-like behavior as well as induced absorption in the extreme ultraviolet by laser dressing of the He 2s2p (¹P^o) and 2p² (¹S^e) double excitation states with an intense 800 nm field. Probing in the vicinity of the 1s² → 2s2p transition at 60.15 eV reveals the formation of an Autler–Townes doublet due to coherent coupling of the double excitation states. Qualitative agreement with the experimental spectra is obtained only when optical field ionization of both double excitation states into the N = 2 continuum is included in the theoretical model. Because the Fano q-parameter of the unperturbed probe transition is finite, the laser-dressed He atom exhibits both enhanced transparency and absorption at negative and positive probe energy detunings, respectively.     

Accurate nonrelativistic energies for 2Pe states of the Li isoelectronic series

Highly accurate upper bounds for several ²P^e states of the Li isoelectronic series obtained by extensive Hylleraas-Cl calculations are given. The best value for the 2²P^e state (1s2p²) of Li is −5.2137392₀ au. The evaluation of the occurring integrals is given explicitly. Additionally, we present some expectation values and isotope energies of the Li isoelectronic series. © 1997 John Wiley & Sons, Inc.     

含硝基二代光致变色液晶树枝状大分子的光化学研究

研究了树外围含36个硝基偶氮苯端基新型二代碳硅烷光致变色液晶树枝状大分子(G₂)在溶液中的最大吸收波长, 摩尔消光系数, 反-顺光异构化反应速率常数, 热回复异构化反应速率常数, 光化学回复异构化反应平衡常数及速率常数. G₂的光致变色反应速率常数的数量级为10^－1 s^－1, 而含偶氮端基侧链聚硅氧烷的光致变色反应速率常数的数量级为10^－8 s^－1, 因此, 液晶树枝状大分子的光响应速率比后者快10⁷倍. G₂的光化学回复异构化反应平衡常数k_t/k_c为1.77～1.97, 有作为光控开关材料的应用前景.     

Triple differential generalized oscillator strength of direct and resonance He(e, 2e)He+ reaction at high incident energies

The triple differential cross section and triple differential generalized oscillator strength of the direct and resonance He(e, 2e)He⁺ reaction in the first Born approximation for incident energiesE ₀≥4keV are calculated. For the direct (e, 2e) process our results obtained in definite structure models of the atom are found to be in good agreement with the available experimental data and theoretical estimates. The resonance profiles calculated in these models exhibit a complicated structure formation of overlapping¹ P and¹ D autoionization states (AIS) excited in the (e, 2e) reaction. The specific kine-matical conditions, when the overlap and interference of the¹ P and¹ D resonances are small and the¹ P and¹ D AIS yields can be measured separately, are discussed. It is also shown that in a certain range of ejection angles and at large momentum transfers (Q>2au) the yield of the¹ D AIS dominates over the¹ P resonance yield.