Carbon-13 NMR microstructural characterization of dichlorocarbene adducts of polybutadiene

¹³C-NMR has been used to examine a number of dichlorocarbene adducts of cis- and trans-polybutadiene prepared in a two-phase system. Dichlorocarbene was generated by reaction of aqueous or solid NaOH or KOH with CHCl₃ in the presence of a phase transfer catalyst. Monomer compositions, comonomer sequence lengths, and stereochemical information were obtained for the resulting polymers. The polymers examined here were stereochemically pure and were treated as simple copolymers. Samples prepared using aqueous NaOH can be described as essentially random copolymers over the entire range of monomer composition. Samples prepared using solid alkali-metal hydroxides contain a higher fraction of blocked units than a polymer of comparable composition prepared using aqueous NaOH. This blockiness can coincide with the presence of two glass transition temperatures and a two-phase morphology as seen by transmission electron microscopy. Fractionation of a substantially blocked sample yielded a chlorine-poor fraction which was a random copolymer and a chlorine-rich fraction which was more blocked than the original unfractionated material.     

1,4 polymerization of isoprene by titanate catalyst systems

Titanates are versatile in the 1,4 polymerization of isoprene. The (R′O)₄Ti/RAlCl₂ catalyst gives either cis- or trans-1,4-polyisoprene, depending on the nature of both the titanate and the solvent. Primary titanates give cis-1,4-polyisoprene in both aliphatic and aromatic solvents. Secondary titanates give cis-polyisoprene in aliphatic solvents, and trans-1,4-polyisoprene in aromatic solvents. Tertiary titanates give trans-polyisoprene in both aliphatic and aromatic solvents. A mechanism is postulated which takes into consideration the role of the solvent. ESR studies of the various titanate–RAlCl₂ catalysts were made; the paramagnetic structures are related to polymerization mechanisms.     

First measurement of the double spin asymmetry in (-->)e(-->)p-->e(prime)pi(+)n in the resonance region

The double spin asymmetry in the (-->)e(-->)p --> e(prime)pi(+)n reaction has been measured for the first time in the resonance region for four-momentum transfer Q2 = 0.35-1.5 GeV(2). Data were taken at Jefferson Lab with the CLAS detector using a 2.6 GeV polarized electron beam incident on a polarized solid NH3 target. Comparison with predictions of phenomenological models shows strong sensitivity to resonance contributions. Helicity-1/2 transitions are found to be dominant in the second and third resonance regions. The measured asymmetry is consistent with a faster rise with Q(2) of the helicity asymmetry A1 for the F(15)(1680) resonance than expected from the analysis of the unpolarized data.     

Q2 Dependence of quadrupole strength in the gamma*p --> Delta(+)(1232) --> p pi(0) transition

Models of baryon structure predict a small quadrupole deformation of the nucleon due to residual tensor forces between quarks or distortions from the pion cloud. Sensitivity to quark versus pion degrees of freedom occurs through the Q2 dependence of the magnetic (M1+), electric (E1+), and scalar (S1+) multipoles in the gamma*p-->Delta(+)-->p pi(0) transition. We report new experimental values for the ratios E(1+)/M(1+) and S(1+)/M(1+) over the range Q2 = 0.4-1.8 GeV2, extracted from precision p(e,e(')p)pi(0) data using a truncated multipole expansion. Results are best described by recent unitary models in which the pion cloud plays a dominant role.     

Proton source size measurements in the eA-->e'ppX reaction

Two-proton correlations at small relative momentum q were studied in the eA(3He,4He,C,Fe)-->e(')ppX reaction at E(0)=4.46 GeV using the CLAS detector at Jefferson Lab. The enhancement of the correlation function at small q was found to be in accordance with theoretical expectations. Sizes of the emission region were extracted, and proved to be dependent on A and on the proton momentum. The size of the two-proton emission region for He was measured in eA reactions for the first time.     

Photoproduction of the omega meson on the proton at large momentum transfer

The differential cross section, dsigma/dt, for omega meson exclusive photoproduction on the proton above the resonance region (2.6相似文献   

Measurement of the proton spin structure function g1(x,Q2) for Q2 from 0.15 to 1.6 GeV2 with CLAS

Double-polarization asymmetries for inclusive ep scattering were measured at Jefferson Lab using 2.6 and 4.3 GeV longitudinally polarized electrons incident on a longitudinally polarized NH3 target in the CLAS detector. The polarized structure function g(1)(x,Q2) was extracted throughout the nucleon resonance region and into the deep inelastic regime, for Q(2)=0.15-1.64 GeV2. The contributions to the first moment Gamma(1)(Q2)= integral g(1)(x,Q2) dx were determined up to Q(2)=1.2 GeV2. Using a parametrization for g(1) in the unmeasured low x regions, the complete first moment was estimated over this Q2 region. A rapid change in Gamma(1) is observed for Q2<1 GeV2, with a sign change near Q(2)=0.3 GeV2, indicating dominant contributions from the resonance region. At Q(2)=1.2 GeV2 our data are below the perturbative QCD evolved scaling value.     

The ep -->e'p eta reaction at and above the S11(1535) baryon resonance

New cross sections for the reaction e p-->e p eta are reported for total center of mass energy W = 1.5--1.86 GeV and invariant momentum transfer Q2 = 0.25--1.5 (GeV/c)(2). This large kinematic range allows extraction of important new information about response functions, photocouplings, and eta N coupling strengths of baryon resonances. Newly observed structure at W approximately 1.65 GeV is shown to come from interference between S and P waves and can be interpreted with known resonances. Improved values are derived for the photon coupling amplitude for the S11(1535) resonance.     

Ionic association in aqueous solutions of strong electrolytes

A more accurate calculation of relaxation effects obtained with the standard Debye-Hückel-Onsager model has been presented recently and is here applied to several aqueous 1:1 electrolytes. The variation of the standard deviation between calculated and observed equivalent conductivities withK _A leads to an ill-defined minimum; but, where data over a wide concentration range are available, the minimum corresponds to values of the contact distancea which approximate to estimates from ionic dimensions. It is therefore proposed that, although preciseK _A values from conductance cannot be determined, the most probable values are those associated with realistic estimates ofa. When data cover a limited concentration range, minimum standard deviations are often indeterminate or vary greatly for duplicate runs. It is shown that reasonable values ofK _A can be obtained from such data if comparison is made at estimated values ofa.Notation The symbols not defined in the text are the following b e ²/kTa for 1:1 electrolytes - e electronic charge - k Boltzmann gas constant - T absolute temperature - dielectric constant of solvent - –(3/2y)(_e0/₀)     

Anionic forensic signatures for sample matching of potassium cyanide using high performance ion chromatography and chemometrics

Potassium cyanide was used as a model toxicant to determine the feasibility of using anionic impurities as a forensic signature for matching cyanide salts back to their source. In this study, portions of eight KCN stocks originating from four countries were separately dissolved in water and analyzed by high performance ion chromatography (HPIC) using an anion exchange column and conductivity detection. Sixty KCN aqueous samples were produced from the eight stocks and analyzed for 11 anionic impurities. Hierarchal cluster analysis and principal component analysis were used to demonstrate that KCN samples cluster according to source based on the concentrations of their anionic impurities. The Fisher-ratio method and degree-of-class separation (DCS) were used for feature selection on a training set of KCN samples in order to optimize sample clustering. The optimal subset of anions needed for sample classification was determined to be sulfate, oxalate, phosphate, and an unknown anion named unk5. Using K-nearest neighbors (KNN) and the optimal subset of anions, KCN test samples from different KCN stocks were correctly determined to be manufactured in the United States. In addition, KCN samples from stocks manufactured in Belgium, Germany, and the Czech Republic were all correctly matched back to their original stocks because each stock had a unique anionic impurity profile. The application of the Fisher-ratio method and DCS for feature selection improved the accuracy and confidence of sample classification by KNN.