Gel-permeation chromatography and cellulose. I. Effect of degree of nitration of cellulose on molecular weight distribution data

Consideration is given to the effect on gel-permeation chromatographic (GPC) data of the extent of substitution in nitrated cellulose. GPC parameters for samples containing 13.55–13.81% nitrogen (14.14% corresponds to complete substitution, DS = 3) were hardly affected by this variation in substitution. Variations that were observed are considered to arise within the samples themselves. Experiments with low molecular weight organic iodides, nitrates, and hydroxyl compounds indicate longer chain lengths than actual; this is attributed to extensive solvation of the substituent groups. The very long chain lengths obtained for cellulose nitrate by the present GPC procedure may arise from such an affect.     

Use of photochemical reactions in flow injection: determination of oxalate in urine

The use of photochemical reactions in flow injection (FI) is reported. The irradiation of an FI reactor with a suitable source facilitates the development of the iron(III)-oxalate reaction, allowing the amperometric determination of the anion in the range 1.0-13.0 micrograms ml-1, with a relative standard deviation of 1.1% and a sampling frequency of 40 h-1. The proposed method was applied successfully to the determination of oxalate in urine samples.     

Facility location in the presence of forbidden regions,I: Formulation and the case of Euclidean distance with one forbidden circle

A constrained form of the Weber problem is formulated in which no path is permitted to enter a prespecified forbidden region $\text{R}$ of the plane. Using the calculus of variations the shortest path between two points $\text{x}\text{,}\text{y}\text{?}\text{R}$ which does not intersect $\text{R}$ is determined. If $\text{d(}\text{x}\text{,}\text{y}\text{)}$ is unconstrained distance, we denote the shortes distance along a feasible path by $\text{d}\text{(}\text{x}\text{y}\text{)}$. The constrained Weber problem is, then: given points $\text{x}{}_{\mathrm{j}}\text{?}\text{R}$ and positive weights w_j, j = 1,2,…,n, find a point $\text{x}\text{?}\text{R}$ such that

$\text{f(}\text{x}\text{)=}\text{Σ}\text{n}\text{j=1}\text{d(}\text{x}\text{,}\text{x}{}_{\mathrm{j}}\text{)}$

is a minimum.An algorithm is formulated for the solution of this problem when $\text{d(}\text{x}\text{,}\text{y}\text{)}$ is Euclidean distance and $\text{R}$ is a single circular region. Numerical results are presented.     

Photoredox-enabled 1,2-dialkylation of α-substituted acrylates via Ireland–Claisen rearrangement

Herein, we report the 1,2-dialkylation of simple feedstock acrylates for the synthesis of valuable tertiary carboxylic acids by merging Giese-type radical addition with an Ireland–Claisen rearrangement. Key to success is the utilization of the reductive radical-polar crossover concept under photocatalytic reaction conditions to force the [3,3]-sigmatropic rearrangement after alkyl radical addition to allyl acrylates. Using readily available alkyl boronic acids as radical progenitors, this redox-neutral, transition-metal-free protocol allows the mild formation of two C(sp³)–C(sp³) bonds, thus providing rapid access to complex tertiary carboxylic acids in a single step. Moreover, this strategy enables the efficient synthesis of highly attractive α,α-dialkylated γ-amino butyric acids (GABAs) when α-silyl amines are used as radical precursors – a structural motif that was still inaccessible in related transformations. Depending on the nature of the radical precursors and their inherent oxidation potentials, either a photoredox-induced radical chain or a solely photoredox mechanism is proposed to be operative.

A photocatalytic 1,2-dialkylation of α-substituted acrylates is enabled by a reaction cascade combining reductive radical-polar crossover with the established Ireland–Claisen rearrangement for the synthesis of valuable tertiary carboxylic acids.     

μ+ depolarization inAlGd alloys

The ⁺ depolarization rate in diluteAlGd alloys containing 50 and 450 atomic ppm Gd was measured in a transverse field of 80 Oe over the temperature range 6–300 K. For both alloys, A increased dramatically above 200 K, reaching values of 0.69 and 0.93 s^–1, respectively, near room temperature. The results are interpreted as providing evidence for a thermally-activated trapping mechanism.This work was supported by the U.S. Department of Energy.     

Muon diffusion and trapping studies in high purity vanadium

We present the first results of a study of the effects of varying impurity concentration on the temperature dependence of the depolarization rate of positive muons implanted into vanadium. Data are reported for the most highly purified polycrystalline sample yet measured, and the same sample subsequently doped with about 500 ppm oxygen by weight. The data for the pure sample shows a low depolarization rate (<.15 sec^–1) at all temperatures measured, showing a broad minimum centered at 35 K, followed by a sharp peak near 90 K and a rapid drop to negligible values at 200 K. The data is contrasted with previously published data [2] on less pure samples, and calls into question previous interpretations of the behavior of the ⁺ at low temperatures in impure vanadium [1] as one-phonon-assisted tunneling.This work was supported by the U. S. Department of Energy     

Interpretation of Polarized Absorption and Emission Spectra of Molecules Incorporated in Stretched Polymer Films

Different methods for the interpretation of linear dichroic spectra of molecules incorporated in uniaxial matrices are discussed. A method based on the combination of both polarized absorption and emission measurements is described for the resolution of absorption and emission spectra into their different polarized components, and for the investigation of molecular distributions in the oriented matrix. The distributions of some planar molecules of different shapes incorporated in stretched polyethylene films are presented.     

Anomalous Energy Minima Surfaces

Previous publications^2–5 have examined the phenomenon of level crossings as predicted by the semiempirical techniques CNDO/2⁶, IMDO⁷, and MINDO/3⁸ for certain molecules when the total energy is viewed as a function of some conformational property. The purpose of this article is to examine this same phenomenon using the extended Hückel method(EHM)⁹, the iterated extended Hückel method(IEHM), and an ab-initio procedure with a minimal STO-3G basis set. The molecule chosen for this study is CO₂ due to its structural simplicity and since previous calculations^2–5 have demonstrated level crossing with this molecule.