Upper limit for thermal direct photon production in heavy-ion collisions at 60 and 200A·GeV

The production of direct photons has been investigated in reactions ofp and¹⁶O projectiles at 60 and 200A·GeV with C and Au nuclei. Photon and ⁰ spectra have been measured in the pseudorapidity range 1.52.1 for the transverse momentum region 0.4 GeV/cp _T 2.8 GeV/c employing the lead-glass spectrometer SAPHIR. An upper limit of 15% at the 90% confidence level for the direct photon signal relative to the neutral pion production is obtained from the comparison of measured photon spectra with Monte Carlo simulations of the hadronic background based on the reconstructed yield of ⁰ and mesons. Consequences for a possible phase transition to a quark-gluon plasma are discussed.     

A well-tested procedure for instrumental neutron activation analysis of silicate rocks and minerals

Procedures for instrumental neutron activation analysis (INAA) have been developed and used on more than a thousand small samples of terrestrial and lunar silicate rocks and minerals for determination of Co, Cr, Fe, Hf, Na, Ni, Sc, Ta, Th, and the rare earths La, Ce, Sm, Eu, Tb, Yb, and Lu. Precision has been determined by repeated analysis of Knippa basalt and DTS-1 to be better than ±5 percent for all elements except Ni, Yb, Lu, and Hf. Mean values and estimates of accuracy are given for Knippa basalt and USGS standards AGV-1, G-2, GSP-1, and W-1. Important features of the method are its precision and ease of data reduction.     

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.     

Concentration profiles of cocaine, pyrolytic methyl ecgonidine and thirteen metabolites in human blood and urine: determination by gas chromatography-mass spectrometry

When cocaine is smoked, a pyrolytic product, methyl ecgonidine (anhydroecgonine methyl ester), is also consumed with the cocaine. The amount of methyl ecgonidine formed depends on the pyrolytic conditions and composition of the illicit cocaine. This procedure describes detection of cocaine and 10 metabolites--cocaethylene, nor-cocaine, nor-cocaethylene, methyl ecgonine, ethyl ecgonine, benzoylecgonine, nor-benzoylecgonine, m-hydroxybenzoylecgonine, p-hydroxybenzoylecgonine and ecgonine--in blood and urine. In addition, the detection of pyrolytic methyl ecgonidine and three metabolites--ecgonidine (anhydroecgonine), ethyl ecgonidine (anhydroecgonine ethyl ester) and nor-ecgonidine (nor-anhydroecgonine)--are included. The newly described metabolites, ethyl ecgonidine and nor-ecgonidine, were synthesized and characterized by gas chromatography-mass spectrometry (GC-MS). All 15 compounds were extracted from 3 mL of blood or urine by solid-phase extraction and identified by a GC-MS method. The overall recoveries were 49% for methyl ecgonine, 35% for ethyl ecgonine, 29% for ecgonine and more than 83% for all other drugs. The limits of detection were between 0.5 and 4.0 ng/mL except for ecgonine, which was 16 ng/mL. Linearity for each analyte was established and in all cases correlation coefficients were 0.9985-1.0000. The procedure was applied to examine the concentration profiles of analytes of interest in post-mortem (PM) blood and urine, and in urine collected from living individuals (LV). These specimens previously were shown to be positive for the cocaine metabolite, benzoylecgonine. Ecgonidine, the major metabolite of methyl ecgonidine, was present in 77% of PM and 88% of the LV specimens, indicating smoking as the major route of cocaine administration. The new pyrolytic metabolites, ethyl ecgonidine and nor-ecgonidine, were present in smaller amounts. The urine concentrations of nor-ecgonidine were 0-163 ng/mL in LV and 0-75 ng/mL in PM specimens. Ethyl ecgonidine was found only in PM urine at concentrations 0-39 ng/mL. Ethanol-related cocaine metabolites, ethyl ecgonine or cocaethylene, were present in 69% of PM and 53% of cocaine-positive LV specimens, implying alcohol consumption with cocaine use. The four major metabolites of cocaine--benzoylecgonine, ecgonine, nor-benzoylecgonine and methyl ecgonine--constituted approximately 88 and 97% of all metabolites in PM and LV specimens, respectively. The concentrations of nor-cocaine and nor-cocaethylene were consistently the lowest of all cocaine metabolites. At benzoylecgonine concentrations below 100 ng/mL, ecgonine was present at the highest concentrations. In 20 urine specimens, benzoylecgonine and ecgonine median concentrations (range) were 54 (0-47) and 418 ng/mL (95-684), respectively. Therefore, detection of ecgonine is advantageous when benzoylecgonine concentrations are below 100 ng/mL.     

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.