Evidence for pi-pi electron donor-acceptor interactions between pi-donor aromatic compounds and pi-acceptor sites in soil organic matter through pH effects on sorption

Elucidation of molecular-level interactions controlling the sorption of organic compounds in soils is of major theoretical and practical interest. Sorption of pi-electron donor compounds, pentamethylbenzene (PMB), naphthalene (NAPH), and phenanthrene (PHEN), in a number of soils was found to increase with decreasing pH in the range of approximately pH 2.5-7. This behavior could not be attributed to pH-dependent alteration of the hydrophobic character of humic substances, pi-H-bonding, interaction with mineral surfaces, interaction with black carbons, solute coplanarity, or pH effects on solute activity coefficient. No significant effect of pH was observed for non-pi-donor hydrophobic compounds, whether planar or not: trans-1,2-dichlorocyclohexane (DCCH), hexachloro-1,3-butadiene (HCBD), 1,2,4-trichlorobenzene (TCB), 2,2',5,5'-tetrachlorobiphenyl, and 3,3',4,4'-tetrachlorobiphenyl. The opposite pH effect was observed for 2-nonanol and 2-nonanone, which are non-pi-donors, but capable of H-bonding. Also, no pH-dependent sorption was observed between the pi-donor PHEN and alumina, a model inorganic surface. We propose that the pi-donor solutes interact with pi-acceptor sites in soil organic matter (SOM), including aromatic rings with multiple carboxyl groups, aromatic amines, or heteroaromatic amines. The pi-acceptor ability of such aromatic moieties would increase with protonation. pi-pi Interactions between PMB, NAPH, and PHEN, and model SOM acceptors, 1,3,5-benzenetricarboxylic acid (BTA), 1,4,5,8-naphthalenetetracarboxylic acid (NTA), and pyridine (PY) in methanol and methanol-water, were verified by the appearance of pH-dependent upfield 1H NMR chemical shifts induced by ring current effects. UV/vis spectra showed pH-dependent charge-transfer bands for various donors with NTA. No NMR shifts or charge-transfer bands were found for nondonor compounds paired with the model acceptors.     

Self-reported injuries among seafarers. Questionnaire validity and results from an international study

International surveys of occupational injuries among seafarers have so far been missing. It was the aim to test the method of self-report of injuries and length of time at risk during the latest duty period and second to study the injury incidence rate among seafarers by use of the method. A pilot study was conducted (n = 1068) in Finland, Denmark, the Philippines, Croatia and Spain using self-completed questionnaires with questions about the person, the ship, the duration of latest duty period and injuries. The duration of the self-reporting duty period was in the Danish part compared with information from the crew register of the Maritime Authority. For seafarers from merchant ships in the Danish sub-study there was acceptable correspondence between the information from the seafarers and the Maritime Authority, but not when referring to ferries and non-specified types of ship. Unadjusted and adjusted injury incidence rates-ratios (IRRs) based on number of injuries per number of work hours were calculated. Adjusted IRRs for ordinary seamen/officers: IRR = 2.43 (95% CI: 1.25-4.72); for age < 35/35+ years: IRR = 1.97 (1.02-3.81); length of tour: 117 days or longer compared with < 117 days: IRR = 0.46 (95% CI: 0.22-0.95); 57-70 working hours per week compared with < 57 h: IRR = 1.26 (0.48-3.29), 71+h compared with < 57 h: IRR = 2.12 (0.84-5.36). Non-significant IRRs >1.00 were found for ships under 10,000 GT compared with larger ships and for own flagged ships compared with ships under flag of convenience. In conclusion, more than 70 h of work per week was related to a higher rate of injuries for seafarers on merchant ships, but the result was not statistically significant. Self-report of the duration of the latest tour of duty is useful for seafarers from merchant ships with short-term employments, but not for ferries and other, non-specified types of ship with other or permanent employment.     

Amplitude-modulated laser imager

Laser systems have been developed to image underwater objects. However, the performance of these systems can be severely degraded in turbid water. We have developed a technique using modulated light to improve underwater detection and imaging. A program, Modulated Vision System (MVS), which is based on a new theoretical approach, has been developed to predict modulated laser imaging performance. Experiments have been conducted in a controlled laboratory environment to test the accuracy of the theory as a function of system and environmental parameters. Results show a strong correlation between experiment and theory and indicate that the MVS program can be used to predict future system performance.     

Effects of fiber-optic probe design and probe-to-target distance on diffuse reflectance measurements of turbid media: an experimental and computational study at 337 nm

Fiber-optic probes are widely used in optical spectroscopy of biological tissues and other turbid media. Only limited information exists, however, on the ways in which the illumination-collection geometry and the overall probe design influence the interrogation of media. We have investigated both experimentally and computationally the effect of probe-to-target distance (PTD) on the diffuse reflectance collected from an isotropically (Lambertian) scattering target and an agar-based tissue phantom. Studies were conducted with three probes characterized by either common (single-fiber) or separate (two bifurcated multifiber probes) illumination and collection channels. This study demonstrates that PTD, probe design, and tissue scattering anisotropy influence the extent of the transport of light into the medium, the light-collection efficiency, and the sampling volume of collected light. The findings can be applied toward optimization of fiber-optic probe designs for quantitative optical spectroscopy of turbid media including biological tissues.     

Performance of different thermoluminescence dosimeters in 90SR+90Y radiation fields

The dosimetry of beta radiation is a difficult process especially because of the low penetration of beta particles in matter. The dosemeter utilised for this kind of procedure needs to approximate an ideal point-like detector: it should be as thin as possible, and its area should be small. The thermoluminescence dosemeters (TLDs) meet with these requirement properties. The aim of this work was to study the dosimetric characteristics of different TLDs to verify the possibility of their use for the calibration of 90Sr+90Y plane applicators. The response reproducibility, calibration curves, TL response as a function of the source-detector distance, the transmission factors and the linearity of the sample response were obtained for several types of dosimetric pellets.     

Preparation and etherification reaction of fatty dichlorocyclopropanes

Dichlorocarbene was added tocis-9-octadecene, methyl oleate, methyl elaidate, and methyl linoleate to form the corresponding mono- or bis-dichlorocyclopropanes in yields of 75–88%. The dichlorocyclopropanes underwent ring-opening substitution on heating with alcohols (or water) to form β-chlorallylic ethers (or alcohols). The ethers were obtained in yields of 46 to 84%. Tetraethylene glycol and methyl lactate, as hydroxyl compounds, gave a polyethenoxy ester and an ether-linked diester, respectively. Presented at AOCS meeting, Toronto, October, 1962. F. Utiliz. Res. & Dev. Div. ARS, U.S.D.A.     

Comparison of Rat Hepatic Cholesterol Biosynthesis During Skim Milk Versus Whey Permeate Ingestion

Whey permeate is an ultrafiltrate of whey that is devoid of protein but contains lactose, salts, and other soluble low molecular weight compounds. These experiments compared cholesterol concentrations of blood plasma, hepatic lipids, and hepatic cholesterol biosynthesis of rats ingesting skim milk powder versus whey permeate powder. Groups of young male rats weighing 90 to 92 g were fed a casein-based diet into which skim milk powder or whey permeate powder was incorporated isocalorically. No effects of skim milk or whey permeate on plasma cholesterol concentrations were observed at any time during 5-wk of feeding. However, 3-hydroxy-3-methylglutaryl coenzyme A reductase activity was increased by either skim milk or whey permeate feeding. Hepatic cholesterol, triglyceride, and phospholipid concentrations at wk 5 were unchanged. Plasma and hepatic cholesterol responses of rats to whey permeate ingestion are similar to those that occur with skim milk consumption, and plasma and hepatic cholesterol concentrations do not reflect necessarily an increase in hepatic cholesterol biosynthesis.     

Cytology,Ultrastructure, Taxonomy,and Phylogenetic Relationships of Great Lakes Filamentous Algae

Recent cytological and ultrastructural work has required revision of previous ideas concerning the taxonomy and phylogenetic relationships of Great Lakes filamentous algae. Characters found to be of phylogenetic importance include the fine structure of dividing cells and reproductive cells, as well as certain biochemical features. A number of modern cellular and evolutionary studies are described which collectively suggest that the Laurentian Great Lakes have been invaded by marine littoral algae several times, by Ulothrix zonata, Cladophora glomerata, and most recently, by Bangia atropurpurea. In each case, physiological adaptation to freshwater has occurred, often accompanied by apparent loss of sexual reproductive cycles     

Comparison of hypnosis plus counseling, counseling alone, and hypnosis alone in a community service smoking withdrawal program.

3- and 10-mo follow-up data on 48 volunteers in a smoking withdrawal program indicate that neither hypnosis alone nor group contact alone yielded satisfactory results; however, the combined use of these procedures yielded a fairly high success rate (56.25 and 50% for the 3- and 10-mo assessments, respectively). (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Minors' consent to treatment: A developmental perspective.

Discusses the cognitive and behavioral characteristics of minors in relation to the question of competence to consent to treatment. The legal standard (knowing, intelligent, and voluntary) used to judge the effectiveness of consent is translated into psychological concepts, especially cognitive abilities. A review of developmental psychological research is presented, which examines these concepts as they relate to minors' abilities to satisfy the legal standard. It is suggested that cognitive developmental stages associated with ages below 11–23 yrs might exclude such minors from meaningful consent. In addition to cognitive considerations, certain results suggest that the tendency toward deference in early adolescence is so normative that capacity for voluntary consent is questionable through age 14, but existing evidence provides no psychological grounds for maintaining the general legal assumption that minors at age 15 and above cannot provide competent consent. (63 ref) (PsycINFO Database Record (c) 2010 APA, all rights reserved)