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Pd-catalyzed transformations of allenyl malonates provide convenient access to functionalized carbocycles, but the influence of the ligand, solvent, base, and reaction conditions on the mechanism, regioselectivity, and product outcome of the cyclization are not well-understood. Additionally, from the perspective of synthetic utility, access to either fully substituted or enantioenriched cyclopentane building blocks has not yet been achieved. This work describes how targeted changes to the reaction conditions enable predictable control over the mechanism of Pd-catalyzed allene cross-coupling/cyclization and cycloisomerization, irrespective of the allene substitution pattern. Both enantioenriched cyclopropanes and cyclopentenes can be obtained through axis-to-center chirality transfer from the allene precursor at room temperature, which is not possible using reported Pd-catalyzed methods that result in racemization of the allene. Finally, the ability to divert the reactivity of the allenyl malonate from cross-coupling/cyclization to cycloisomerization by a simple switch of the ligand on Pd from a bidentate phosphine to an electron-poor triphenylphosphite is demonstrated.

Main Conclusion: Odontarrhena is a highly diverse genus of Ni-hyperaccumulators. Here, we demonstrate substantial inability to accumulate Ni in the facultative serpentinophyte O. sibirica, which seems a unique case among the numerous species of the genus that grow on ultramafic soils. Odontarrhena is the most diverse genus of Ni-accumulating plants in W Eurasia, with most taxa growing obligatorily or facultatively on ultramafic soils. A notable exception may be O. sibirica, a facultative serpentinophyte from the E Mediterranean and W Asia in which accumulation ability is still enigmatic. We addressed this issue using observational and experimental methods. Atomic Absorption Analysis of 33 herbarium specimens and plant and soil samples from seven ultramafic and non-ultramafic sites in Greece revealed shoot Ni values always much lower than 1000 µg g -1 , non-significant differences between plants from the two soil types and no relationship with soil pH. Only two Turkish specimens from waste mines had shoot Ni concentration > 1000 µg g -1 . The reasons for this deviating result remain obscure, but may be associated with inherent peculiarities of the local populations. When cultivated together with congeneric Ni-accumulating species on the same natural ultramafic soil, only O. sibirica was unable to accumulate the metal. Although plant growth was stimulated in hydroponics at relatively low NiSO 4 levels (50-150 µM), as typical for hyperaccumulators, Ni-accumulation occurred only at higher concentrations which had a toxic effect. This peculiar combination of Ni-response traits could be the result of a partial evolutionary loss of ability with respect to all other Ni-accumulating congeneric species. For this, O. sibirica could represent a unique model system for further studies on the evolutionary dynamics, physiological mechanisms and genetic control of metal accumulation and homeostasis.

Metal-catalyzed allene cycloisomerizations provide rapid entry into five-membered carbocyclic frameworks, a common motif in natural products and pharmaceuticals. While both Au(I) and Pd(0)-catalyzed allene cycloisomerizations give 5- endo - dig cyclization, Pd prefers the syn diastereomer in contrast to the anti isomer observed with Au. The change in stereoselectivity is proposed to arise from buildup of A 1,3 strain during the key carbopalladation step to furnish the cycloisomerized products in moderate to good dr with yields comparable to Au(I) catalysts.

The cytotoxicity of dialkylated lariat ethers has been previously attributed to their ionophoric properties. Herein, we provide evidence that these effects are due to loss of membrane integrity rather than ion transport, a finding with important implications for the future design of synthetic ionophores., Competing Interests: Conflicts of interest There are no conflicts to declare.

Nanostructuring of thermoelectric materials can lead to thermal-to-electrical conversion efficiencies comparable with mechanical energy conversion. Theory predicts that characteristic length scales of <10 nm are necessary to achieve high thermoelectric figures of merit (zT > 3). While sub-10 nm diameter nanowire arrays have been difficult to fabricate, we present here a novel template for sub-10 nm thermoelectric nanowire array fabrication using anodized aluminum oxide followed by silica wall coating for pore confinement. Electrodeposited bismuth telluride nanowires displayed increasing electrical-to-thermal conductivity ratio as the pore diameter decreased, in agreement with theoretical predictions. Achieving the desired stoichiometric ratio of Bi 2 Te 3 through electrodeposition was non-trivial, which limited the Seebeck coefficient of the nanowires. However, hydrolysis of the nanopore walls led to improved electrodeposition, achieving near stoichiometric bismuth-to-tellurium ratios and ultimately p-type thermoelectric nanowire arrays with a Seebeck coefficient of up to 79 μV K -1 .

Site- and regiocontrolled Au-catalyzed allene carbocyclizations furnish highly substituted cyclopentenes in >1:1 dr. Significant substitution on the substrate is tolerated, with potential to install five contiguous stereocenters after alkene functionalization. Major challenges include identifying a Au/Cu catalyst that controls both the relative rates of allene epimerization/cyclization and the facial selectivity in addition of a metal enolate to the allene. Experiments to achieve stereodivergent cyclizations and transform key cyclopentenes into useful synthetic building blocks are described.

Phytomining technology employs hyperaccumulator plants to take up metal in harvestable plant biomass. Harvesting, drying and incineration of the biomass generates a high-grade bio-ore. We propose that "agromining" (a variant of phytomining) could provide local communities with an alternative type of agriculture on degraded lands; farming not for food crops, but for metals such as nickel (Ni). However, two decades after its inception and numerous successful experiments, commercial phytomining has not yet become a reality. To build the case for the minerals industry, a large-scale demonstration is needed to identify operational risks and provide "real-life" evidence for profitability.

A series of field trials were conducted to investigate the potential of Noccaea caerulescens F.K. Mey [syn. Thlaspi caerulescens J &C Presl. (see Koch and Al-Shehbaz 2004)] populations (genotypes) derived from southern France to phytoextract localized Cd/Zn contamination in Thailand. Soil treatments included pH variation and fertilization level and application of fungicide. N. caerulescens populations were transplanted to the field plots three months after germination and harvested in May, prior to the onset of seasonal rains. During this period growth was rapid with shoot biomass ranging from 0.93-2.2 g plant(-1) (280-650 kg ha(-1)) DW. Shoot Cd and Zn concentrations for the four populations evaluated ranged from 460-600 and 2600-2900 mg kg(-1) DW respectively. Cadmium and Zn Translocation Factors (shoot/root) for the populations tested ranged from 0.91-1.0 and 1.7-2.1 and Bioaccumulation Factors ranged from 12-15 and 1.2-1.3. We conclude that optimizing the use of fungicidal sprays, acidic soil pH, planting density and increasing the effective cropping period will increase rates of Cd and Zn removal enough to facilitate practical Cd phytoextraction from rice paddy soils in Thailand.

Past applications of biosolids to soils at some locations added higher Cd levels than presently permitted. Cadmium phytoextraction would alleviate current land use constraints. Unamended farm soil, and biosolids amended farm and mine soils were obtained from a Fulton Co., IL biosolids management facility. Soils contained 0.16, 22.8, 45.3 mg Cd kg(-1) and 43.1, 482, 812 mg Zn kg(-1) respectively with initial pH 6.0, 6.1, 6.4. In greenhouse studies, Swiss chard (Beta vulgaris var. cicla), a Cd-accumulator maize (inbred B37 Zea mays) and a southern France Cd-hyperaccumulator genotype of Noccaea caerulescens were tested for Cd accumulation and phytoextraction. Soil pH was adjusted from ∼5.5-7.0. Additionally 100 rice (Oryza sativa) genotypes and the Ni-hyperaccumulator Alyssum murale were screened for potential phytoextraction use. Chard suffered phytotoxicity at low pH and accumulated up to 90 mg Cd kg(-1) on the biosolids amended mine soil. The maize inbred accumulated up to 45 mg Cd kg(-1) with only mild phytotoxicity symptoms during early growth at pH>6.0. N. caerulescens did not exhibit phytotoxicity symptoms at any pH, and accumulated up to 235 mg Cd kg(-1) in 3 months. Reharvested N. caerulescens accumulated up to 900 mg Cd kg(-1) after 10 months. Neither Alyssum nor 90% of rice genotypes survived acceptably. Both N. caerulescens and B37 maize show promise for Cd phytoextraction in IL and require field evaluation; both plants could be utilized for nearly continuous Cd removal. Other maize inbreds may offer higher Cd phytoextraction at lower pH, and mono-cross hybrids higher shoot biomass yields. Further, maize grown only for biomass Cd maximum removal could be double-cropped.

Approximately 500 species of plants are known to hyperaccumulate heavy metals and metalloids. The majority are obligate metallophytes, species that are restricted to metalliferous soils. However, a smaller but increasing list of plants are "facultative hyperaccumulators" that hyperaccumulate heavy metals when occurring on metalliferous soils, yet also occur commonly on normal, non-metalliferous soils. This paper reviews the biology of facultative hyperaccumulators and the opportunities they provide for ecological and evolutionary research. The existence of facultative hyperaccumulator populations across a wide edaphic range allows intraspecific comparisons of tolerance and uptake physiology. This approach has been used to study zinc and cadmium hyperaccumulation by Noccaea (Thlaspi) caerulescens and Arabidopsis halleri, and it will be instructive to make similar comparisons on species that are distributed even more abundantly on normal soil. Over 90% of known hyperaccumulators occur on serpentine (ultramafic) soil and accumulate nickel, yet there have paradoxically been few experimental studies of facultative nickel hyperaccumulation. Several hypotheses suggested to explain the evolution of hyperaccumulation seem unlikely when most populations of a species occur on normal soil, where plants cannot hyperaccumulate due to low metal availability. In such species, it may be that hyperaccumulation is an ancestral phylogenetic trait or an anomalous manifestation of physiological mechanisms evolved on normal soils, and may or may not have direct adaptive benefits., (Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.)

Background and Aims: The analysis of herbarium specimens has previously been used to prospect for 'new' hyperaccumulators, while the use of foliar manganese (Mn) concentrations as a taxonomic tool has been suggested. On the basis of their geographic and taxonomic affiliations to known Mn hyperaccumulators, six eastern Australian genera from the Queensland Herbarium collection were sampled for leaf tissue analyses., Methods: ICP-OES was used to measure Mn and other elemental concentrations in 47 species within the genera Austromyrtus, Lenwebbia, Gossia (Myrtaceae), Macadamia (Proteaceae), Maytenus and Denhamia (Celastraceae)., Key Results: The resulting data demonstrated (a) up to seven 'new' Mn hyperaccumulators, mostly tropical rainforest species; (b) that one of these 'new' Mn hyperaccumulators also had notably elevated foliar Ni concentrations; (c) evidence of an interrelationship between foliar Mn and Al uptake among the Macadamias; (d) considerable variability of Mn hyperaccumulation within Gossia; and (e) the possibility that Maytenus cunninghamii may include subspecies., Conclusions: Gossia bamagensis, G. fragrantissima, G. sankowsiorum, G. gonoclada and Maytenus cunninghamii were identified as 'new' Mn hyperaccumulators, while Gossia lucida and G. shepherdii are possible 'new' Mn hyperaccumulators. Of the three Myrtaceae genera examined, Mn hyperaccumulation appears restricted to Gossia, supporting its recent taxonomic revision. In the context of this present investigation and existing information, a reassesment of the general definition of Mn hyperaccumulation may be warranted. Morphological variation of Maytenus cunninghamii at two extremities was consistent with variation in Mn accumulation, indicating two possible 'new' subspecies. Although caution should be exercised in interpreting the data, surveying herbarium specimens by chemical analysis has provided an effective means of assessing foliar Mn accumulation. These findings should be followed up by field studies.

There are very few practical demonstrations of the phytoextraction of metals and metalloids from soils and sediments beyond small-scale and short-term trials. The two approaches used have been based on using 1) hyperaccumulator species, such as Thlaspi caerulescens (Pb, Zn, Cd, Ni), Alyssum spp. (Ni, Co), and Pteris vittata (As) or 2) fast-growing plants, such as Salix and Populus spp. that accumulate above-average concentrations of only a smaller number of the more mobile trace elements (Cd, Zn, B). Until we have advanced much more along the pathway of genetic isolation and transfer of hyperaccumulator traits into productive plants, there is a high risk in marketing either approach as a technology or stand-alone solution to clean up contaminated land. There are particular uncertainties over the longer-term effectiveness of phytoextraction and associated environmental issues. Marginally contaminated agricultural soils provide the most likely land use where phytoextraction can be used as a polishing technology. An alternative and more useful practical approach in many situations currently would be to give more attention to crops selected for phytoexclusion: selecting crops that do not translocate high concentrations of metals to edible parts. Soils of brownfield, urban, and industrial areas provide a large-scale opportunity to use phytoremediation, but the focus here should be on the more realistic possibilities of risk-managed phytostabilization and monitored natural attenuation. We argue that the wider practical applications of phytoremediation are too often overlooked. There is huge scope for cross-cutting other environmental agenda, with synergies that involve the recovery and provision of services from degraded landscapes and contaminated soils. An additional focus on biomass energy, improved biodiversity, watershed management, soil protection, carbon sequestration, and improved soil health is required for the justification and advancement of phytotechnologies.

Single-walled carbon nanotube (SWNT) bundles are selectively removed from an aqueous dispersion containing individually suspended carbon nanotubes coated with gum Arabic via interfacial trapping. The suspensions are characterized with absorbance, fluorescence, and Raman spectroscopy as well as atomic force microscopy (AFM) and rheology. The resulting aqueous suspensions have better dispersion quality after interfacial trapping and can be further improved by altering the processing conditions. A two-step extraction process offers a simple and fast approach to preparing high-quality dispersions of individual SWNTs comparable to ultracentrifugation. Partitioning of SWNTs to the liquid-liquid interface is described by free energy changes. SWNT bundles prefer to reside at the interface over individually suspended SWNTs because of greater free energy changes.

Understanding the relative importance of the abiotic environment and species interactions in determining the distribution and abundance of organisms has been a challenge in ecological research. Serpentine substrata are stressful environments for plant growth due to multiple limitations, collectively called the "serpentine syndrome". In the present review, our aim is not only to describe recent work in serpentine ecology, but also to highlight specific mechanisms of species tolerance and adaptation to serpentine soils and their effects on community structure and ecosystem functioning. We present hypotheses of the development of serpentine endemism and a description of functional traits of serpentine plants together with a synthesis of species interactions in serpentine soils and their effects on community structure and ecosystem productivity. In addition, we propose hypotheses about the effects of the 'serpentine syndrome' on ecosystem processes including productivity and decomposition.

Thlaspi caerulescens is known to hyperaccumulate high quantities of Cd with Cd concentrations up to 3000 mg kg(-1) in some populations from south of France. However, within these populations, the Cd concentrations can vary widely from plant to plant in a way that appears to be not entirely due to variations in soil Cd. The aim of this work was to investigate the variability in the Cd uptake ability of individual plants within a population and among seedlings grown from seeds from a single plant. Ten populations of T. caerulescens plants were selected from four locations (V: Viviez; SF: Saint Félix-de-Pallières; LB: Le Bleymard; CMA: Col du Mas de l'Air) depending of the extent and soil homogeneity of the site. One population from CMA consisted of the progeny of a single maternal plant. Hundred plants of each population were grown for three months in the same homogeneous and lightly Cd-polluted soil (about 20 mg total Cd kg(-1) dry soil). Cadmium uptake behavior of the plants was monitored by labeling the soil with 109Cd. To allow partial plant destruction, radioanalysis was performed on the largest leaf of each plant as an indicator of the total Cd concentration in plant shoots. Results showed significant differences in biomass production and Cd uptake by T. caerulescens between sites and between populations within sites. We observed a wide intra-population variation in biomass, Cd concentration and total Cd uptake. For these properties, 1 to 5 percents of the plants in each population varied by more than a factor of two from the mean values. The mean Cd uptake by the single-plant population from CMA was more than 40% higher than for the population at large. T. caerulescens would respond to traditional selection methods, which would significantly improve the phytoextraction of Cd.

We report on the second phase of a programme to select a relative of Arabidopsis thaliana for use in large-scale molecular genetic studies of nickel (Ni) and zinc (Zn) hyperaccumulation. We also report on the relatedness among Thlaspi caerulescens accessions and the utility of using O-acetyl-L-serine as a marker for Ni and Zn hyperaccumulation potential. Twenty-seven new accessions of metal-accumulating species collected in the Czech Republic, France, Greece, Italy, Slovenia and the USA during Spring-Summer 2002 were evaluated. The criteria established for selection were hyperaccumulation of metals (Ni and Zn); compact growth habit; reasonable time to flowering; production of > or = 1000 seeds per plant; self-fertility; compact diploid genome; high sequence similarity to A. thaliana; > or = 0.1% transformation efficiency with easy selection. We conclude that the best candidate identified in the first phase was the best candidate overall: T. caerulescens accession St Félix de Pallières.

Two strategies of phytoextraction have been shown to have promise for practical soil remediation: domestication of natural hyperaccumulators and bioengineering plants with the genes that allow natural hyperaccumulators to achieve useful phytoextraction. Because different elements have different value, some can be phytomined for profit and others can be phytoremediated at lower cost than soil removal and replacement. Ni phytoextraction from contaminated or mineralized soils offers economic return greater than producing most crops, especially when considering the low fertility or phytotoxicity of Ni rich soils. Only soils that require remediation based on risk assessment will comprise the market for phytoremediation. Improved risk assessment has indicated that most Zn + Cd contaminated soils will not require Cd phytoextraction because the Zn limits practical risk from soil Cd. But rice and tobacco, and foods grown on soils with Cd contamination without corresponding 100-fold greater Zn contamination, allow Cd to readily enter food plants and diets. Clear evidence of human renal tubular dysfunction from soil Cd has only been obtained for subsistence rice farm families in Asia. Because of historic metal mining and smelting, Zn + Cd contaminated rice soils have been found in Japan, China, Korea, Vietnam and Thailand. Phytoextraction using southern France populations of Thlaspi caerulescens appears to be the only practical method to alleviate Cd risk without soil removal and replacement. The southern France plants accumulate 10-20-fold higher Cd in shoots than most T. caerulescens populations such as those from Belgium and the UK. Addition of fertilizers to maximize yield does not reduce Cd concentration in shoots; and soil management promotes annual Cd removal. The value of Cd in the plants is low, so the remediation service must pay the costs of Cd phytoextraction plus profits to the parties who conduct phytoextraction. Some other plants have been studied for Cd phytoextraction, but annual removals are much lower than the best T. caerulescens. Improved cultivars with higher yields and retaining this remarkable Cd phytoextraction potential are being bred using normal plant breeding techniques.

Leptoplax emarginata and Bornmuellera tymphaea are nickel hyperaccumulators of the Brassicaceae family endemic to serpentine soils in Greece. The aims of this work were to compare the growth and uptake behavior of these plants with the Ni hyperaccumulator species Thlaspi caerulescens and Alyssum murale, and to evaluate their effect on soil Ni availability. Plants were grown for 3 mo on three soils that differ in Ni availability. Ni availability in soils was measuredby isotopic exchange kinetics and DTPA-TEA extractions. Results showed that L. emarginata produced significantly more biomass than other plants. On the serpentine soil, B. tymphaea showed the highest Ni concentration in shoots. However, Niphytoextraction on the three soils was maximal with L. emarginata. The high initial Ni availability of soil Serp (470.5 mg kg(-1)) was the main explanation for the high Ni concentrations measured in plant shoots grown on this soil, compared to those grown on soils Calc and Silt A. murale was the least efficient in reducing Ni availability on the serpentine soil L. emarginata appeared as the most efficient species for Ni phytoextraction and decrease of the Ni available pool.

The perennial herb Phytolacca acinosa Roxb. (Phytolaccaceae), which occurs in Southern China, has been found to be a new manganese hyperaccumulator by means of field surveys on Mn-rich soils and by glasshouse experiments. This species not only has remarkable tolerance to Mn but also has extraordinary uptake and accumulation capacity for this element. The maximum Mn concentration in the leaf dry matter was 19,300 microg/g on Xiangtan Mn tailings wastelands, with a mean of 14,480 microg/g. Under nutrient solution culture conditions, P. acinosa could grow normally with Mn supplied at a concentration of 8000 micromol/l, although with less biomass than in control samples supplied with Mn at 5 micromol/l. Manganese concentration in the shoots increased with increasing external Mn levels, but the total mass of Mn accumulated in the shoots first increased and then decreased. At an Mn concentration of 5000 micromol/l in the culture solution, the Mn accumulation in the shoot dry matter was highest (258 mg/plant). However, the Mn concentration in the leaves reached its highest value (36,380 microg/g) at an Mn supply level of 12,000 micromol/l. These results confirm that P. acinosa is an Mn hyperaccumulator which grows rapidly, has substantial biomass, wide distribution and a broad ecological amplitude. This species provides a new plant resource for exploring the mechanism of Mn hyperaccumulation, and has potential for use in the phytoremediation of Mn-contaminated soils.

•   Molecular phylogeny based on ribosomal internal transcribed spacer (ITS) sequences was studied to investigate the phyletic relationships among some nickel (Ni)-hyperaccumulating and nonhyperaccumulating species of the genus Alyssum in relation to their geographic distribution and Ni-hyperaccumulating phenotype. •   Thirty-seven samples belonging to 32 taxa were analysed by sequencing the polymerase chain reaction-amplified ITS region and performing neighbor joining, maximum parsimony and maximum likelihood phylogenetic analyses. •   The ITS region in the sampled species varied from 221 to 307 bp of ITS1 and from 194 to 251 bp of ITS2. A total of 765 characters was used to infer the phylogeny and the average nucleotide variation detected was 15.15%. •   Nickel-hyperaccumulation could have been lost or acquired independently more than once during the speciation of the genus. The geographical location of species could not be related to phylogenetic affinities.

•  Here we report on the first phase of a funded programme to select a wild relative of Arabidopsis thaliana for use in large-scale genomic strategies, including forward and reverse genetic screens for the identification of genes involved in metal hyperaccumulation. •  Twenty accessions of metal accumulating species of the Brassicaceae collected from Austria, France, Turkey and the USA during spring-summer 2001 were evaluated. •  The criteria established for selection were: hyperaccumulation of metal (Ni, Zn); compact growth habit; reasonable time to flowering; production of ≥ 1000 seeds per plant; self-fertility; a compact diploid genome; high sequence identity with A. thaliana; and ≥ 0.1% transformation efficiency with easy selection. As part of this selection process we also report, for the first time, the stable genetic transformation of various hyperaccumulator species with both the green fluorescence protein (GFP) and the bar selectable marker. •  We conclude that metal hyperaccumulation ability, self-fertility, seed set, transformation efficiency and a diploid genome were the most important selection criteria. Based on an overall assessment of the performance of all 20 accessions, Thlaspi caerulescens Félix de Pallières showed the most promise as a model hyperaccumulator.

Extraordinary uptake of nickel (Ni), reaching concentrations of 0.1-5.0%, c. 1000 times greater than those usually found in flowering plants, has been observed previously in c, 190 species that grow on Ni-rich serpentine soils derived from ultramafic rocks in various parts of the world. These so-called hyperaccumulators of Ni include c. 50 species from the rich ultramafic flora of New Caledonia and c. 80 species from the Brassicaceae of Mediterranean Europe and Turkey. A study of a limited part (the families Buxaceae and Euphorbiaceae) of the very large ultramafic flora of Cuba has now identified this as the home of at least 80 hyperaccumulators, the largest number jet found in any one country. The more frequent incidence here of this unusual form of plant behaviour is linked to the very long period (r. 10-30 million years) during which some of the Cuban ultramafic substrata are believed to have been continuously available for colonization; the distribution of Ni hyperaccumulators between older and younger ultrarnafic soils in Cuba mirrors the overall incidence of endemic species in these areas.

Heavy metai uptake, accumulation and tolerance were investigated in five British populations of the metallophyte Thlaspi caerulescens from metalliferous sites from the north and south Pennines orefields. Analysis of field samples showed mean shoot Zn, Pb and Cd concentrations of up to 21000, 660 and 164/zMug g -1 respectively. A solution culture experiment designed to investigate both tolerance and metal accumulation is reported. Indices of tolerance of five populations to 12 metals (Ag, Al, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Zn) showed few population differences but unexpectedly high tolerance to metals not present at elevated concentrations in the parent soils. This was paralleled by exceptionally high uptakes of all metals studied. Zn, Cd, Co, Mn and Ni were readily transported to the shoot whereas Al, Cr Cu, Fe and Pb were predominantly immobilized in the roots. The data suggest common mechanisms of absorption and transport of several metals in this species.

Ninety-six male Sprague-Dawley rats were randomly assigned to eight dietary treatments. Rats were fed, with ad libitum access, diets containing 10% dietary fiber as cellulose (control), pectin, psyllium or oat bran with or without 0.3% added cholesterol for 3 wk. Among cholesterol-fed rats, liver total cholesterol was significantly lower in rats fed diets supplemented with either pectin or psyllium compared with those fed cellulose. In contrast, rats fed oat bran with cholesterol had significantly higher liver cholesterol concentrations compared with cellulose-fed animals. Liver total lipid concentrations were significantly lower in groups fed pectin and psyllium with or without dietary cholesterol compared with cellulose-fed controls. Pectin feeding with or without dietary cholesterol significantly lowered plasma total cholesterol compared with cellulose feeding. Oat bran had no effect on plasma total cholesterol compared with control diets. Hepatic sterol synthesis was significantly greater for animals fed soluble dietary fibers compared with those fed cellulose, but the effect on intestinal sterol synthesis was less pronounced.

Sprague-Dawley rats were fed diets containing 7.5% dietary fiber as cellulose (control), pectin, psyllium or oat bran with or without 0.3% added cholesterol for 3 wk. Among rats fed cholesterol, liver total lipid and cholesterol concentrations were significantly lower in groups fed pectin, psyllium and oat bran compared with cellulose-fed controls. Cholesterol feeding resulted in significantly greater liver cholesterol in rats fed cellulose, psyllium and oat bran but not in those fed pectin. Among rats fed cholesterol, total serum cholesterol levels were significantly lower in those fed pectin than in those fed psyllium, oat bran or cellulose. When cholesterol was fed, the oat bran-fed group had significantly higher butyrate and the pectin-fed group had significantly higher propionate concentrations in the hepatic portal vein than did cellulose-fed controls. The groups fed psyllium, oat bran and pectin all had significantly higher fecal neutral sterols than did the cellulose-fed group when cholesterol was fed. Without dietary cholesterol only pectin-fed rats had significantly higher fecal excretion of neutral sterols than those fed cellulose. Dietary fiber did not influence fecal acidic sterol excretion. However, the addition of cholesterol to these fiber diets was accompanied by a significantly higher bile acid excretion than that of animals fed cellulose without cholesterol. The results of this study indicate that soluble dietary fibers may exert their hypocholesterolemic effect by increasing excretion of fecal neutral sterols.

Aeolanthus biformifolius (Labiatae) from Shaba Province, Zaïre, has been shown to be a hyperaccumulator of copper. The copper content of the total plant during the rest period after the rainy season was 1.3 percent (dry weight basis) and is easily the highest copper concentration ever found in living material. This species should be classified as a "copper flower" because of its exclusive occurrence over mineralized ground.

Marked hypertriglyceridemia and hypercholesterolemia accompanied by angina and a left cerebral thrombosis occurred in a long-term hemodialysis patient following 5 1/2 weeks of oral treatment with oxymetholone, 100 mg/day, a synthetic androgen. After androgen therapy was discontinued, over a three-month period, plasma lipid values progressively decreased below pretreatment values, and clinical symptoms disappeared. During rechallenge with oxymetholone, serum lipid values increased substantially, and the lipoprotein pattern changed from a type IV to a type V. Detailed lipid studies showed subnormal postheparin lipolytic activity and a fast-migrating pre-beta-lipoprotein in a very-low-density lipoproteins (VLDL) fraction. Because of the data linking lipid abnormalities to atherosclerosis and the acceleration of atherosclerosis in long-term hemodialysis patients, great caution should be exercised in administering androgenic steroids to these patients.

A condition clinically identical to human conjunctival primary acquired melanosis (PAM) was induced in 16 of 20 Dutch (pigmented) rabbits after weekly topical 60-microliters applications of a 1% solution of 7,12-dimethylbenz[a]anthracene (DMBA) in acetone. Pigment stippling appeared in the conjunctiva as early as 5 weeks after the initial carcinogen application. Confluent patches of flat pigmentation appeared over the palpebral conjunctiva 18 weeks after the onset of treatment and showed progressive lateral enlargement and darkening. Histologically, a spectrum of changes from increased melanin production and melanocytic hyperplasia without atypia (resembling the human condition of PAM without atypia) through atypical melanocytic hyperplasia (resembling human PAM with atypia) was identified. The development of this model permits further investigations to explore and explain the clinically observed phenomenon of waxing and waning of PAM and its promotion to conjunctival malignant melanoma.

Sebertia acuminata (Sapotaceae) from New Caledonia has been shown to be a hyperaccumulator of nickel. The nickel content of the latex (25.74 percent on a dry weight basis) is easily the highest nickel concentration ever found in living material. The nickel is in the form of a low-molecular-weight, water-soluble organic complex.

Herbarium and field specimens (over 300) of all of the Flacourtiaceae of New Caledonia were analysed for nickel in order to identify hyperaccumulators (greater than 1000 microgram/g dry mass) and to assess nickel accumulation in relation to the evolutionary status of 'nickel plants' of New Caledonia. One hyperaccumulator was identified in the genus Lasiochlamys, ten among Xylosoma, one among Casearia and seven among Homalium. Although these Homalium nickel plants had previously been recorded, fresh data for these and other Homalium are presented. The remarkable tolerance of Flacourticeae to ultrabasic rocks is shown by the fact that 75% of the species are found on such substrates. The number of hyperaccumulators was greatest in the genera Xylosoma and Homalium. The Flacourtiaceae are among the most primitive of all angiosperms and in common with other primitive hyperaccumulators, contain nickel as a complex with citric acid. The only advanced New Caledonian nickel plant (Psychotria douarrei) has most of its nickel bound with ligands other than citric acid, a feature of other advanced hyperaccumulators. It is postulated that nickel complexing with citric acid may be a primitive character. Most of the New Caledonian nickel plants belong to the order Violales of subclass Dilleniidae. It is suggested that hyperaccumulation of nickel is an evolutionary character which occurs in long-indisturbed floras such as that of New Caledonia.

Clearances of inulin, 125I-iothalamate, and 99mTc-Sn-DTPA were measured simultaneously in five mongrel dogs exhibiting a wide range of glomerular filtration rates (GFR). Standard constant-infusion inulin clearance was compared to radionuclide clearances after subcutaneous injection of the emitters mixed with aqueous epinephrine. All three substances were found to have virtually identical clearances. The accuracy, accessibility, low cost, low radiation hazard, and short half-life of 99mTc-Sn-DTPA make it an excellent substance for measuring GFR. The subcutaneous technique offers an accuracy comparable to the more difficult constant-infusion method.

Four young adult (18 to 26 years old), nonobese human subjects (two men and two women) with insulin-dependent diabetes mellitus volunteered to consume a series of three diets: baseline (normal daily intake), wheat bran (normal daily intake + 78 gm wheat bran per day), and cellulose (normal daily intake + 30 gm cellulose per day). Wheat bran and cellulose diets both contained 60 gm dietary fiber, with 50% of the dietary fiber from wheat bran or cellulose, respectively. Each patient served as his or her own control. Randomized diets were of 6 weeks' duration, separated by a 4-week "recovery" period. At the conclusion of each diet, subjects were hospitalized and underwent 12 hours of computer-controlled, insulin-glucose infusions. Significant decreases were seen in fasting cholesterol (p less than .05), but the decreases seemed to result largely from the significant reductions in high-density lipoprotein cholesterol. A large reduction in triglycerides was noted with cellulose feeding but not with wheat bran. The mean daily insulin dose decreased (p less than .05) in response to fiber addition (8% and 10% decrease for wheat bran and cellulose feeding, respectively). Mean biostator insulin requirements decreased 11% with wheat bran (p less than .05) but not with cellulose. During biostator monitoring, subjects experienced delayed postprandial blood glucose and insulin-infusion rate peaks with both wheat bran and cellulose feeding. The wheat bran diet reduced peak blood glucose concentration and peak insulin infusion rate in comparison with baseline and cellulose diets. The data suggest that high levels of cellulose or wheat bran are of marginal benefit to insulin-dependent diabetic subjects.

We investigated whether X-irradiation could induce the enzyme superoxide dismutase (SOD) in intestinal muscle. Groups of rats received abdominal irradiation and the time course and dose response for SOD activity determined. Jejunal smooth muscle homogenates were analyzed for the activities of copper/zinc (CuZn) and manganese (Mn) SOD activity and for a mitochondrial marker enzyme, citrate synthase. A progressive rise in Mn SOD activity occurred at 20, 46, and 72 h after 1500 R. No significant changes in Cu-Zn SOD activity occurred at any time after 1500 R. At 20 h after 250 R of X-irradiation, Mn SOD activity increased but no further increase occurred at higher irradiation exposures. At the same time, CuZn SOD activity at 20 h after irradiation was greater than controls only at an exposure of 1000 R (p less than 0.05). Using Western blotting, we were able to clearly demonstrate an increase in immunoreactive Mn SOD protein in muscle samples 20 h after 1500 R. The rise in Mn SOD is not simply due to increase in mitochondrial numbers or increase in all mitochondrial enzyme activities because activity of the mitochondrial marker enzyme citrate synthase was decreased after X-irradiation. Transmission electron microscopic studies demonstrated damage to mitochondria after a dose of 3000 R. The data yield evidence that free radicals play a role in irradiation-induced intestinal smooth muscle injury.

Ultrasonography has become an essential tool in the practice of modern obstetrics. Its usefulness in the evaluation of a pelvic mass in gynecologic practice remains unclear. The present investigation is a comparison of pelvic examination findings and preoperative ultrasound findings in 72 patients who underwent exploratory laparotomy for a pelvic mass at the Nation Naval Medical Center. Of the 72 patients, 65 (90%) were correctly diagnosed as having a pelvic mass by both pelvic examination and ultrasonography. The ultrasound study had a 5.6% false-negative rate (4 patients), and 4.4% (3 patients) had false-positive pelvic examinations. There was no significant difference by chi 2 analysis in accuracy between ultrasonography and pelvic examination in detection, estimation of size, or determining the unilateral or bilateral position of the mass (P less than .05). Ultrasonography was significantly more accurate in determining the cystic or solid nature of the mass (P greater than .05). In no patient was the decision to perform exploratory laparotomy altered by the preoperative ultrasound study. It is concluded from this investigation that routine ultrasonography is not necessary in the preoperative evaluation of a pelvic mass unless the cystic or solid nature of the mass will modify the patient's treatment.