Polymer–Ferrocene Conjugates Containing an Ester Function in the Connecting Links

Ferrocene, the parent of the metallocene family of organotransition metal compounds, has come to occupy a significant niche in cancer research. Developmental work in the authors' laboratory has been focused on the synthesis of antiproliferative ferrocene conjugates in which the bioactive ferrocene unit is covalently, yet bioreversibly bound (anchored) to water-soluble carrier polymers designed in accordance with requisite biomedical specifications. The anchoring link in most of these conjugates has been an aliphatic spacer containing the biofissionable amide group. In this communication the synthesis of a class of ferrocene conjugates is reported in which the ferrocene group is carrier-anchored through spacers containing an ester link, of interest here because of potentially different drug release behavior. The carriers are polyamides equipped with variously spaced hydroxyl side groups, to which the ferrocenylation agent, 4-ferrocenylbutanoic acid, is connected through esterification. The coupling reactions, mediated by carbodiimide agent and catalyzed by 4-(dimethylamino)pyridine, are carried out in DMF at temperatures not exceeding 65°C, and the water-soluble product polymers are isolated in yields of typically 70–85% by precipitation, aqueous dialysis, and freeze-drying. With the molar feed ratios chosen in these coupling experiments, the incorporation of ferrocene, assessed by ¹H NMR spectroscopy, corresponds to iron contents of roughly 2.5–5.5%, by mass. The conjugates will be included in a forthcoming bioactivity screening program.     

Competitive adsorption of sulfolane and thiolane on clay materials

Groundwater samples directly beneath a waste disposal site have been shown to contain a higher concentration of sulfolane and a relatively low concentration of thiolane. The sulfolane is a source compound of thiolane, a reduced form of sulfolane. In subsequent analyses of groundwater samples, these compounds have been detected from all of the monitoring wells in the study area. Since these compounds are present together in an aquifer, a possible competition, that can happen in such a system, has been investigated. Thiolane is a nonpolar heterocyclic organic compound whereas sulfolane is a weakly acidic dipolar solvent. As expected, thiolane adsorbs more strongly onto clay than sulfolane in a single solute system. For regression of bisolute system using Matlab to obtain Q (maximum number of moles of solute adsorbed per unit weight of adsorbent), k₁ (constants related to the energy of adsorption for sulfolane), and k₂ (constants related to the energy of adsorption for thiolane), the k₁ value (sulfolane) is smaller than the k₂ value (thiolane) which reflects that thiolane is more strongly adsorbed than sulfolane. This is strongly consistent with the result obtained from single solute system. The Q for the sulfolane and combined data is the same that indicates that the sulfolane data is dominantly fitted because the concentrations of sulfolane are much greater than those of thiolane in the experiments. In combined data regression, the suppression of sulfolane adsorption on clay was also observed by the presence of thiolane.     

Analysis of the Notched Coating Adhesion Test

An analysis of the notched coating adhesion (NCA) test is presented. This simple adhesion test method is appropriate for measuring the interfacial fracture toughness of some classes of coatings and open-faced adhesive bonds. The NCA specimen consists of a single substrate coated with a thin layer of adhesive. The coating is notched to sever the coating and induce sharp interfacial debonds, and the specimen is then loaded in tension. The substrate strain at which coating debonding occurs is recorded and used to determine the critical strain energy release rate. Yielding of the substrate is permitted, and does not significantly affect the calculation of the strain energy release rate. Analytical and finite element analysis are used to quantify the available strain energy release rate for both steady state and laterally-constrained cases. The available strain energy release rate is shown to be quite insensitive to the initial debond length. The specimen geometry results in a mode mix which causes the adhesive to debond along the interface.     

Residential energy consumption across different population groups: comparative analysis for Latino and non-Latino households in USA

Residential energy cost is an important part of the household budget and could vary significantly across different population groups in many countries. In the United States, many studies have analyzed household fuel consumption by fuel type, including electricity, natural gas, fuel oil, and liquefied petroleum gas (LPG), and by geographic areas. Past research has also demonstrated significant variation in residential energy use across various population groups, including white, black, and Latino. However, our research shows that residential energy demand by fuel type for Latinos, the fastest growing population group, has not been explained by economic and non-economic factors in any statistical model in public domain. The purpose of this paper was to discuss energy demand and expenditure patterns for Latino and non-Latino households in hhe United States as a case example of analyzing residential energy consumption across different population groups in a country. The linear expenditure system model developed by Stone and Geary is the basis of the statistical model developed to explain fuel consumption and expenditures for Latino households. For comparison, the models are also developed for non-Latino, black, and non-black households. These models estimate energy consumption of and expenditures for electricity, natural gas, fuel oil, and LPG by various households at the national level. Significant variations in the patterns of these fuels consumption for Latinos and non-Latinos are highlighted. The model methodology and results of this research should be useful to energy policymakers in government and industry, researches, and academicians who are concerned with economic and energy issues related to various population groups in their country.     

Silk maysin content and resistance of commercial corn [maize] hybrids to kernel contamination by aflatoxin

Several phenols and related compounds have been shown to have detrimental effects on insects while others have antibiotic activity against fungi which attack higher plants. Insects have also been implicated as contributors to preharvest contamination of corn [maize], Zea mays L, by aflatoxin. The objectives, therefore, were to determine (a) if commercial corn hybrids vary in their silk maysin content and aflatoxin contamination of the grain, and (b) if grain aflatoxin contamination is correlated with maysin and related compounds. During 4 years of testing, 16 corn hybrids varied significantly for silk maysin content and grain aflatoxin contamination. Based on correlations, grain aflatoxin content of the hybrids tested was not significantly associated with maysin, chlorogenic acid, and 3′-methoxymaysin contents. It was concluded that other untested phenolic compounds in the category of compounds analyzed in the present study could be involved in resistance to aflatoxin formation, and that other classes of compounds should also now be assessed to locate major chemical resistance components.     

Primary care physicians' willingness to offer a new genetic test to tailor smoking treatment, according to test characteristics

Emerging pharmacogenetics research may improve clinical outcomes for common complex conditions typically treated in primary care settings. Physicians' willingness to offer genetically-tailored treatments to their patients will be critical to realizing this potential. According to recent research, it is likely that genotypes used to tailor smoking will have pleiotropic associations with other addictions and diseases, and may have different frequencies across populations. These additional features may pose an additional barrier to adoption. To assess physicians' willingness to offer a new test to individually tailor smoking treatment according to specific test characteristics, we conducted a national mailed survey of 2,000 U.S. primary care physicians (response rate: 62.3%). Physicians responded to a baseline scenario describing a new test to tailor smoking treatment, and three additional scenarios describing specific test characteristics based on published research; there was random assignment to one of two survey conditions in which the test was described as a genetic or non-genetic test. Our findings indicate physicians' self-reported likelihood (0-100 scale) that they would offer a new test to tailor smoking cessation treatment ranged from 69%-78% across all scenarios. Relative to baseline scenario responses, physicians were significantly less likely to offer the test when informed that the same genotypes assessed for treatment tailoring: (1) may also identify individuals predisposed to become addicted to nicotine (p<.001), (2) differ in frequency by race (p<.004), and (3) may have associations with other conditions (e.g., alcohol and cocaine addiction, attention deficit hyperactivity disorder ADHD and Tourette Syndrome) (p<.01). Describing a new test to individually tailor smoking treatment as a "genetic" versus non-genetic test significantly reduced physicians' likelihood of offering the test across all scenarios, regardless of specific test characteristics (p<.0007). Effective education of primary care physicians will be critical to successful integration of promising new pharmacogenetic treatment strategies for smoking.     

Relation between the redox state of iron-based nanoparticles and their cytotoxicity toward Escherichia coli

Iron-based nanoparticles have been proposed for an increasing number of biomedical or environmental applications although in vitro toxicity has been observed. The aim of this study was to understand the relationship between the redox state of iron-based nanoparticles and their cytotoxicity toward a Gram-negative bacterium, Escherichia coli. While chemically stable nanoparticles (gammaFe2O3) have no apparent cytotoxicity, nanoparticles containing ferrous and, particularly, zerovalent iron are cytotoxic. The cytotoxic effects appear to be associated principally with an oxidative stress as demonstrated using a mutant strain of E. coli completely devoid of superoxide dismutase activity. This stress can result from the generation of reactive oxygen species with the interplay of oxygen with reduced iron species (Fe(II) and/or Fe(0)) or from the disturbance of the electronic and/or ionic transport chains due to the strong affinity of the nanoparticles for the cell membrane.     

Regulating the geological sequestration of CO2

Governments worldwide should provide incentives for initial large-scale GS projects to help build the knowledge base for a mature, internationally harmonized GS regulatory framework. Health, safety, and environmental risks of these early projects can be managed through modifications of existing regulations in the EU, Australia, Canada, and the U.S. An institutional mechanism, such as the proposed Federal Carbon Sequestration Commission in the U.S., should gather data from these early projects and combine them with factors such as GS industrial organization and climate regime requirements to create an efficient and adaptive regulatory framework suited to large-scale deployment. Mechanisms to structure long-term liability and fund long-term postclosure care must be developed, most likely at the national level, to equitably balance the risks and benefits of this important climate change mitigation technology. We need to do this right. During the initial field experiences, a single major accident, resulting from inadequate regulatory oversight, anywhere in the world, could seriously endanger the future viability of GS. That, in turn, could make it next to impossible to achieve the needed dramatic global reductions in CO2 emissions over the next several decades. We also need to do it quickly. Emissions are going up, the climate is changing, and impacts are growing. The need for safe and effective CO2 capture with deep GS is urgent.     

Modeling the effects and uncertainties of contaminated sediment remediation scenarios in a Norwegian fjord by Markov chain Monte Carlo simulation

Multimedia environmental fate models are useful tools to investigate the long-term impacts of remediation measures designed to alleviate potential ecological and human health concerns in contaminated areas. Estimating and communicating the uncertainties associated with the model simulations is a critical task for demonstrating the transparency and reliability of the results. The Extended Fourier Amplitude Sensitivity Test(Extended FAST) method for sensitivity analysis and Bayesian Markov chain Monte Carlo (MCMC) method for uncertainty analysis and model calibration have several advantages over methods typically applied for multimedia environmental fate models. Most importantly, the simulation results and their uncertainties can be anchored to the available observations and their uncertainties. We apply these techniques for simulating the historical fate of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in the Grenland fjords, Norway, and for predicting the effects of different contaminated sediment remediation (capping) scenarios on the future levels of PCDD/Fs in cod and crab therein. The remediation scenario simulations show that a significant remediation effect can first be seen when significant portions of the contaminated sediment areas are cleaned up, and that increase in capping area leads to both earlier achievement of good fjord status and narrower uncertainty in the predicted timing for this.