Assembly of Nanocrystal Arrays by Block‐Copolymer‐Directed Nucleation

Growing in line: The surface chemistry of self‐assembled nanostructured block copolymers is used to control the sites at which semiconducting metal sulfide nanocrystals nucleate and grow on a surface directly from aqueous solutions. This process is a new and general strategy for the bottom‐up assembly of functional nanocrystalline materials for a variety of applications.

     

Masking effect of anti-androgens on androgenic activity in European river sediment unveiled by effect-directed analysis

This study shows that the androgen receptor agonistic potency is clearly concealed by the effects of androgen receptor antagonists in a total sediment extract, demonstrating that toxicity screening of total extracts is not enough to evaluate the full in vitro endocrine disrupting potential of a complex chemical mixture, as encountered in the environment. The anti-androgenic compounds were masking the activity of androgenic compounds in the extract with relatively high anti-androgenic potency, equivalent to 200 nmol flutamide equivalents/g dry weight. A two-step serial liquid chromatography fractionation of the extract successfully separated anti-androgenic compounds from androgenic compounds, resulting in a total androgenic potency of 3,820 pmol dihydrotestosterone equivalents/g dry weight. The fractionation simplified the chemical identification analysis of the original complex sample matrix. Seventeen chemical structures were tentatively identified. Polyaromatic hydrocarbons, a technical mixture of nonylphenol and dibutyl phthalate were identified to contribute to the anti-androgenic potency observed in the river sediment sample. With the GC/MS screening method applied here, no compounds with AR agonistic disrupting potencies could be identified. Seventy-one unidentified peaks, which represent potentially new endocrine disrupters, have been added to a database for future investigation.     

Semiconductor surface-induced 1,3-hydrogen shift: the role of covalent vs zwitterionic character

X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR) are used to compare the reaction of 1,2-cyclohexanedione (1,2-CHD) with Si(001) and diamond(001) surface dimers under ultra-high-vacuum conditions. 1,2-CHD is known to undergo a keto-enol tautomerization, with the monoenol being the primary equilibrium species in the solid and gas phases. XPS and FTIR data demonstrate that 1,2-CHD reacts with diamond(001) through the OH group of the monoenol, resulting in only one O atom being bonded to the surface. In contrast, XPS and FTIR data suggest that both oxygen atoms in the 1,2-CHD molecule bond via Si-O-C linkages to the Si(001) surface dimer, and that the molecule undergoes an intramolecular 1,3-H shift. While the Si(001) and diamond(001) surfaces are both comprised of surface dimers, the diamond(001) dimer is symmetric, with little charge separation, whereas the Si(001) dimer is tilted and exhibits zwitterionic character. The different reaction products that are observed when clean Si(001) and diamond(001) surfaces are exposed to 1,2-CHD demonstrate the importance of charge separation in promoting a 1,3-H shift and provide new mechanistic insights that may be applicable to a variety of organic reactions.     

Effect of ozone oxidation on single-walled carbon nanotubes

Exposing single-walled carbon nanotubes to room-temperature UV-generated ozone leads to an irreversible increase in their electrical resistance. We demonstrate that the increased resistance is due to ozone oxidation on the sidewalls of the nanotubes rather than at the end caps. Raman and X-ray photoelectron spectroscopies show an increase in the defect density due to the oxidation of the nanotubes. Using ultraviolet photoelectron spectroscopy, we show that these defects represent the removal of pi-conjugated electron states near the Fermi level, leading to the observed increase in electrical resistance. Oxidation of carbon nanotubes is an important first step in many chemical functionalization processes. Because the oxidation rate can be controlled with short exposures, UV-generated ozone offers the potential for use as a low-thermal-budget processing tool.     

Supplier-initiated outsourcing: A methodology to exploit synergy in transportation

Over the last decades, transportation has been evolving from a necessary, though low priority function to an important part of business that can enable companies to attain a competitive edge over their competitors. To cut down transportation costs, shippers often outsource their transportation activities to a logistics service provider of their choice. This paper proposes a new procedure that puts the initiative with the service provider instead: supplier-initiated outsourcing. This procedure is based on both operations research and game theoretical insights. To stress the contrast between the traditional push approach of outsourcing, and the here proposed pull approach where the service provider is the initiator of the shift of logistics activities from the shipper to the logistics service provider, we will refer to this phenomenon as insinking. Insinking has the advantage that the logistics service provider can proactively select a group of shippers with a strong synergy potential. Moreover, these synergies can be allocated to the participating shippers in a fair and sustainable way by means of a so-called Shapley Monotonic Path of customized tariffs. Insinking is illustrated by means of a practical example based on data from the Dutch grocery transportation sector.     

FTIR Emission Spectra, Molecular Constants, and Potential Curve of Ground State GeO

Extensive new high-temperature, high-resolution FTIR emission spectroscopy measurements for the five common isotopomers of GeO are combined with previous diode laser and microwave measurements in combined isotopomer analyses. New Dunham expansion parameters and an accurate analytical potential energy function are determined for the ground X1Sigma+ state. Copyright 1999 Academic Press.     

Neighbor games and the leximax solution

Neighbor games arise from certain matching or sequencing situations in which only some specific pairs of players can obtain a positive gain. As a consequence, the class of neighbor games is the intersection of the class of assignment games (Shapley and Shubik (1972)) and the class of component additive games (Curiel et al. (1994)). We first present some elementary features of neighbor games. After that we provide a polynomially bounded algorithm of order p ³ for calculating the leximax solution (cf. Arin and Iñarra (1997)) of neighbor games, where p is the number of players. This authors work has been supported by CentER and the Department of Econometrics, Tilburg University and by the Foundation for the Hungarian Higher Education and Research (AMFK).     

Nanoscale battery cathode materials induce DNA damage in bacteria

The increasing use of nanoscale lithium nickel manganese cobalt oxide (Li_xNi_yMn_zCo_1−y−zO₂, NMC) as a cathode material in lithium-ion batteries poses risk to the environment. Learning toxicity mechanisms on molecular levels is critical to promote proactive risk assessment of these complex nanomaterials and inform their sustainable development. We focused on DNA damage as a toxicity mechanism and profiled in depth chemical and biological changes linked to DNA damage in two environmentally relevant bacteria upon nano-NMC exposure. DNA damage occurred in both bacteria, characterized by double-strand breakage and increased levels of many putative chemical modifications on bacterial DNA bases related to direct oxidative stress and lipid peroxidation, measured by cutting-edge DNA adductomic techniques. Chemical probes indicated elevated intracellular reactive oxygen species and transition metal ions, in agreement with DNA adductomics and gene expression analysis. By integrating multi-dimensional datasets from chemical and biological measurements, we present rich mechanistic insights on nano-NMC-induced DNA damage in bacteria, providing targets for biomarkers in the risk assessment of reactive materials that may be extrapolated to other nano–bio interactions.

The increasing use of nanoscale lithium nickel manganese cobalt oxide (Li_xNi_yMn_zCo_1−y−zO₂, NMC) as a cathode material in lithium-ion batteries poses risk to the environment. We report DNA damage that occurs in bacteria after nano-NMC exposure with rich chemical details.