Formation of Extended Covalently Bonded Ni Porphyrin Networks on the Au（lll） Surface

The growth and ordering of {5,10,15,20-tetrakis(4-bromophenyl)porphyrinato}nickel(II) (NiTBrPP) molecules on the Au(111) surface have been investigated using scanning tunnelling microscopy, X-ray absorption, core-level photoemission, and microbeam low-energy electron diffraction. When deposited onto the substrate at room temperature, the NiTBrPP forms a well-ordered close-packed molecular layer in which the molecules have a flat orientation with the porphyrin macrocycle plane lying parallel to the substrate. Annealing of the NiTBrPP layer on the Au(111) surface at 525 K leads to dissociation of bromine from the porphyrin followed by the formation of covalent bonds between the phenyl substituents of the porphyrin. This results in the formation of continuous covalently bonded porphyrin networks, which are stable up to 800 K and can be recovered after exposure to ambient conditions. By controlling the experimental conditions, a robust, extended porphyrin network can be prepared on the Au(111) surface that has many potential applications such as protective coatings, in sensing or as a host structure for molecules and clusters.     

China's Eco-Cities as Variegated1 Urban Sustainability: Dongtan Eco-City and Chongming Eco-Island

Proliferating environmental sustainability policy frameworks suggest that sustainability and economic competitiveness are essentially interdependent and mutually enhancing. Under these policy discourses, cities are designated as strategic geographical locales for fulfilling the green capitalist goal of reconciling the contradictions between the environment and development that have long bedeviled capitalism. While most urban sustainability agendas are crafted based on the experience of post-industrial countries, the promise of green capitalism and sustainability faces different challenges where industrial production still dominates the economy. However, research on whether and how urban sustainability policies are geographically variegated is still sparse, particularly beyond western (post)industrial capitalism. Examining the Dongtan eco-city project and the associated Chongming eco-island project in Shanghai, we interrogate how sustainability is imagined and practiced on the ground within the distinctive Chinese context. The meanings of sustainability in Dongtan and Chongming reflect the context of Chinese urbanization in the Shanghai area. Both Dongtan and Chongming seek to develop green technologies as a way to resolve the dilemma of being caught between urbanization and agriculture. This approach is also shaped by Chongming's island geography as enabling a self-sufficient development trajectory, and its desire to attract a cosmopolitan population. Through these place-specific contexts, the ecology and economy of Dongtan and Chongming become intertwined, producing and reproducing a variegated form of urban sustainability, and of “green capitalism.”     

Temporal variation of contact networks in granular materials

For analogue granular materials simulated using DEM, contact networks are often drawn by joining the centroids of contacting particles. Although a limited amount of research has been done to characterise the temporal aspects of such contact networks at a micro-scale, many simple questions regarding the duration of contacts in evolving granular systems remain unanswered. This paper addresses this gap in the existing knowledge by using the open-source code LAMMPS to run and analyse nine (3D) triaxial simulations of 20,164 polydisperse spherical particles. Contacts which exist for a long duration are preferentially oriented in the direction of the major principal stress while the fabric anisotropy for contacts with a given duration increases with duration. Regardless of simulation conditions, there is a linear relationship between the percentage of contacts present for a given duration and contact duration, despite the non-linear overall behaviour of the material. The forces transmitted by contacts increase, on average, with increasing duration. The total number of unique contacts which appear during triaxial compression increases linearly after 10 % axial strain, although the number of contacts, both total and subdivided into strong and weak force subnetworks, remains quite stable. The majority of contacts in these evolving granular systems, even those participating in strong force chains, are formed and lost repeatedly.     

Synergistic Gold(I)/Trimethylsilyl Catalysis: Efficient Alkynylation of N,O‐Acetals and Related Pro‐Electrophiles

We report a unique mechanism‐guided reaction that enhances and expands the chemical space that readily generated gold(I) acetylides currently operate in. Our strategy exploits the propensity of gold(I) carbophilic catalysts with specific counteranions (LAuX – X=triflate or triflimidate) to efficiently activate and desilylate trimethylsilylalkynes, thereby mediating the in situ formation of equal and catalytic quantities of a silyl Lewis acid (TMSX) of tunable strength and a nucleophilic gold(I) acetylide. This unprecedented manifold opens avenues for developing synergistic silyl‐gold(I)‐catalyzed alkynylation strategies of diverse pro‐electrophiles which were heretofore unattainable, the proof of concept being principally exemplified herein with the first catalytic alkynylation of N,O‐acetals. The reaction proceeds at low catalyst loading, employs mild reaction conditions, is easily scalable, and affords propargylic lactam products in good to excellent yields. Furthermore, it is fully amenable to a diverse array of structure and function substrates, and also expands to other pro‐electrophiles beyond N,O‐acetals. Control experiments have been carried out that strongly support our dual reaction mechanism proposal which, furthermore, itself outlines an inextricable link between the strength of the ancillary silyl Lewis acid (TMSOTf versus TMSNTf₂) and the coordinating ability of the gold counter anion employed. This underlying feature of our system underscores its significant potential and flexibility, which indeed manifests with the demonstration that by carefully selecting the gold counter ion, it is possible to manipulate the strength of the ancillary silyl Lewis acid so that it can be tailored to the ionizing ability of a particular pro‐electrophile.

     

Tuning Cellular Response to Nanoparticles via Surface Chemistry and Aggregation

The aggregation of gold nanoparticles (Au NPs) in cell media is a common phenomenon that can influence NP‐cell interactions. Here, we control Au NP aggregation in cell media and study the impact of Au NP aggregation on human dermal fibroblast (HDF) cells. By first adding Au NPs to fetal bovine serum (FBS) and then subsequently to a buffer, aggregation can be avoided. Aggregation of Au NPs also can be avoided by coating Au NPs with other biomolecules such as lipids. The aggregation state of the Au NPs influences cellular toxicity and Au NP uptake: non‐aggregated cationic Au NPs are four‐fold less toxic to HDF cells than aggregated cationic Au NPs, and the uptake of non‐aggregated anionic citrate Au NPs is three orders of magnitude less than that of aggregated citrate Au NPs. Upon uptake of Au NPs, cellular F‐actin fiber formation is disrupted and actin dots are predominant. When lipid‐coated Au NPs are doped with a fluorescent lipid (F‐lipid) and incubated with HDF cells, the fluorescence from the F‐lipid was found throughout the cell, showing that lipids can dissociate from the Au NP surface upon entering the cell.     

Energy Infrastructure Development Faces Impediments

While political opposition or regulatory agencies themselves may impede natural gas infrastructure projects, it is often the various environmental and citizen groups protesting these projects that create significant challenges. From the Keystone XL oil pipeline to liquefied natural gas (LNG) export terminals, the strategies for derailing or slowing these projects often depend on the statutory and regulatory tools available, which differ by the governing statute—e.g., the Natural Gas Act (NGA) and the Interstate Commerce Act. Of course, other statutes, such as the National Environmental Policy Act (NEPA), influence how the applicable agency reviews a natural gas infrastructure project.     

Selective Inhibition of Heparan Sulphate and Not Chondroitin Sulphate Biosynthesis by a Small,Soluble Competitive Inhibitor

The glycosaminoglycan, heparan sulphate (HS), orchestrates many developmental processes. Yet its biological role has not yet fully been elucidated. Small molecule chemical inhibitors can be used to perturb HS function and these compounds provide cheap alternatives to genetic manipulation methods. However, existing chemical inhibition methods for HS also interfere with chondroitin sulphate (CS), complicating data interpretation of HS function. Herein, a simple method for the selective inhibition of HS biosynthesis is described. Using endogenous metabolic sugar pathways, Ac₄GalNAz produces UDP-GlcNAz, which can target HS synthesis. Cell treatment with Ac₄GalNAz resulted in defective chain elongation of the polymer and decreased HS expression. Conversely, no adverse effect on CS production was observed. The inhibition was transient and dose-dependent, affording rescue of HS expression after removal of the unnatural azido sugar. The utility of inhibition is demonstrated in cell culture and in whole organisms, demonstrating that this small molecule can be used as a tool for HS inhibition in biological systems.     

Comparison of the molecular mass and optical properties of colored dissolved organic material in two rivers and coastal waters by flow field-flow fractionation

Colored dissolved organic material (CDOM) is an important sunlight absorbing substance affecting the optical properties of natural waters. However, little is known about its structural and optical properties mainly due to its complex matrix and the limitation of the techniques available. A comparison of two southwestern Florida rivers [the Caloosahatchee River (CR) and the Shark River (SR)] was done in terms of molecular mass (MM) and diffusion coefficients (D). The novel technique Frit inlet/frit outlet-flow field-flow fractionation (FIFO-FIFFF) with absorbance and fluorescence detectors was used to determine these properties. The SR receives organic material from the Everglades. By contrast, the CR arises from Lake Okeechobee in central Florida, receiving anthropogenic inputs, farming runoff, and natural organics. Both rivers discharge to the Gulf of Mexico. Fluorescence identified, for both rivers, two different MM distributions in low salinity water samples: the first was centered at approximately 1.7 kDa (CR) and approximately 2 kDa (SR); the second centered at approximately 13 kDa for both rivers, which disappeared gradually in the river plumes to below detection limit in coastal waters. Absorbance detected only one MM distribution centered at approximately 2 kDa (CR) and 2.2-2.4 kDa (SR). Fluorescence in general peaked at a lower MM than absorbance, suggesting a different size distribution for fluorophores vs chromophores. A photochemical study showed that, after sunlight, irradiated freshwater samples have similar characteristics to more marine waters, including a shift in MM distribution of chromophores. The differences observed between the rivers in the optical characteristics, MM distributions, and D values suggest that the CDOM sources, physical, and photochemical degradation processes are different for these two rivers.     

Environmental and human impact of an old-timer incinerator in terms of dioxin and PCB level: a case study

The impact of a recently closed old municipal solid waste incinerator (MSWI) on polychlorodibenzo-p-dioxin (PCDD), polychlorodibenzofuran (PCDF), and polychlorinated biphenyl (PCB) levels in the surrounding environment and resident serum has been studied in a small rural area of France. Studied soils and eggs from chickens foraging on these soils were sampled in the vicinity of the MSWI underthe prevailing wind stream, while comparison samples were collected outside the assumed impact zone. PCB levels observed in soils and eggs did not differ statistically from comparison sites. This confirmed the low impact of MSWI PCB emission on environmental media, compared to other well-known sources. PCDD/PCDF levels in soils and eggs were significantly higher than in comparison samples, pointing out the impact of MSWI emission on the surrounding environment. The high dioxin concentrations in eggs set aside for private consumption would increase the dioxin intake for the studied population. Blood specimens of 10 nonoccupationally exposed volunteers who had lived within a 2 km radius of the incinerator for at least 25 years have been analyzed. When adjusted for age, PCB and PCDD/F blood levels were higher than general European populations and comparable to a similarly exposed Belgian population.     

Feasibility of Including Green Tea Products for an Analytically Verified Dietary Supplement Database

The Dietary Supplement Ingredient Database (DSID) is a federally funded, publicly accessible dietary supplement database that currently contains analytically derived information on micronutrients in selected adult and children's multivitamin and mineral (MVM) supplements. Other constituents in dietary supplement products such as botanicals are also of interest and thus are being considered for inclusion in the DSID. Thirty‐eight constituents, mainly botanicals were identified and prioritized by a federal interagency committee. Green tea was selected from this list as the botanical for expansion of the DSID. This article describes the process for prioritizing dietary ingredients in the DSID. It also discusses the criteria for inclusion of these ingredients, and the approach for selecting and testing products for the green tea pilot study.