A guide to modern methods for poly(thio)ether synthesis using Earth-abundant metals.

Polyethers and polythioethers have a long and storied history dating back to the start of polymer science as a distinct field. As such, these materials have been utilized in a wide range of commercial applications and fundamental studies. The breadth of their material properties and the contexts in which they are applied is ultimately owed to their diverse monomer pre-cursors, epoxides and thiiranes, respectively. The facile polymerization of these monomers, both historically and contemporaneously, across academia and industry, has occurred through the use of Earth-abundant metals as catalysts and/or initiators. Despite this, polymerization methods for these monomers are underutilized compared to other monomer classes like cyclic olefins, vinyls, and (meth)acrylates. We feel a focused review that clearly outlines the benefits and shortcomings of extant synthetic methods for poly(thio)ethers along with their proposed mechanisms and quirks will help facilitate the utilization of these methods and by extension the unique polymer materials they create. Therefore, this Feature Article briefly describes the applications of poly(thio)ethers before discussing the feature-set of each poly(thio)ether synthetic method and qualitatively scoring them on relevant metrics (e.g., ease-of-use, molecular weight control, etc.) to help would-be poly(thio)ether-makers find an appropriate synthetic approach. The article is concluded with a look ahead at the future of poly(thio)ether synthesis with Earth-abundant metals.

Coupling of crop and livestock production can reduce the agricultural GHG emission from smallholder farms.

Ensuring global food security and environmental sustainability is dependent upon the contribution of the world's hundred million smallholder farms, but the contributions of smallholder farms to global agricultural greenhouse gas (GHG) emissions have been understudied. We developed a localized agricultural life cycle assessment (LCA) database to calculate GHG emissions and made the first extensive assessment of the smallholder farms' GHG emission reduction potentials by coupling crop and livestock production (CCLP), a redesign of current practices toward sustainable agriculture in China. CCLP can reduce the GHG emission intensity by 17.67%, with its own feed and manure returning to the field as an essential path. Scenario analysis verified that greater GHG emission reduction (28.09%-41.32%) will be achieved by restructuring CCLP. Therefore, this mixed farming is a mode with broader benefits to provide sustainable agricultural practices for reducing GHG emissions fairly.

Molecular View on Mechanical Reinforcement in Polymer Nanocomposites.

The microscopic origin of mechanical enhancement in polymer nanocomposite (PNC) melts is investigated through the combination of rheology and small-angle neutron scattering. It is shown that in the absence of an extensive particle network, the molecular deformation of polymer chains dominates the stress response on intermediate time scales. Quantitative analyses of small-angle neutron scattering spectra, however, reveal no enhanced structural anisotropy in the PNCs, compared with the pristine polymers under the same deformation conditions. These results demonstrate that the mechanical reinforcement of PNCs is not due to molecular overstraining, but instead a redistribution of strain field in the polymer matrix, akin to the classical picture of hydrodynamic effect of nanoparticles.

Assembly of Indole Cores through a Palladium-Catalyzed Metathesis of Ar-X σ-Bonds.

We describe the development of a new method for construction of highly substituted indole scaffolds through the strategic utilizing of the metathesis of Ar-X σ-bonds based on the dynamic nature of palladium-based oxidative addition/reductive elimination. A suitable and simple catalytic system has provided an appropriate platform for a productive ligand exchange and consecutive carbopalladation/C-H activation/amination of phosphine ligands with alkynes and aromatic/aliphatic amines for construction of structurally diverse indoles.

Forty years of reform and opening up: China's progress toward a sustainable path.

After 40 years of reform and "opening up," China has made remarkable economic progress. Such economic prosperity, however, has been coupled with environmental degradation. We analyze diverse long-term data to determine whether China is experiencing a decoupling of economic growth and environmental impacts, and where China stands with respect to the Sustainable Development Goals (SDGs) in terms of reducing regional division, urban-rural gap, social inequality, and land-based impacts on oceans. The results highlight that China's desire to achieve "ecological civilization" has resulted in a decoupling trend for major pollutants since 2015, while strong coupling remains with CO2 emissions. Progress has been made in health care provision, poverty reduction, and gender equity in education, while income disparity continues between regions and with rural-urban populations. There is a considerable way to go toward achieving delivery of the SDGs; however, China's progress toward economic prosperity and concomitant sustainability provides important insights for other countries.

Out-of-plane orientation alignment and reorientation dynamics of gold nanorods in polymer nanocomposite films.

In this work, we develop a novel, in situ characterization method to measure the orientation order parameter and investigate the reorientation and reshaping dynamics of polymer grafted gold nanorods (AuNRs) in polymer nanocomposite (PNC) thin films. The long aspect-ratio of AuNRs results in two well-defined plasmon resonance modes, allowing the optical properties of the PNC to be tuned over a wide spectral range. The alignment of the AuNRs in a particular direction can also be used to further tune these optical properties. We utilize variable angle spectroscopic ellipsometry as a unique technique to measure the optical properties of PNC films containing AuNRs at various angles of incidence, and use effective index of refraction analysis of the PNC to relate the birefringence in the film due to changes of the plasmon coupling to the orientation order parameter of AuNRs. Polymer thin films (ca. 70 nm) of either polystyrene (PS) or poly(methyl methacrylate) (PMMA) containing PS grafted AuNRs are probed with ellipsometry, and the resulting extinction coefficient spectra compare favorably with more traditional analytical techniques, electron microscopy (EM) and optical absorbance (vis-NIR) spectroscopy. Furthermore, variable angle spectroscopic ellipsometry measures optical birefringence, which allows us to determine the in- and out-of plane order of the AuNRs, a property that is not easily accessible using other measurement techniques. Additionally, this technique is applied in situ to demonstrate that AuNRs undergo a rapid (ca. 1-5 hours) reorientation before undergoing a slower (ca. 24 hours) rod to sphere shape transition. The reorientation behavior is different depending on the polymer matrix used. In the athermal case (i.e. PS matrix), the AuNRs reorient isotropically, while in PMMA the AuNRs do not become isotropic, which we hypothesize is due to PMMA preferentially wetting the silica substrate, leaving less vertical space for the AuNRs to reorient.

Dispersion of PMMA-grafted, mesoscopic iron-oxide rods in polymer films.

This study investigates the parameters that affect the dispersion of polymer grafted mesoscopic iron-oxide rods (FeMRs) in polymer matrices. FeMRs (212 nm long by 36 nm in diameter) are grafted with poly(methyl methacrylate) (PMMA) at three different brush molecular weights: 3.7 kg mol(-1), 32 kg mol(-1), and 160 kg mol(-1). Each FeMR sample was cast in a polymer thin film consisting of either PMMA or poly(ethylene oxide) (PEO) each at a molecular weight much higher or much lower than the brush molecular weight. We find that the FeMRs with 160 kg mol(-1) brush disperse in all matrices while the FeMRs with 32 kg mol(-1) and 3.7 kg mol(-1) brushes aggregate in all matrices. We perform simple free energy calculations, taking into account steric repulsion from the brush and van der Waals attraction between FeMRs. We find that there is a barrier for aggregation for the FeMRs with the largest brush, while there is no barrier for the other FeMRs. Therefore, for these mesoscopic particles, the brush size is the main factor that determines the dispersion state of FeMRs in polymer matrices with athermal or weakly attractive brush-matrix interactions. These studies provide new insight into the mechanisms that affect dispersion in polymer matrices of mesoscopic particles and therefore guide the design of composite films with well-dispersed mesoscopic particles.

Fine Golden Rings: Tunable Surface Plasmon Resonance from Assembled Nanorods in Topological Defects of Liquid Crystals.

Unprecedented, reversible, and dynamic control over an assembly of gold nanorods dispersed in liquid crystals (LC) is demonstrated. The LC director field is dynamically tuned at the nanoscale using microscale ring confinement through the interplay of elastic energy at different temperatures, thus fine-tuning its core replacement energy to reversibly sequester nanoscale inclusions at the microscale. This leads to shifts of 100 nm or more in the surface plasmon resonance peak, an order of magnitude greater than any previous work with AuNR composites.

Addressing China's grand challenge of achieving food security while ensuring environmental sustainability.

China's increasingly urbanized and wealthy population is driving a growing and changing demand for food, which might not be met without significant increase in agricultural productivity and sustainable use of natural resources. Given the past relationship between lack of access to affordable food and political instability, food security has to be given a high priority on national political agendas in the context of globalization. The drive for increased food production has had a significant impact on the environment, and the deterioration in ecosystem quality due to historic and current levels of pollution will potentially compromise the food production system in China. We discuss the grand challenges of not only producing more food but also producing it sustainably and without environmental degradation. In addressing these challenges, food production should be considered as part of an environmental system (soil, air, water, and biodiversity) and not independent from it. It is imperative that new ways of meeting the demand for food are developed while safeguarding the natural resources upon which food production is based. We present a holistic approach to both science and policy to ensure future food security while embracing the ambition of achieving environmental sustainability in China. It is a unique opportunity for China to be a role model as a new global player, especially for other emerging economies.

Impacts of soil and water pollution on food safety and health risks in China.

Environmental pollution and food safety are two of the most important issues of our time. Soil and water pollution, in particular, have historically impacted on food safety which represents an important threat to human health. Nowhere has that situation been more complex and challenging than in China, where a combination of pollution and an increasing food safety risk have affected a large part of the population. Water scarcity, pesticide over-application, and chemical pollutants are considered to be the most important factors impacting on food safety in China. Inadequate quantity and quality of surface water resources in China have led to the long-term use of waste-water irrigation to fulfill the water requirements for agricultural production. In some regions this has caused serious agricultural land and food pollution, especially for heavy metals. It is important, therefore, that issues threatening food safety such as combined pesticide residues and heavy metal pollution are addressed to reduce risks to human health. The increasing negative effects on food safety from water and soil pollution have put more people at risk of carcinogenic diseases, potentially contributing to 'cancer villages' which appear to correlate strongly with the main food producing areas. Currently in China, food safety policies are not integrated with soil and water pollution management policies. Here, a comprehensive map of both soil and water pollution threats to food safety in China is presented and integrated policies addressing soil and water pollution for achieving food safety are suggested to provide a holistic approach.

Assessing recovery from acidification of European surface waters in the year 2010: evaluation of projections made with the MAGIC model in 1995.

In 1999 we used the MAGIC (Model of Acidification of Groundwater In Catchments) model to project acidification of acid-sensitive European surface waters in the year 2010, given implementation of the Gothenburg Protocol to the Convention on Long-Range Transboundary Air Pollution (LRTAP). A total of 202 sites in 10 regions in Europe were studied. These forecasts can now be compared with measurements for the year 2010, to give a "ground truth" evaluation of the model. The prerequisite for this test is that the actual sulfur and nitrogen deposition decreased from 1995 to 2010 by the same amount as that used to drive the model forecasts; this was largely the case for sulfur, but less so for nitrogen, and the simulated surface water [NO3(-)] reflected this difference. For most of the sites, predicted surface water recovery from acidification for the year 2010 is very close to the actual recovery observed from measured data, as recovery is predominantly driven by reductions in sulfur deposition. Overall these results show that MAGIC successfully predicts future water chemistry given known changes in acid deposition.

Gold nanorod linking to control plasmonic properties in solution and polymer nanocomposites.

A novel, solution-based method is presented to prepare bifunctional gold nanorods (B-NRs), assemble B-NRs end-to-end in various solvents, and disperse linked B-NRs in a polymer matrix. The B-NRs have poly(ethylene glycol) grafted along its long axis and cysteine adsorbed to its ends. By controlling cysteine coverage, bifunctional ligands or polymer can be end-grafted to the AuNRs. Here, two dithiol ligands (C6DT and C9DT) are used to link the B-NRs in organic solvents. With increasing incubation time, the nanorod chain length increases linearly as the longitudinal surface plasmon resonance shifts toward lower adsorption wavelengths (i.e., red shift). Analogous to step-growth polymerization, the polydispersity in chain length also increases. Upon adding poly(ethylene glycol) or poly(methyl methacrylate) to chloroform solution with linked B-NR, the nanorod chains are shown to retain end-to-end linking upon spin-casting into PEO or PMMA films. Using quartz crystal microbalance with dissipation (QCM-D), the mechanism of nanorod linking is investigated on planar gold surfaces. At submonolayer coverage of cysteine, C6DT molecules can insert between cysteines and reach an areal density of 3.4 molecules per nm(2). To mimic the linking of Au NRs, this planar surface is exposed to cysteine-coated Au nanoparticles, which graft at 7 NPs per µm(2). This solution-based method to prepare, assemble, and disperse Au nanorods is applicable to other nanorod systems (e.g., CdSe) and presents a new strategy to assemble anisotropic particles in organic solvents and polymer coatings.

A facile route to synthesize nanogels doped with silver nanoparticles.

In this work, we describe a simple method to prepare hybrid nanogels consisting of a biocompatible core-shell polymer host containing silver nanoparticles. First, the nanogels (NG, ~160 nm) containing a lysozyme rich core and a dextran rich shell, are prepared via Maillard and heat-gelation reactions. Second, silver nanoparticles (Ag NPs, ~5nm) are synthesized in situ in the NG solution without requiring additional reducing agents. This approach leads to stable Ag NPs located in the NG. Furthermore, we demonstrate that the amount of Ag NPs in the NG can be tuned by varying silver precursor concentration. Hybrid nanogels with silver nanoparticles have potential in antimicrobial, optical and therapeutic applications.

Polymer single crystal templated janus nanoparticles.

Top-selective surface modification has been widely used for the synthesis of Janus nanoparticles (NPs). Herein we demonstrate that polymer single crystals can serve as generic substrates to immobilize NPs and the resultant NPs are Janus in nature. This technique is generic because various NPs as well as polymer single crystal substrates can be used. Single crystals of poly(ethylene oxide), polycaprolactone, and polyethylene-block-poly(ethylene oxide) have been successfully used to immobilize gold, magnetic, and semiconducting NPs. Subsequent dissolution of the single crystals led to various types of Janus NPs and NP clusters with different polymer brushes.

Joint pollution control at a catchment scale: compliance costs and policy implications.

Agricultural activities are one of the major drivers of increased nutrient levels such as nitrogen (N) and phosphorus (P) to both terrestrial and aquatic ecosystems. Elevated nutrient concentrations are associated with degraded water quality that can result in potential impacts for human health and the environment. A recent European study has identified elevated concentrations of N and P for many European river monitoring stations. In many cases the management of N and P has been considered separately here we address the multi-dimensional issue of water quality where the simultaneous management and control of both N and P is considered desirable. Using an integrated modelling approach various nutrient management scenarios are examined. It is found that although the control of N and P involve different farm adjustments and induce different land use changes there is a certain degree of complementarity between these two nutrient controls. The policy implication of ignoring such complementarity is that the appropriate environmental taxes to control the required nutrient losses are overestimated, resulting in unnecessary welfare losses to the society.

Sustainability of Scottish water quality in the early 21st century.

This paper reviews some of the current water quality issues relating to the surface waters of Scotland and highlights some of the key issues likely to be significant over the next decade. The sustainable management of water quality requires an appreciation of the temporal and spatial assessment of the resource, together with an identification of reference or natural conditions from which to determine change, and the elucidation of the drivers of change. Only through this integrated approach, can appropriate management strategies be developed and prioritised, bearing in mind that impacts may be decoupled from sources in both time and space. This paper highlights recent trends in water quality (from a hydrochemical perspective) with separation into three broad groups: rivers, lochs and estuaries. For rivers, a general reduction in concentration of determinants that are more indicative of urban point sources (phosphorus, ammonium, suspended solids, biochemical oxygen demand etc.) is apparent, while in more agriculturally-dominated areas, an increase in concentration of solutes that are considered more diffuse in origin, (e.g. nitrate) is reported. The increasing contribution to total loads from diffuse pollutants is a priority area for both research and policy. Current scientific challenges are to define the most appropriate spatial context within which regional water quality issues can be monitored and managed. It is likely that future emphasis will be placed on making an initial ecoregion based grouping in conjunction with physically defined catchment, which will be used to quantify site-specific impacts. Such an organisational approach will provide a mechanism that enables a targeted monitoring strategy to be developed. This will allow the establishment of ecologically based targets for water quality, and an improved understanding the biogeochemistry of pollution reversibility and ecosystem recovery. It is also fundamental to the development of tools through which to predict the time scale and magnitude of any recovery, such that environmental benefit can be optimised against realistic socio-economic constraints. The inter-relations between water quality objectives and the development of legislation for water resources management in Europe are discussed.