These new polymers unexpectedly showed much narrower band gaps than conventional substituted polyacetylenes by >0.2 eV. Interestingly, computational studies showed much smaller bond length alternation in the conjugated backbone containing cyclobutenes, resulting in highly delocalized π electrons along the polymer chain and lower band gaps.Site-specific modification of proteins with functional molecules provides powerful tools for researching and engineering proteins. Here we report a new chemical conjugation method which photocages highly reactive but chemically selective moieties, enabling the use of protein-inert amines for selective protein modification. New amino acids FnbY and FmnbY, bearing photocaged quinone methides (QMs), were genetically incorporated into proteins. Upon light activation, they generated highly reactive QM, which rapidly reacted with amine derivatives. This method features a rare combination of desired properties including fast kinetics, small and stable linkage, compatibility with low temperature, photocontrollability, and widely available reagents. Moreover, labeling via FnbY occurs on the β-carbon, affording the shortest linkage to protein backbone which is essential for advanced studies involving orientation and distance. We installed various functionalities onto proteins and attached a spin label as close as possible to the protein backbone, achieving high resolution in double electron-electron paramagnetic resonance distance measurements.Ubiquitous organo-ferrihydrite coprecipitates (OFC) significantly affect the mobility and availability of Cr in soil through sorption, but the underlying sorption mechanisms remain unclear at the molecular level. Due to the potential formation of OFC in agricultural soils with returned crop straws, we synthesized OFC with rice/rape straw-derived carbon (C) sources and different loadings. The molecular sorption mechanisms of Cr(III) to the synthesized OFC under different conditions were investigated by Cr K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy and scanning transmission X-ray microscopy (STXM). Cr(III) sorption by OFC decreased with increasing C loading and decreasing pH, regardless of C sources. Moreover, inhibition of Cr(III) sorption to OFC with high C loading occurred when ionic strength (IS) increased, suggesting the presence of outer-sphere complexed Cr(III). EXAFS analysis revealed that more Cr(III) were bound to ferrihydrite of the OFC at a relatively high pH, and organically bound Cr(III) enhanced when increasing C loading and decreasing IS. STXM analysis strongly suggested that C loading reduced Cr(III) sorption through blocking the binding sites on the ferrihydrite, which overwhelmed Cr(III) retention by the direct binding of Cr(III) to carboxyl of the particulate organic matter (OM) and OM coated on the Fh fractions of the OFC. These findings facilitated the comprehensive understanding of the sorption mechanisms of Cr(III) to OFC at the molecular level, which will assist the prediction of Cr(III) mobility in soils, particularly for Cr(III)-contaminated agricultural soils with the application of crop straws.Green policies currently incentivize concrete producers to replace portland cement with industrial byproducts to reduce their greenhouse gas (GHG) emissions. However, policies are based on attributional life cycle assessments (LCAs) that do not account for market constraints and consider byproducts either available burden-free to the user (cutoff approach) or partially responsible for the emissions generated in the upstream processes (allocation). The goal of this study was to investigate whether these approaches (and incentives) could lead to a mismanagement of byproducts and to suboptimal solutions in terms of regional GHG emissions. The use of ground granulated blast-furnace slag (GGBS) in Ontario was studied, and an optimization model to find the least GHG-intense way of using GGBS was developed. Results showed that producers should replace 30 to 40% of portland cement in high-strength concrete to minimize the regional GHG emissions associated with concrete. However, traditional LCA approaches do not suggest this solution and are estimated to lead to up to a 10% increase in concrete GHG emissions in Ontario. The substitution method, which assigns emissions or credits to byproducts based on emissions associated with the products they may displace, can yield decisions consistent with the regional emission optimization model. A revision of current policies is recommended to include market constraints.Aberrantly processed or mutant proteins misfold and assemble into a variety of soluble oligomers and insoluble aggregates, a process that is associated with an increasing number of diseases that are not curable or manageable. Herein, we present a chemical toolbox, AggFluor, that allows for live cell imaging and differentiation of complex aggregated conformations in live cells. Based on the chromophore core of green fluorescent proteins, AggFluor is comprised of a series of molecular rotor fluorophores that span a wide range of viscosity sensitivity. As a result, these compounds exhibit differential turn-on fluorescence when incorporated in either soluble oligomers or insoluble aggregates. This feature allows us to develop, for the first time, a dual-color imaging strategy to distinguish unfolded protein oligomers from insoluble aggregates in live cells. Furthermore, we have demonstrated how small molecule proteostasis regulators can drive formation and disassembly of protein aggregates in both conformational states. selleckchem In summary, AggFluor is the first set of rationally designed molecular rotor fluorophores that evenly cover a wide range of viscosity sensitivities. This set of fluorescent probes not only change the status quo of current imaging methods to visualize protein aggregation in live cells but also can be generally applied to study other biological processes that involve local viscosity changes with temporal and spatial resolutions.Ca2+ is the third-most prevalent metal ion in the environment. EF hands are common Ca2+-binding motifs found in both extracellular and intracellular proteins of eukaryotes and prokaryotes. Cytoplasmic EF hand proteins often mediate allosteric control of signal transduction pathway components in response to intracellular Ca2+ concentration fluctuations by coupling Ca2+ binding to changes in protein structure. We show that an extracellular structural Ca2+-binding site mediates protein thermostabilization by such conformational coupling as well. Binding Ca2+ to the EF hand of the extracellular (periplasmic) Escherichia coli glucose-galactose binding protein thermostabilizes this protein by ∼17 K relative to its Ca2+-free form. Using statistical thermodynamic analysis of a fluorescent conjugate of ecGGBP that reports simultaneously on ligand binding and multiple conformational states, we found that its Ca2+-mediated stabilization is determined by conformational coupling mechanisms in two independent conformational exchange reactions.