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Semiconducting polymers are at the forefront of next-generation organic electronics due to their robust mechanical and optoelectronic properties. However, their extended π-conjugation often leads to materials with low solubilities in common organic solvents, thus requiring processing in high-boiling-point and toxic halogenated solvents to generate thin-film devices. To address this environmental concern, a natural product-inspired side-chain engineering approach was used to incorporate galactose-containing moieties into semiconducting polymers toward improved processability in greener solvents. Novel isoindigo-based polymers with different ratios of galactose-containing side chains were synthesized to improve the solubilities of the organic semiconductors in alcohol-based solvents. The addition of carbohydrate-containing side chains to π-conjugated polymers was found to considerably impact the intermolecular aggregation of the materials and their microstructures in the solid state as confirmed by atomic force microscopy and grazing-incidence wide-angle X-ray scattering. The charge transport characteristics of the new semiconductors were evaluated by the fabrication of organic field-effect transistors prepared from both toxic halogenated and greener alcohol-based solvents. Importantly, the incorporation of carbohydrate-containing side chains was shown to have very little detrimental impact on the electronic properties of the polymer when processed from green solvents.Analytical characterization of extensively modified proteins (such as haptenated carrier proteins in synthetic vaccines) remains a challenging task due to the high degree of structural heterogeneity. Native mass spectrometry (MS) combined with limited charge reduction allows these obstacles to be overcome and enables meaningful characterization of a heavily haptenated carrier protein CRM197 (inactivated diphtheria toxin conjugated with nicotine), a major component of a smoking cessation vaccine. The extensive conjugation results in a near-continuum distribution of ionic signal in electrospray ionization (ESI) mass spectra of haptenated CRM197 even after size-exclusion chromatographic fractionation. However, supplementing the ESI MS measurements with limited charge reduction of ionic populations selected within narrow m/z windows gives rise to well-resolved charge ladders, from which both masses and charge states of the ionic species can be readily deduced. Application of this technique to a research-grade material of CRM197/H7 conjugate not only reveals its marginal conformational stability (manifested by the appearance of high charge-density ions in ESI MS) but also establishes a role of the extent of haptenation as a major factor driving the loss of the higher order structure integrity. The unique information provided by native MS used in combination with limited charge reduction provides a strong argument for this technique to become a standard/required tool in the analytical arsenal in the field of biotechnology and biopharmaceutical analysis, where protein conjugates are becoming increasingly common.Signal amplification is ubiquitous in biology and engineering. Protein enzymes, such as DNA polymerases, can routinely achieve &gt;106-fold signal increase, making them powerful tools for signal enhancement. Considerable signal amplification can also be achieved using nonenzymatic, cascaded nucleic acid strand exchange reactions. However, the practical application of such kinetically trapped circuits has so far proven difficult due to uncatalyzed leakage of the cascade. [https://www.selleckchem.com/products/e-7386.html E-7386 in vitro] We now demonstrate that strategically positioned mismatches between circuit components can reduce unprogrammed hybridization reactions and therefore greatly diminish leakage. In consequence, we were able to synthesize a three-layer catalytic hairpin assembly cascade that could operate in a single tube and that yielded 3.7 × 104-fold signal amplification in only 4 h, a greatly improved performance relative to previous cascades. This advance should facilitate the implementation of nonenzymatic signal amplification in molecular diagnostics, as well as inform the design of a wide variety of increasingly intricate nucleic acid computation circuits.Self-assembly of thermally responsive polypeptides into unique nanostructures offers intriguing attributes including dynamic physical dimensions, biocompatibility, and biodegradability for the smart bio-nanomaterials. As elastin-based polypeptide (EBP) fusion proteins with lower critical solution temperature (LCST) are studied as drug delivery systems, EBP block copolypeptides with the resilin-based polypeptide (RBP) displaying an upper critical solution temperature (UCST) have been of great interest. In this study, we report thermally triggered, dynamic self-assembly of EBP- and RBP-based diblock copolypeptides into switched nanostructures with reversibility under physiological conditions. Molecular DNA clones encoding for the EBP-RBP diblocks at different block length ratios were biosynthesized via recursive directional ligation and overexpressed, followed by nonchromatographic purification by inverse transition cycling. Genetically engineered diblock copolypeptides composed of the EBP with an LCST and the RBP with a UCST showed converse phase transition behaviors with both a distinct LCST and a distinct UCST (LCST less then UCST). As temperature increased, three phases of these EBP-RBP diblocks were observed (1) self-assembled micelles or vesicles below both LCST and UCST, (2) whole aggregates above LCST and below UCST, and (3) reversed micelles above both LCST and UCST. In conclusion, these stimuli-triggered, dynamic protein-based nanostructures are promising for advanced drug delivery systems, regenerative medicine, and biomedical nanotechnology.Transmission electron microscopy and spectroscopy currently enable the acquisition of spatially resolved spectral information from a specimen by focusing electron beams down to a sub-angstrom spot and then analyzing the energy of the inelastically scattered electrons with few-meV energy resolution. This technique has recently been used to experimentally resolve vibrational modes in 2D materials emerging at mid-infrared frequencies. Here, on the basis of first-principles theory, we demonstrate the possibility of identifying single isotope atom impurities in a nanostructure through the trace that they leave in the spectral and spatial characteristics of the vibrational modes. Specifically, we examine a hexagonal boron nitride molecule as an example of application, in which the presence of a single isotope impurity is revealed through changes in the electron spectra, as well as in the space-, energy-, and momentum-resolved inelastic electron signal. We compare these results with conventional far-field spectroscopy, showing that electron beams offer superior spatial resolution combined with the ability to probe the complete set of vibrational modes, including those that are optically dark.