Engineered Proteins in Materials Research

Peptides and proteins have attracted scientific and technological interest largely because of their intriguing properties as catalysts, receptors, signalling molecules, and therapeutic agents. In attempts to understand and exploit these properties, protein engineering has been used primarily to obtain precious proteins in increased quantities, or to explore systematic alterations in protein sequence through site-directed mutagenesis. Design of protein structures de novo ("from scratch") has attracted less attention, and has been directed in the main toward studies of protein folding (Kamtekar et al., 1993). Such studies represent a key element in the current vigorous investigation of the connections between amino acid sequence and the three-dimensional structures of isolated protein chains in aqueous solution. This chapter describes protein engineering of quite another sort, in which the proteinacious nature of the product is less important than its macromolecular character

Core-Clickable PEG-Branch-Azide Bivalent-Bottle-Brush Polymers by ROMP: Grafting-Through and Clicking-To

The combination of highly efficient polymerizations with modular "click" coupling reactions has enabled the synthesis of a wide variety of novel nanoscopic tructures. Here we demonstrate the facile synthesis of a new class of clickable, branched nanostructures, polyethylene glycol (PEG)-branch-azide bivalent-brush polymers, facilitated by "graft-through" ring-opening metathesis polymerization of a branched norbornene-PEG-chloride macromonomer followed by halide-azide exchange. The resulting bivalent-brush polymers possess azide groups at the core near a polynorbornene backbone with PEG chains extended into solution; the structure resembles a unimolecular micelle. We demonstrate copper-catalyzed azide-alkre cycloaddition (CuAAC) "click-to" coupling of a photocleavable doxorubicin (DOX)-alkyne derivative to the azide core. The CuAAC coupling was quantitative across a wide range of nanoscopic sizes (similar to 6-similar to 50 nrn); UV photolysis of the resulting DOX-loaded materials yielded free DOX that was therapeutically effective against human cancer cells

Controlled Assembly of Macromolecular β-Sheet Fibrils

Construction of functional molecular devices by directed assembly processes is one of the main challenges in the field of nanotechnology. Many approaches to this challenge use biological assembly as a source of inspiration for the build up of new materials with controlled organization at the nanoscale. In particular, the self-assembly properties of β-sheet peptides have been used in the design of supramolecular materials, such as tapes, nanotubes, and fibrils

Template-Directed Olefin Cross Metathesis

A template containing two secondary dialkylammonium ion recognition sites for encirclement by olefin-bearing dibenzo[24]crown-8 derivatives has been used to promote olefin cross metatheses with ruthenium-alkylidene catalysts. For monoolefin monomers, the rates of metatheses and yields of the dimers are both amplified in the presence of the template. Likewise, for a diolefin monomer, the yield of the dimer is enhanced in the presence of the template under conditions where higher oligomers are not formed

A Genetically Encoded AND Gate for Cell-Targeted Metabolic Labeling of Proteins

We describe a genetic AND gate for cell-targeted metabolic labeling and proteomic analysis in complex cellular systems. The centerpiece of the AND gate is a bisected methionyl-tRNA synthetase (MetRS) that charges the Met surrogate azidonorleucine (Anl) to tRNAMet. Cellular protein labeling occurs only upon activation of two different promoters that drive expression of the N- and C-terminal fragments of the bisected MetRS. Anl-labeled proteins can be tagged with fluorescent dyes or affinity reagents via either copper-catalyzed or strain-promoted azide–alkyne cycloaddition. Protein labeling is apparent within 5 min after addition of Anl to bacterial cells in which the AND gate has been activated. This method allows spatial and temporal control of proteomic labeling and identification of proteins made in specific cellular subpopulations. The approach is demonstrated by selective labeling of proteins in bacterial cells immobilized in the center of a laminar-flow microfluidic channel, where they are exposed to overlapping, opposed gradients of inducers of the N- and C-terminal MetRS fragments. The observed labeling profile is predicted accurately from the strengths of the individual input signals

KELT-18b: Puffy Planet, Hot Host, Probably Perturbed

We report the discovery of KELT-18b, a transiting hot Jupiter in a 2.87-day orbit around the bright ( V = 10.1), hot, F4V star BD+60 1538 (TYC 3865-1173-1). We present follow-up photometry, spectroscopy, and adaptive optics imaging that allow a detailed characterization of the system. Our preferred model fits yield a host stellar temperature of K and a mass of , situating it as one of only a handful of known transiting planets with hosts that are as hot, massive, and bright. The planet has a mass of , a radius of , and a density of , making it one of the most inflated planets known around a hot star. We argue that KELT-18b’s high temperature and low surface gravity, which yield an estimated ∼600 km atmospheric scale height, combined with its hot, bright host, make it an excellent candidate for observations aimed at atmospheric characterization. We also present evidence for a bound stellar companion at a projected separation of ∼1100 au, and speculate that it may have contributed to the strong misalignment we suspect between KELT-18\u27s spin axis and its planet’s orbital axis. The inferior conjunction time is 2457542.524998 ± 0.000416 (BJD TDB ) and the orbital period is 2.8717510 ± 0.0000029 days. We encourage Rossiter–McLaughlin measurements in the near future to confirm the suspected spin–orbit misalignment of this system

“I’m only a dog!” : the Rwandan genocide, dehumanisation and the graphic novel

Graphic novels written in response to the 1994 Rwandan genocide do not confine their depictions of traumatic violence to humans, but extend their coverage to show how the genocide impacted on animals and the environment. Through analysis of the presentation of people and their relationships with other species across a range of graphic narratives, this article shows how animal imagery was used to justify inhumane actions during the genocide, and argues that representations of animals remain central to the recuperation processes in a post-genocide context too. Whilst novels and films that respond to the genocide have been the focus of scholarly work (Dauge-Roth, 2010), the graphic novel has yet to receive substantial critical attention. This article therefore unlocks the archive of French-, Dutch- and English-language graphic narratives written in response to the genocide by providing the first in-depth, comparative analysis of their animal representations. It draws on recent methodological approaches derived from philosophy (Derrida, [2008] trans. 2009), postcolonial ecocriticism (Huggan and Tiffin, 2010) and postcolonial trauma theory (Craps, 2012) in order show how human-centred strategies for recovery, and associated symbolic orders that forcefully position the animal outside of human law, continue to engender unequal and potentially violent relationships between humans, and humans and other species. In this way, graphic narratives that gesture towards more equitable relationships between humans, animals and the environment can be seen to support the processes of recovery and reconciliation in post-genocide Rwanda

Grand Challenges in Chemistry for 2016 and Beyond

When several ACS Central Science Editors met for dinner at the 2015 Pacifichem meeting, conversation turned to the grand challenges facing science and society, and those we felt chemistry was in a unique position to solve. With the New Year, we thought we would share our ideas in our first editorial of 2016. The arenas in which we see chemistry having the largest influence are the molecular bases of disease and aging, alternative energy advancement, and the conservation of our elemental resources