Design Principles for Aqueous Interactive Materials: Lessons from Small Molecules and Stimuli-Responsive Systems.

Interactive materials are at the forefront of current materials research with few examples in the literature. Researchers are inspired by nature to develop materials that can modulate and adapt their behavior in accordance with their surroundings. Stimuli-responsive systems have been developed over the past decades which, although often described as "smart," lack the ability to act autonomously. Nevertheless, these systems attract attention on account of the resultant materials' ability to change their properties in a predicable manner. These materials find application in a plethora of areas including drug delivery, artificial muscles, etc. Stimuli-responsive materials are serving as the precursors for next-generation interactive materials. Interest in these systems has resulted in a library of well-developed chemical motifs; however, there is a fundamental gap between stimuli-responsive and interactive materials. In this perspective, current state-of-the-art stimuli-responsive materials are outlined with a specific emphasis on aqueous macroscopic interactive materials. Compartmentalization, critical for achieving interactivity, relies on hydrophobic, hydrophilic, supramolecular, and ionic interactions, which are commonly present in aqueous systems and enable complex self-assembly processes. Relevant examples of aqueous interactive materials that do exist are given, and design principles to realize the next generation of materials with embedded autonomous function are suggested.JAM thanks ESPRC for an IAA KTF M is grateful for a Newton International Fellowship OAS is thankful to ERC Consolidator Grant CAM-RI

Gateway vectors for efficient artificial gene assembly in vitro and expression in yeast Saccharomyces cerevisiae

Peer reviewedPublisher PD

Non-relativistic effective theory of dark matter direct detection

Dark matter direct detection searches for signals coming from dark matter scattering against nuclei at a very low recoil energy scale ~ 10 keV. In this paper, a simple non-relativistic effective theory is constructed to describe interactions between dark matter and nuclei without referring to any underlying high energy models. It contains the minimal set of operators that will be tested by direct detection. The effective theory approach highlights the set of distinguishable recoil spectra that could arise from different theoretical models. If dark matter is discovered in the near future in direct detection experiments, a measurement of the shape of the recoil spectrum will provide valuable information on the underlying dynamics. We bound the coefficients of the operators in our non-relativistic effective theory by the null results of current dark matter direct detection experiments. We also discuss the mapping between the non-relativistic effective theory and field theory models or operators, including aspects of the matching of quark and gluon operators to nuclear form factors.Comment: 35 pages, 3 figures, Appendix C.3 revised, acknowledgments and references adde

BLUF Domain Function Does Not Require a Metastable Radical Intermediate State

BLUF (blue light using flavin) domain proteins are an important family of blue light-sensing proteins which control a wide variety of functions in cells. The primary light-activated step in the BLUF domain is not yet established. A number of experimental and theoretical studies points to a role for photoinduced electron transfer (PET) between a highly conserved tyrosine and the flavin chromophore to form a radical intermediate state. Here we investigate the role of PET in three different BLUF proteins, using ultrafast broadband transient infrared spectroscopy. We characterize and identify infrared active marker modes for excited and ground state species and use them to record photochemical dynamics in the proteins. We also generate mutants which unambiguously show PET and, through isotope labeling of the protein and the chromophore, are able to assign modes characteristic of both flavin and protein radical states. We find that these radical intermediates are not observed in two of the three BLUF domains studied, casting doubt on the importance of the formation of a population of radical intermediates in the BLUF photocycle. Further, unnatural amino acid mutagenesis is used to replace the conserved tyrosine with fluorotyrosines, thus modifying the driving force for the proposed electron transfer reaction; the rate changes observed are also not consistent with a PET mechanism. Thus, while intermediates of PET reactions can be observed in BLUF proteins they are not correlated with photoactivity, suggesting that radical intermediates are not central to their operation. Alternative nonradical pathways including a keto–enol tautomerization induced by electronic excitation of the flavin ring are considered

Stealth Supersymmetry

We present a broad class of supersymmetric models that preserve R-parity but lack missing energy signatures. These models have new light particles with weak-scale supersymmetric masses that feel SUSY breaking only through couplings to the MSSM. This small SUSY breaking leads to nearly degenerate fermion/boson pairs, with small mass splittings and hence small phase space for decays carrying away invisible energy. The simplest scenario has low-scale SUSY breaking, with missing energy only from soft gravitinos. This scenario is natural, lacks artificial tunings to produce a squeezed spectrum, and is consistent with gauge coupling unification. The resulting collider signals will be jet-rich events containing false resonances that could resemble signatures of R-parity violation. We discuss several concrete examples of the general idea, and emphasize gamma + jet + jet resonances, displaced vertices, and very large numbers of b-jets as three possible discovery modes.Comment: 12 pages, 4 figure

The AdS/QCD Correspondence: Still Undelivered

We consider the particle spectrum and event shapes in large N gauge theories in different regimes of the short-distance 't Hooft coupling, lambda. The mesons in the small lambda limit should have a Regge spectrum in order to agree with perturbation theory, while generically the large lambda theories with gravity duals produce spectra reminiscent of KK modes. We argue that these KK-like states are qualitatively different from QCD modes: they are deeply bound states which are sensitive to short distance interactions rather than the flux tube-like states expected in asymptotically free, confining gauge theories. In addition, we also find that the characteristic event shapes for the large lambda theories with gravity duals are close to spherical, very different from QCD-like (small lambda, small N) and Nambu-Goto-like (small lambda, large N) theories which have jets. This observation is in agreement with the conjecture of Strassler on event shapes in large 't Hooft coupling theories, which was recently proved by Hofman and Maldacena for the conformal case. This conclusion does not change even when considering soft-wall backgrounds in the gravity dual. The picture that emerges is the following: theories with small and large lambda are qualitatively different, while theories with small and large N are qualitatively similar. Thus it seems that it is the relative smallness of the 't Hooft coupling in QCD that prevents a reliable AdS/QCD correspondence from emerging, and that reproducing characteristic QCD-like behavior will require genuine stringy dynamics to be incorporated into any putative dual theory.Comment: 32 pages, 15 figures; references added, minor changes, history clarifie

Searches for Long Lived Neutral Particles

An intriguing possibility for TeV scale physics is the existence of neutral long lived particles (LOLIPs) that subsequently decay into SM states. Such particles are many cases indistinguishable from missing transverse energy (MET) at colliders. We propose new methods to search for these particles using neutrino telescopes. We study their detection prospects, assuming production either at the LHC or through dark matter (DM) annihilations in the Sun and the Earth. We find that the sensitivity for LOLIPs produced at the LHC is limited by luminosity and detection energy thresholds. On the other hand, in the case of DM annihilation into LOLIPs, the sensitivity of neutrino telescopes is promising and may extend beyond the reach of upcoming direct detection experiments. In the context of low scale hidden sectors weakly coupled to the SM, such indirect searches allow to probe couplings as small as 10^-15.Comment: 22 pages, 6 figure

Abelian Hidden Sectors at a GeV

We discuss mechanisms for naturally generating GeV-scale hidden sectors in the context of weak-scale supersymmetry. Such low mass scales can arise when hidden sectors are more weakly coupled to supersymmetry breaking than the visible sector, as happens when supersymmetry breaking is communicated to the visible sector by gauge interactions under which the hidden sector is uncharged, or if the hidden sector is sequestered from gravity-mediated supersymmetry breaking. We study these mechanisms in detail in the context of gauge and gaugino mediation, and present specific models of Abelian GeV-scale hidden sectors. In particular, we discuss kinetic mixing of a U(1)_x gauge force with hypercharge, singlets or bi-fundamentals which couple to both sectors, and additional loop effects. Finally, we investigate the possible relevance of such sectors for dark matter phenomenology, as well as for low- and high-energy collider searches.Comment: 43 pages, no figures; v2: to match JHEP versio

Engineering tyrosine-based electron flow pathways in proteins: The case of aplysia myoglobin

Tyrosine residues can act as redox cofactors that provide an electron transfer ("hole-hopping") route that enhances the rate of ferryl heme iron reduction by externally added reductants, for example, ascorbate. Aplysia fasciata myoglobin, having no naturally occurring tyrosines but 15 phenylalanines that can be selectively mutated to tyrosine residues, provides an ideal protein with which to study such through-protein electron transfer pathways and ways to manipulate them. Two surface exposed phenylalanines that are close to the heme have been mutated to tyrosines (F42Y, F98Y). In both of these, the rate of ferryl heme reduction increased by up to 3 orders of magnitude. This result cannot be explained in terms of distance or redox potential change between donor and acceptor but indicates that tyrosines, by virtue of their ability to form radicals, act as redox cofactors in a new pathway. The mechanism is discussed in terms of the Marcus theory and the specific protonation/deprotonation states of the oxoferryl iron and tyrosine. Tyrosine radicals have been observed and quantified by EPR spectroscopy in both mutants, consistent with the proposed mechanism. The location of each radical is unambiguous and allows us to validate theoretical methods that assign radical location on the basis of EPR hyperfine structure. Mutation to tyrosine decreases the lipid peroxidase activity of this myoglobin in the presence of low concentrations of reductant, and the possibility of decreasing the intrinsic toxicity of hemoglobin by introduction of these pathways is discussed. © 2012 American Chemical Society