Three-Photon Excitation of InGaN Quantum Dots.

We demonstrate that semiconductor quantum dots can be excited efficiently in a resonant three-photon process, while resonant two-photon excitation is highly suppressed. Time-dependent Floquet theory is used to quantify the strength of the multiphoton processes and model the experimental results. The efficiency of these transitions can be drawn directly from parity considerations in the electron and hole wave functions in semiconductor quantum dots. Finally, we exploit this technique to probe intrinsic properties of InGaN quantum dots. In contrast to nonresonant excitation, slow relaxation of charge carriers is avoided, which allows us to measure directly the radiative lifetime of the lowest energy exciton states. Since the emission energy is detuned far from the resonant driving laser field, polarization filtering is not required and emission with a greater degree of linear polarization is observed compared to nonresonant excitation.

N-terminal modification of proteins with o-aminophenols.

The synthetic modification of proteins plays an important role in chemical biology and biomaterials science. These fields provide a constant need for chemical tools that can introduce new functionality in specific locations on protein surfaces. In this work, an oxidative strategy is demonstrated for the efficient modification of N-terminal residues on peptides and N-terminal proline residues on proteins. The strategy uses o-aminophenols or o-catechols that are oxidized to active coupling species in situ using potassium ferricyanide. Peptide screening results have revealed that many N-terminal amino acids can participate in this reaction, and that proline residues are particularly reactive. When applied to protein substrates, the reaction shows a stronger requirement for the proline group. Key advantages of the reaction include its fast second-order kinetics and ability to achieve site-selective modification in a single step using low concentrations of reagent. Although free cysteines are also modified by the coupling reaction, they can be protected through disulfide formation and then liberated after N-terminal coupling is complete. This allows access to doubly functionalized bioconjugates that can be difficult to access using other methods.

Mild bioconjugation through the oxidative coupling of ortho-aminophenols and anilines with ferricyanide.

Using a small-molecule-based screen, ferricyanide was identified as a mild and efficient oxidant for the coupling of anilines and o-aminophenols on protein substrates. This reaction is compatible with thiols and 1,2-diols, allowing its use in the creation of complex bioconjugates for use in biotechnology and materials applications.

Host-microbe co-metabolism via MCAD generates circulating metabolites including hippuric acid.

The human gut microbiota produces dozens of small molecules that circulate in blood, accumulate to comparable levels as pharmaceutical drugs, and influence host physiology. Despite the importance of these metabolites to human health and disease, the origin of most microbially-produced molecules and their fate in the host remains largely unknown. Here, we uncover a host-microbe co-metabolic pathway for generation of hippuric acid, one of the most abundant organic acids in mammalian urine. Combining stable isotope tracing with bacterial and host genetics, we demonstrate reduction of phenylalanine to phenylpropionic acid by gut bacteria; the host re-oxidizes phenylpropionic acid involving medium-chain acyl-CoA dehydrogenase (MCAD). Generation of germ-free male and female MCAD-/- mice enabled gnotobiotic colonization combined with untargeted metabolomics to identify additional microbial metabolites processed by MCAD in host circulation. Our findings uncover a host-microbe pathway for the abundant, non-toxic phenylalanine metabolite hippurate and identify ß-oxidation via MCAD as a novel mechanism by which mammals metabolize microbiota-derived metabolites.

Ideal refocusing of an optically active spin qubit under strong hyperfine interactions.

Combining highly coherent spin control with efficient light-matter coupling offers great opportunities for quantum communication and computing. Optically active semiconductor quantum dots have unparalleled photonic properties but also modest spin coherence limited by their resident nuclei. The nuclear inhomogeneity has thus far bound all dynamical decoupling measurements to a few microseconds. Here, we eliminate this inhomogeneity using lattice-matched GaAs-AlGaAs quantum dot devices and demonstrate dynamical decoupling of the electron spin qubit beyond 0.113(3) ms. Leveraging the 99.30(5)% visibility of our optical π-pulse gates, we use up to Nπ = 81 decoupling pulses and find a coherence time scaling of [Formula: see text]. This scaling manifests an ideal refocusing of strong interactions between the electron and the nuclear spin ensemble, free of extrinsic noise, which holds the promise of lifetime-limited spin coherence. Our findings demonstrate that the most punishing material science challenge for such quantum dot devices has a remedy and constitute the basis for highly coherent spin-photon interfaces.

Room-temperature optically detected magnetic resonance of single defects in hexagonal boron nitride.

Optically addressable solid-state spins are important platforms for quantum technologies, such as repeaters and sensors. Spins in two-dimensional materials offer an advantage, as the reduced dimensionality enables feasible on-chip integration into devices. Here, we report room-temperature optically detected magnetic resonance (ODMR) from single carbon-related defects in hexagonal boron nitride with up to 100 times stronger contrast than the ensemble average. We identify two distinct bunching timescales in the second-order intensity-correlation measurements for ODMR-active defects, but only one for those without an ODMR response. We also observe either positive or negative ODMR signal for each defect. Based on kinematic models, we relate this bipolarity to highly tuneable internal optical rates. Finally, we resolve an ODMR fine structure in the form of an angle-dependent doublet resonance, indicative of weak but finite zero-field splitting. Our results offer a promising route towards realising a room-temperature spin-photon quantum interface in hexagonal boron nitride.

Charge-transfer heptamethine dyes for NIR singlet oxygen generation.

A heptamethine-based charge-transfer dye was designed based on previous evidence of triplet state formation in orthogonal charge-transfer partners and calculations suggesting the formation of a charge-transfer state in heptamethine dye derivatives. An acridinium derivative of IR-1061 was subsequently synthesized and characterized, demonstrating photochemical reactivity at wavelengths over 1000 nm.

Deterministic optical polarisation in nitride quantum dots at thermoelectrically cooled temperatures.

We report the successful realisation of intrinsic optical polarisation control by growth, in solid-state quantum dots in the thermoelectrically cooled temperature regime (≥200 K), using a non-polar InGaN system. With statistically significant experimental data from cryogenic to high temperatures, we show that the average polarisation degree of such a system remains constant at around 0.90, below 100 K, and decreases very slowly at higher temperatures until reaching 0.77 at 200 K, with an unchanged polarisation axis determined by the material crystallography. A combination of Fermi-Dirac statistics and k·p theory with consideration of quantum dot anisotropy allows us to elucidate the origin of the robust, almost temperature-insensitive polarisation properties of this system from a fundamental perspective, producing results in very good agreement with the experimental findings. This work demonstrates that optical polarisation control can be achieved in solid-state quantum dots at thermoelectrically cooled temperatures, thereby opening the possibility of polarisation-based quantum dot applications in on-chip conditions.

Wafer-scale Fabrication of Non-Polar Mesoporous GaN Distributed Bragg Reflectors via Electrochemical Porosification.

Distributed Bragg reflectors (DBRs) are essential components for the development of optoelectronic devices. For many device applications, it is highly desirable to achieve not only high reflectivity and low absorption, but also good conductivity to allow effective electrical injection of charges. Here, we demonstrate the wafer-scale fabrication of highly reflective and conductive non-polar gallium nitride (GaN) DBRs, consisting of perfectly lattice-matched non-polar (11-20) GaN and mesoporous GaN layers that are obtained by a facile one-step electrochemical etching method without any extra processing steps. The GaN/mesoporous GaN DBRs exhibit high peak reflectivities (>96%) across the entire visible spectrum and wide spectral stop-band widths (full-width at half-maximum >80 nm), while preserving the material quality and showing good electrical conductivity. Such mesoporous GaN DBRs thus provide a promising and scalable platform for high performance GaN-based optoelectronic, photonic, and quantum photonic devices.

Suitability of analytical methods to measure solubility for the purpose of nanoregulation.

Solubility is an important physicochemical parameter in nanoregulation. If nanomaterial is completely soluble, then from a risk assessment point of view, its disposal can be treated much in the same way as "ordinary" chemicals, which will simplify testing and characterisation regimes. This review assesses potential techniques for the measurement of nanomaterial solubility and evaluates the performance against a set of analytical criteria (based on satisfying the requirements as governed by the cosmetic regulation as well as the need to quantify the concentration of free (hydrated) ions). Our findings show that no universal method exists. A complementary approach is thus recommended, to comprise an atomic spectrometry-based method in conjunction with an electrochemical (or colorimetric) method. This article shows that although some techniques are more commonly used than others, a huge research gap remains, related with the need to ensure data reliability.

Multivalent viral capsids with internal cargo for fibrin imaging.

Thrombosis is the cause of many cardiovascular syndromes and is a significant contributor to life-threatening diseases, such as myocardial infarction and stroke. Thrombus targeted imaging agents have the capability to provide molecular information about pathological clots, potentially improving detection, risk stratification, and therapy of thrombosis-related diseases. Nanocarriers are a promising platform for the development of molecular imaging agents as they can be modified to have external targeting ligands and internal functional cargo. In this work, we report the synthesis and use of chemically functionalized bacteriophage MS2 capsids as biomolecule-based nanoparticles for fibrin imaging. The capsids were modified using an oxidative coupling reaction, conjugating ∼90 copies of a fibrin targeting peptide to the exterior of each protein shell. The ability of the multivalent, targeted capsids to bind fibrin was first demonstrated by determining the impact on thrombin-mediated clot formation. The modified capsids out-performed the free peptides and were shown to inhibit clot formation at effective concentrations over ten-fold lower than the monomeric peptide alone. The installation of near-infrared fluorophores on the interior surface of the capsids enabled optical detection of binding to fibrin clots. The targeted capsids bound to fibrin, exhibiting higher signal-to-background than control, non-targeted MS2-based nanoagents. The in vitro assessment of the capsids suggests that fibrin-targeted MS2 capsids could be used as delivery agents to thrombi for diagnostic or therapeutic applications.