Tailoring of Visible to Near-Infrared Active 2D MXene with Defect-Enriched Titania-Based Heterojunction Photocatalyst for Green H2 Generation.

A wide solar light absorption window and its utilization, long-term stability, and improved interfacial charge transfer are the keys to scalable and superior solar photocatalytic performance. Based on this objective, a noble metal-free composite photocatalyst is developed with conducting MXene (Ti3C2) and semiconducting cauliflower-shaped CdS and porous Cu2O. XPS, HRTEM, and ESR analyses of TiOy@Ti3C2 confirm the formation of enough defect-enriched TiOy (where y is < 2) on the surface of Ti3C2 during hydrothermal treatment, thus creating a third semiconducting site with enough oxygen vacancy. The final material, TiOy@Ti3C2/CdS/Cu2O, shows a broad absorption window from 300 to 2000 nm, covering the visible to near-infrared (NIR) range of the solar spectrum. Photocatalytic H2 generation activity is found to be 12.23 and 16.26 mmol g-1 h-1 in the binary (TiOy@Ti3C2/CdS) and tertiary composite (TiOy@Ti3C2/CdS/Cu2O), respectively, with good repeatability under visible-NIR light using lactic acid as the hole scavenger. A clear increase of efficiency by 1.53 mmol g-1 h-1 in the tertiary composite due to NIR light absorption supports the intrinsic upconversion of electrons, which will open a new prospective of solar light utilization. Decreased charge-transfer resistance from the EIS plot and a decrease in PL intensity established the improved interfacial charge separation in the tertiary composite. Compared to pure CdS, H2 generation efficiency is 29.6 times higher on the noble metal-free tertiary composite with an apparent quantum efficiency of 12.34%. Synergistic effect of defect-enriched TiOy formation, creation of proper dual p-n junction on a Ti3C2 sheet as supported by the Mott-Schottky plot, significant NIR light absorption, increased electron mobility, and charge transfer on the conductive Ti3C2 layer facilitate the drastically increased hydrogen evolution rate even after several cycles of repetition. Expectantly, the 2D MXene-based heterostructure with defect-enriched dual p-n junctions of desired interface engineering will facilitate scalable photocatalytic water splitting over a broad range of the solar spectrum.

Higher-order olfactory neurons in the lateral horn support odor valence and odor identity coding in Drosophila.

Understanding neuronal representations of odor-evoked activities and their progressive transformation from the sensory level to higher brain centers features one of the major aims in olfactory neuroscience. Here, we investigated how odor information is transformed and represented in higher-order neurons of the lateral horn, one of the higher olfactory centers implicated in determining innate behavior, using Drosophila melanogaster. We focused on a subset of third-order glutamatergic lateral horn neurons (LHNs) and characterized their odor coding properties in relation to their presynaptic partner neurons, the projection neurons (PNs) by two-photon functional imaging. We show that odors evoke reproducible, stereotypic, and odor-specific response patterns in LHNs. Notably, odor-evoked responses in these neurons are valence-specific in a way that their response amplitude is positively correlated with innate odor preferences. We postulate that this valence-specific activity is the result of integrating inputs from multiple olfactory channels through second-order neurons. GRASP and micro-lesioning experiments provide evidence that glutamatergic LHNs obtain their major excitatory input from uniglomerular PNs, while they receive an odor-specific inhibition through inhibitory multiglomerular PNs. In summary, our study indicates that odor representations in glutamatergic LHNs encode hedonic valence and odor identity and primarily retain the odor coding properties of second-order neurons.

Olfactory processing in the lateral horn of Drosophila.

Sensing olfactory signals in the environment represents a crucial and significant task of sensory systems in almost all organisms to facilitate survival and reproduction. Notably, the olfactory system of diverse animal phyla shares astonishingly many fundamental principles with regard to anatomical and functional properties. Binding of odor ligands by chemosensory receptors present in the olfactory peripheral organs leads to a neuronal activity that is conveyed to first and higher-order brain centers leading to a subsequent odor-guided behavioral decision. One of the key centers for integrating and processing innate olfactory behavior is the lateral horn (LH) of the protocerebrum in insects. In recent years the LH of Drosophila has garnered increasing attention and many studies have been dedicated to elucidate its circuitry. In this review we will summarize the recent advances in mapping and characterizing LH-specific cell types, their functional properties with respect to odor tuning, their neurotransmitter profiles, their connectivity to pre-synaptic and post-synaptic partner neurons as well as their impact for olfactory behavior as known so far.

Odor mixtures of opposing valence unveil inter-glomerular crosstalk in the Drosophila antennal lobe.

Evaluating odor blends in sensory processing is a crucial step for signal recognition and execution of behavioral decisions. Using behavioral assays and 2-photon imaging, we have characterized the neural and behavioral correlates of mixture perception in the olfactory system of Drosophila. Mixtures of odors with opposing valences elicit strong inhibition in certain attractant-responsive input channels. This inhibition correlates with reduced behavioral attraction. We demonstrate that defined subsets of GABAergic interneurons provide the neuronal substrate of this computation at pre- and postsynaptic loci via GABAB- and GABAA receptors, respectively. Intriguingly, manipulation of single input channels by silencing and optogenetic activation unveils a glomerulus-specific crosstalk between the attractant- and repellent-responsive circuits. This inhibitory interaction biases the behavioral output. Such a form of selective lateral inhibition represents a crucial neuronal mechanism in the processing of conflicting sensory information.

Aggregation induced non-emissive-to-emissive switching of molecular platinum clusters.

We show here for the first time the Aggregation Induced Emission (AIE) mechanism and solvatochromic impact on Pt-SG (SG-deprotonated glutathione) nanoclusters. In this work, the AIE properties of Pt-SG clusters were investigated through computational and spectroscopic investigations. Computational data established that aggregation triggers a distinct change in the frontier molecular orbitals (FMOs) from metal d-orbital centered FMOs in the monomer to metal-thiolate and thiolate centered FMOs in the dimer improving the radiative decay process. Solvent dependent photoluminescence studies proved that a Lewis-acidic environment can significantly perturb the metal-thiolate and thiolate centered FMOs that are involved in the electronic transitions as predicted by our computational work. These semiconducting clusters exhibit a large Stokes shift and zero spectral overlap between absorption and emission which makes this Pt-SG cluster an excellent material for solar concentrators and solid-state light emitters. This AIE-OFF-ON emission was utilized to delineate a proof-of-concept sensor device that is sensitive to temperature and an acid/base.

Not all pycnodysostosis-related mutants of human cathepsin K are inactive - crystal structure and biochemical studies of an active mutant I249T.

Human cathepsin K (CTSK) is a collagenolytic lysosomal cysteine protease that plays an important role in bone turnover. Mutation in CTSK gene is associated with loss of collagenolytic activity of CTSK leading to an autosomal recessive bone disorder called pycnodysostosis. Although a number of pycnodysostotic missense mutations have been reported, underlying mechanism of the disease is not clear. In this study, we investigated in vitro six recombinant pycnodysostosis-related mutants of human CTSK (G79E, I249T, G243E, G303E, G319C and Q187P). While all the mutants, like wild-type, show similar high levels of expression in Escherichia coli, four of them (G79E, G303E, G319C and Q187P) are inactive, unstable and spontaneously degrade during purification process. In contrast, proteolytic/collagenolytic activity, zymogen activation kinetics and stability of G243E and I249T mutants are nominally affected. Crystal structure of I249T at 1.92 Å resolution shows that the mutation in R-domain causes conformational changes of a surface loop in the L-domain although the catalytic cleft remains unaltered. Molecular simulation, normal mode analysis and fluorescence lifetime measurement eliminated the possibility that the change in L-domain surface loop orientation is a crystallization artefact. CD-based thermal melting profile indicates that stability of I249T is significantly higher than wild-type. Our studies first time reports that pycnodysostosis-related mutations do not always lead to complete loss of general proteolytic activity or specific collagenolytic activity of CTSK. The first crystal structure of a pycnodysostotic mutant (I249T) provides critical information that may pave new avenues towards understanding the disease at molecular level. DATABASE: The atomic co-ordinates and structure factors for I249T mutant of human CTSK (codes 5Z5O) have been deposited in the Protein Data Bank (http://wwpdb.org/).

Decoupled in-plane Dipole Resonance Modulated Colorimetric Assay-Based Optical Ruler for Ultra-Trace Gold (Au) Detection.

Decoupling of different plasmon resonance modes (in-plane, and out-of-plane dipole and quadrupole resonances) by tuning nanoparticle's size and shape offers a new field of plasmonics as colorimetric assay-based optical-ruler for ultra-trace sensing. Driven by its low cost, easy to perform and efficient way to measure trace level (up to 30 ppt in presence of common mining elements in natural gold ore) abundance, this study develops a highly selective and ultrasensitive turn-on colorimetric sensor to detect gold-ion from environmental samples. Different level of gold-ion tracer makes size variable spherical- and disc-shaped silver nanoparticles when added to a 'growth solution' which results decoupling of in-plane dipole resonance from in-plane quadrupole and out-of-plane dipole resonances with a wide range of in-plane dipole plasmon tunability to generate different colors. This color-coded sensing of gold-ion shows high selectivity and ultrasensitivity over other metal ions in the ppt level with an impurity aberration limit of 1 ppm. A plausible explanation explains the possible role of catalytic gold-ion to initiate unfavorable silver ion (Ag+) reduction by ascorbic acid to generate silver nanoparticles. Proposed technology has been applied in real mining sample (Bugunda Gold Deposit, Tajikistan) to detect gold concentration from ores to find potential application in mining technology.