Autonomous Artificial Olfactory Sensor Systems with Homeostasis Recovery via a Seamless Neuromorphic Architecture.

Neuromorphic olfactory systems have been actively studied in recent years owing to their considerable potential in electronic noses, robotics, and neuromorphic data processing systems. However, conventional gas sensors typically have the ability to detect hazardous gas levels but lack synaptic functions such as memory and recognition of gas accumulation, which are essential for realizing human-like neuromorphic sensory system. In this study, a seamless architecture for a neuromorphic olfactory system capable of detecting and memorizing the present level and accumulation status of nitrogen dioxide (NO) during continuous gas exposure, regulating a self-alarm implementation triggered after 147 and 85 s at a continuous gas exposure of 20 and 40 ppm, respectively.

Accelerated Intramolecular Charge Transfer in Tetracyanobutadiene- and Expanded Tetracyanobutadiene-Incorporated Asymmetric Triphenylamine-Quinoxaline Push-Pull Conjugates.

The excited-state properties of an asymmetric triphenylamine-quinoxaline push-pull system wherein triphenylamine and quinoxaline take up the roles of an electron donor and acceptor, respectively, are initially investigated. Further, in order to improve the push-pull effect, powerful electron acceptors, viz., 1,1,4,4-tetracyanobutadiene (TCBD) and cyclohexa-2,5-diene-1,4-diylidene-expanded tetracyanobutadiene (also known as expanded-TCBD or exTCBD), have been introduced into the triphenylamine-quinoxaline molecular framework using a catalyst-free [2 + 2] cycloaddition-retroelectrocyclization reaction.

Charge Resonance and Photoinduced Charge Transfer in Bis(,-dimethylaminophenyl-tetracyanobutadiene)-diketopyrrolopyrrole Multimodular System.

Intervalence charge transfer (IVCT) or charge resonance is often observed in redox-active systems encompassed of two identical electroactive groups, where one of the groups is either oxidized or reduced and serves as a model system to improve our fundamental understanding of charge transfer. This property has been explored in the present study in a multimodular push-pull system carrying two ,-dimethylaminophenyl-tetracyanobutadiene (DMA-TCBD) entities covalently linked to the opposite ends of bis(thiophenyl)diketopyrrolopyrrole (TDPP). Electrochemical or chemical reduction of one of the TCBDs promoted electron resonance between them, exhibiting an IVCT absorption peak in the near-infrared area.

Highly Coupled Heterobicycle-Fused Porphyrin Dimers: Excitonic Coupling and Charge Separation with Coordinated Fullerene, C.

Porphyrin dimers have been widely explored and studied owing to their importance in photosynthetic systems. A vast variety of dimers linked by different groups and at different angles have been synthesized and studied; however, the means by which to synthesize rigidly fused porphyrins with direct conjugation of the chromophores remains limited. Such a class of porphyrins may possess interesting properties that unconjugated or stacked dimers may not exhibit.

A Carbon Nanotube Binding BODIPY-C Nano Tweezer: Charge Stabilization through Sequential Electron Transfer.

Electron donor-acceptor (DA) hybrids comprised of single-wall carbon nanotubes (SWCNTs) are promising functional materials for light energy conversion. However, the DA hybrids built on SWCNTs have failed to reveal the much-sought long-lived charge separation (CS) due to the close proximity of the DA entities facilitating charge recombination. Here, we address this issue and report an elegant strategy to build multi-modular DA hybrids capable of producing long-lived CS states.

Aromatic heterobicycle-fused porphyrins: impact on aromaticity and excited state electron transfer leading to long-lived charge separation.

A new synthetic method to fuse benzo[4,5]imidazo[2,1-]isoindole to the porphyrin periphery at the β,β-positions has been developed, and its impact on the aromaticity and electronic structures is investigated. Reactivity investigation of the fused benzoimidazo-isoindole component reveals fluorescence quenching of a zinc porphyrin (AMIm-2) upon treatment with a Brønsted acid. The reaction of the zinc porphyrin (AMIm-2) with methyl iodide initiated a new organic transformation, resulting in the ring-opening of isoindole with the formation of an aldehyde and dimethylation of the benzoimidazo component.

Near-IR Intramolecular Charge Transfer in Strongly Interacting Diphenothiazene-TCBD and Diphenothiazene-DCNQ Push-Pull Triads.

Three types of phenothiazines dimers (PTZ-PTZ, 1-3), covalently linked with one or two acetylene linkers, were synthesized by copper-mediated Eglinton and Pd-catalyzed Sonogashira coupling reactions in excellent yields. The dimers 1-3 were further engaged in [2+2] cycloaddition-retroelectrocyclization reactions with strong electron acceptors, tetracyanoethylene (TCNE) and 7,7,8,8-tetracyanoquinodimethane (TCNQ) to yield tetracyanobutadiene (TCBD, 1 a-3 a), and dicyanoquinodimethane (DCNQ, 1 b-3 b) functionalized donor-acceptor (D-A) conjugates, respectively. The conjugates were examined by a series of spectral, computational, and electrochemical studies.

Formation and Photoinduced Electron Transfer in Porphyrin- and Phthalocyanine-Bearing N-Doped Graphene Hybrids Synthesized by Click Chemistry.

Graphene doped with heteroatoms such as nitrogen, boron, and phosphorous by replacing some of the skeletal carbon atoms is emerging as an important class of two-dimensional materials as it offers the much-needed bandgap for optoelectronic applications and provides better access for chemical functionalization at the heteroatom sites. Covalent grafting of photosensitizers onto such doped graphenes makes them extremely useful for light-induced applications. Herein, we report the covalent functionalization of N-doped graphene (NG) with two well-known electron donor photosensitizers, namely, zinc porphyrin (ZnP) and zinc phthalocyanine (ZnPc), using the simple click chemistry approach.

Symmetrically Ion-Gated In-Plane Metal-Oxide Transistors for Highly Sensitive and Low-Voltage Driven Bioelectronics.

To provide a unique opportunity for on-chip scaled bioelectronics, a symmetrically gated metal-oxide electric double layer transistor (EDLT) with ion-gel (IG) gate dielectric and simple in-plane Corbino electrode architecture is proposed. Using amorphous indium-gallium-zinc oxide (a-IGZO) semiconductor and IG dielectric layers, low-voltage driven EDLTs with high ionotronic effects can be realized. More importantly, in contrast to the conventional asymmetric rectangular EDLTs which can cause non-uniform potential variation in the active channel layer and eventually degrade the sensing performance, the new symmetrical in-plane type EDLTs achieve high and spatially uniform ion responsive behaviors.

Charge-Transfer in Panchromatic Porphyrin-Tetracyanobuta-1,3-Diene-Donor Conjugates: Switching the Role of Porphyrin in the Charge Separation Process.

Using a combination of cycloaddition-retroelectrocyclization reaction, free-base and zinc porphyrins (H P and ZnP) are decorated at their β-pyrrole positions with strong charge transfer complexes, viz., tetracyanobuta-1,3-diene (TCBD)-phenothiazine (3 and 4) or TCBD-aniline (7 and 8), novel class of push-pull systems. The physico-chemical properties of these compounds (MP-Donor and MP-TCBD-Donor) have been investigated using a range of electrochemical, spectroelectrochemical, DFT as well as steady-state and time-resolved spectroscopic techniques.

Photoinduced Charge Separation Prompted Intervalence Charge Transfer in a Bis(thienyl)diketopyrrolopyrrole Bridged Donor-TCBD Push-Pull System.

Intervalence charge transfer (IVCT), a phenomenon observed in molecular systems comprised of two redox centers differing in oxidation states by one unit, is reported in a novel, newly synthesized, multi-modular donor-acceptor system comprised of central bis(thienyl)diketopyrrolopyrrole (TDPP) hosting two phenothiazine-tetracyanobutadiene (PTZ-TCBD) entities on the opposite sides. One-electron reduction of TCBD promoted electron exchange between the two TCBD resulting in IVCT transition in the near-infrared region. The stabilization energy, -ΔG and comproportionation equilibrium constant, K calculated from peak potentials of the split reduction waves were found to be 1.

Symmetric and Asymmetric Push-Pull Conjugates: Significance of Pull Group Strength on Charge Transfer and Separation.

The effect of acceptor strength on excited-state charge transfer (CT) and charge separation (CS) in central phenothiazine (PTZ)-derived symmetric (PTZ-(TCBD-TPA)) and asymmetric (PTZ-(TCBD/DCNQ-TPA)) push-pull conjugates, in which triphenylamine (TPA) acts as end capping and 1,1,4,4-tetracyanobuta-1,3-diene (TCBD) and cyclohexa-2,5-diene-1,4-ylidene-expanded TCBD (DCNQ) act as electron acceptor units, is reported. Due to strong push-pull effects, intramolecular CT was observed in the ground state, extending the absorption into the near-infrared region. Electrochemical, spectroelectrochemical, and computational studies coupled with energy-level calculations predicted both and to be efficient candidates for ultrafast CT.

Unveiling the Photoinduced Electron-Donating Character of MoS in Covalently Linked Hybrids Featuring Perylenediimide.

The covalent functionalization of MoS with a perylenediimide (PDI) is reported and the study is accompanied by detailed characterization of the newly prepared MoS -PDI hybrid material. Covalently functionalized MoS interfacing organic photoactive species has shown electron and/or energy accepting, energy reflecting or bi-directional electron accepting features. Herein, a rationally designed PDI, unsubstituted at the perylene core to act as electron acceptor, forces MoS to fully demonstrate for the first time its electron donor capabilities.

Formation of Highly Efficient, Long-Lived Charge Separated States in Star-Shaped Ferrocene-Diketopyrrolopyrrole-Triphenylamine Donor-Acceptor-Donor Conjugates.

The significance of multiple number of donor-acceptor entities on a central electron donor in a star-shaped molecular system in improving light energy harvesting ability is reported. For this, donor-acceptor-donor type conjugates comprised up to three entities ferrocenyl (Fc)-diketopyrrolopyrrole (DPP) onto a central triphenylamine (TPA), (4-6) by the Pd-catalyzed Sonogashira cross-coupling reactions have been newly synthesized and characterized. Donor-acceptor conjugates possessing diketopyrrolopyrrole (1 to 3 entities) onto the central triphenylamine, (1-3) served as reference dyads while monomeric DPP and Fc-DPP served as control compounds.

Excited-State Electron Transfer in 1,1,4,4-Tetracyanobuta-1,3-diene (TCBD)- and Cyclohexa-2,5-diene-1,4-diylidene-Expanded TCBD-Substituted BODIPY-Phenothiazine Donor-Acceptor Conjugates.

A new set of donor-acceptor (D-A) conjugates capable of undergoing ultrafast electron transfer were synthesized using 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY)-substituted phenothiazine, SM1-SM3, by a Pd-catalyzed Sonogashira cross-coupling reaction and a [2+2] cycloaddition-electrocyclic ring-opening reaction. The incorporation of 1,1,4,4-tetracyanobuta-1,3-diene (TCBD) and cyclohexa-2,5-diene-1,4-diylidene-expanded TCBD (abbreviated as DCNQ=dicyanodiquinodimethane) in BODIPY-substituted phenothiazine resulted in significant perturbation of the optical and electronic properties. The absorption spectrum of both SM2 and SM3 showed red shifted absorption as compared to SM1.

Push-Pull Porphyrins via β-Pyrrole Functionalization: Evidence of Excited State Events Leading to High-Potential Charge-Separated States.

A new set of free-base and zinc(II)-metallated, β-pyrrole-functionalized unsymmetrical push-pull porphyrins were designed and synthesized via β-mono- and dibrominated tetraphenylporphyrins using Sonogashira cross-coupling reactions. The ability of donors and acceptors on the push-pull porphyrins to produce high-potential charge separated states was investigated. The porphyrins were functionalized at the opposite β,β'-pyrrole positions of porphyrin ring bearing triphenylamine push groups and naphthalimide pull groups.

Excited-State Charge Transfer in Covalently Functionalized MoS with a Zinc Phthalocyanine Donor-Acceptor Hybrid.

The functionalization of MoS is of paramount importance for tailoring its properties towards optoelectronic applications and unlocking its full potential. Zinc phthalocyanine (ZnPc) carrying an 1,2-dithiolane oxide linker was used to functionalize MoS at defect sites located at the edges. The structure of ZnPc-MoS was fully assessed by complementary spectroscopic, thermal, and microscopy imaging techniques.

Interfacing Transition Metal Dichalcogenides with Carbon Nanodots for Managing Photoinduced Energy and Charge-Transfer Processes.

Exfoliated semiconducting MoS and WS were covalently functionalized with 1,2-dithiolane-modified carbon nanodots (CNDs). The newly synthesized CND-MoS and CND-WS hybrids were characterized by spectroscopic, thermal, and electron microscopy imaging methods. Based on electronic absorption and fluorescence emission spectroscopy, modulation of the optoelectronic properties of TMDs by interfacing with CNDs was accomplished.

Mediastinal Tuberculous Lymphadenitis Diagnosed by Endosonographic Fine Needle Aspiration.

Isolated mediastinal tuberculous lymphadenitis is clinically rare. Its clinical presentation may mimic an esophageal submucosal tumor by extrinsic compression. A 26-year-old woman was referred to our hospital for an esophageal subepithelial tumor.

Primary cardiac angiosarcoma: a prolonged response to surgical resection followed by concurrent chemoradiotherapy with docetaxel.

Introduction: Primary cardiac cancer is a very rare disease, among which primary cardiac angiosarcoma is one of the most frequent type and is characterized by extremely poor prognosis without established optimal treatment.

Case Description: Here we report a case of primary cardiac angiosarcoma with hemorrhagic pericardial effusion who achieved a durable response with tumor excision followed by concurrent chemoradiotherapy with docetaxel. A sixty year old man was presented with dyspnea and was diagnosed with primary cardiac angiosarcoma with hemorrhagic pericardial effusion.

Hyperglycemia decreases the expression of ATP synthase β subunit and enolase 2 in glomerular epithelial cells.

Glomerular epithelial cells (GECs) are known to play a key role in maintaining the structure and function of the glomerulus. GEC injury induced by hyperglycemia is present in early-stage diabetic nephropathy (DN), which is the most common cause of renal failure. In an attempt to identify target proteins involved in the pathogenesis of GEC injury at early DN, we performed the proteomic analysis using primary cultures of GECs, prepared from the dissected rat glomeruli.