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 (NO2) 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. Thin-film-transistor type gas sensors utilizing carbon nanotube semiconductors detect NO2 gas molecules through carrier trapping and exhibit long-term retention properties, which are compatible with neuromorphic excitatory applications. Additionally, the neuromorphic inhibitory performance is also characterized via gas desorption with programmable ultraviolet light exposure, demonstrating homeostasis recovery. These results provide a promising strategy for developing a facile artificial olfactory system that demonstrates complicated biological synaptic functions with a seamless and simplified system architecture.

Charge Resonance and Photoinduced Charge Transfer in Bis(N,N-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 N,N-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. The comproportionation energy, -ΔGcom, and equilibrium constant, Kcom, evaluated from the split reduction peak were, respectively, 1.06 × 104 J/mol and 72.3 M-1. Excitation of the TDPP entity in the system promoted the thermodynamically feasible sequential charge transfer and separation of charges in benzonitrile, wherein the IVCT peak formed upon charge separation served as a signature peak in characterizing the product. Further, transient data analyzed using Global Target Analysis revealed the charge separation to take place in a ps time scale (k ∼ 1010 s-1) as a result of close positioning and strong electronic interaction between the entities. The significance of IVCT in probing excited-state processes is evidenced by the present study.

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. The presence of these electron acceptors caused strong ground-state polarization extending the absorption well into the near-IR region accompanied by strong fluorescence quenching due to intramolecular charge transfer (CT). Systematic studies were performed using a suite of spectral, electrochemical, computational, and pump-probe spectroscopic techniques to unravel the intramolecular CT mechanism and to probe the role of TCBD and exTCBD in promoting excited-state CT and separation events. Faster CT in exTCBD-derived compared to that in TCBD-derived push-pull systems has been witnessed in polar benzonitrile.

Highly Coupled Heterobicycle-Fused Porphyrin Dimers: Excitonic Coupling and Charge Separation with Coordinated Fullerene, C60.

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. In this study, bisbenzimidazole-fused porphyrin dimers and their mono- and bis-zinc derivatives are synthesized and characterized. As a consequence of excitonic coupling, these dimers exhibit a split Soret band irrespective of the metal ion in the porphyrin cavity. Steady-state fluorescence and excitation spectra followed by femtosecond transient absorption spectral studies of the heterometallated dimer, (free-base and zinc porphyrin) reveals the occurrence of efficient singlet-singlet energy transfer (>95 % efficiency and rate constant >1012  s-1 ) within the dyad. Further, donor-acceptor conjugates were formed by metal-ligand axial coordination of phenyl imidazole functionalized C60 and were characterized by a variety of physicochemical techniques. Excited state charge separation from both singlet and triplet excited states of ZnP in the conjugates has been established. The lifetime of the final charge-separated state was in the 30-40 µs range revealing charge stabilization. Interestingly, no charge separation in the conjugate derived from the heterometallated dimer was observed wherein excitation transfer dominated the process. The present study brings out the importance of the rigid π-spacer connecting porphyrin dimers in governing the energy and electron transfer events when coupled with an electron acceptor.

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-a]isoindole to the porphyrin periphery at the ß,ß-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. The fused benzoimidazo-isoindole component acted as a good ligand to bind platinum(ii), forming novel homobimetallic and heterobimetallic porphyrin complexes. The fusion of benzoimidazo-isoindole on the porphyrin ring resulted in bathochromically shifted absorptions and emissions, reflecting the extended conjugation of the porphyrin π-system. Time-resolved emission and transient absorption spectroscopy revealed stable excited state species of the benzoimidazo-isoindole fused porphyrins. Zinc porphyrin AMIm-2 promoted excited state electron transfer upon coordinating with an electron acceptor, C60, generating a long-lived charge-separated state, in the order of 37.4 µs. The formation of the exceptionally long-lived charge-separated state is attributed to the involvement of both singlet and triplet excited states of AMIm-2, which is rarely reported in porphyrins.

A Carbon Nanotube Binding BODIPY-C60 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. For this, a nano tweezer featuring V-shape configured BODIPY was synthesized to host SWCNTs of different diameters via π-stacking. Supported by spectral, electrochemical, and computational studies, the established energy scheme revealed the possibility of sequential electron transfer. Systematic pump-probe studies covering wide spatial and temporal scales provided evidence of CS from the initial 1 BODIPY* ultimately resulting in C60 ⋅- -BODIPY-SWCNT⋅+ CS states of lifetimes in the 20-microsecond range.

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. Strong ground state polarization leading to new optical transitions was witnessed in both series of D-A conjugates. In the case of DCNQ derived D-A system 1 b, the optical coverage extended until 1200 nm in benzonitrile, making this a rare class of D-A ICT system. Multiple redox processes were witnessed in these D-A systems, and the frontier orbitals generated on DFT optimized structures further supported the ICT phenomenon. Photochemical studies performed using femtosecond pump-probe studies confirmed solvent polarity dependent excited state charge transfer and separation in these novel multi-modular D-A conjugates. The charge-separated states lasted up to 70 ps in benzonitrile while in toluene slightly prolonged lifetime of up to 100 ps was witnessed. The significance of phenothiazine dimer in wide-band optical capture all the way into the near-IR region and promoting ultrafast photoinduced charge transfer in the D-A-D configured multi-modular systems, and the effect of donor-acceptor distance and the solvent polarity was the direct outcome of the present study.

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. Covalent attachment of ZnP and ZnPc at the N-sites of NG in NG-ZnP and NG-ZnPc hybrids was confirmed by using a range of spectroscopic, thermogravimetric and imaging techniques. Ground- and excited-state interactions in NG-ZnP and NG-ZnPc were monitored by using spectral and electrochemical techniques. Efficient quenching of photosensitizer fluorescence in these hybrids was observed, and the relatively easier oxidations of ZnP and ZnPc supported excited-state charge-separation events. Photoinduced charge separation in NG-ZnP and NG-ZnPc hybrids was confirmed by using the ultrafast pump-probe technique. The measured rate constants were of the order of 1010  s,-1 thus indicating ultrafast electron transfer phenomena.

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. The symmetrically gated a-IGZO EDLTs exhibited a responsivity of 129.4% to 5 ppm mercury (Hg2+ ) ions which are approximately three times higher than that with conventional electrode structure (responsivity of 38.5%). To confirm the viability of the new device architectures and the findings, the detailed mechanism of the symmetric gating effects in the in-plane EDLTs with a variety of electrical characterization and 3D fine element analysis simulations is also discussed.

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 (H2 P and ZnP) are decorated at their ß-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. Ground-state charge transfer interactions between the porphyrin and the electron-withdrawing TCBD directly attached to the porphyrin π-system extended the absorption features well into the near-infrared region. To visualize the photo-events, energy level diagrams with the help of free-energy calculations have been established. Switching the role of porphyrin from the initial electron acceptor to electron donor was possible to envision. Occurrence of photoinduced charge separation has been established by complementary transient absorption spectral studies followed by global and target data analyses. Better charge stabilization in H2 P derived over ZnP derived conjugates, and in phenothiazine derived over aniline derived conjugates has been possible to establish. These findings highlight the importance of the nature of porphyrins and second electron donor in governing the ground and excited state charge transfer events in closely positioned donor-acceptor conjugates.

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, -ΔGcom and comproportionation equilibrium constant, Kcom calculated from peak potentials of the split reduction waves were found to be 1.06×104  J mol-1 , and 72.3 M-1 , respectively. Further, the IVCT transition was also witnessed during the process of thermodynamically feasible electron transfer upon excitation of the TDPP entity in the system, and served as a diagnostic marker to characterize the electron transfer product. Subsequent transient absorption spectral studies and data analysis by Global and Target analyses revealed occurrence of ultrafast charge separation (kcs ≈1010  s-1 ) owing to the close proximity and good communication between the entities of the multi-modular donor-acceptor system. The role of central TDPP in promoting IVCT is borne out from the present investigation.

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 1 (PTZ-(TCBD-TPA)2) and asymmetric 2 (PTZ-(TCBD/DCNQ-TPA)2) 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 1 and 2 to be efficient candidates for ultrafast CT. Subsequent femtosecond transient absorption studies along with global target analysis, performed in both polar and nonpolar solvents, confirmed such processes in which the CS was efficient in asymmetric 2, having both TCBD and DCNQ acceptors in polar benzonitrile, while in toluene, only CT was witnessed. This work highlights the significance of the number and strength of electron acceptor entities and the role of solvent polarity in multimodular push-pull systems to achieve ultrafast CS.

Unveiling the Photoinduced Electron-Donating Character of MoS2 in Covalently Linked Hybrids Featuring Perylenediimide.

The covalent functionalization of MoS2 with a perylenediimide (PDI) is reported and the study is accompanied by detailed characterization of the newly prepared MoS2 -PDI hybrid material. Covalently functionalized MoS2 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 MoS2 to fully demonstrate for the first time its electron donor capabilities. The photophysical response of MoS2 -PDI is visualized in an energy-level diagram, while femtosecond transient absorption studies disclose the formation of MoS2 .+ -PDI.- charge separated state. The tunable electronic properties of MoS2 , as a result of covalently linking photoactive organic species with precise characteristics, unlock their potentiality and enable their application in light-harvesting and optoelectronic devices.

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. Both DPP and Fc-DPP carrying conjugates exhibited red-shifted absorption compared to their respective control compounds revealing existence of ground state interactions. Furthermore, DPP fluorescence in 4-6 was found to be quantitatively quenched while for 1-3, this property varied between 73-65 % suggesting occurrence moderate amounts of excited state events. The electrochemical investigations exhibited an additional low potential oxidation in the case of Fc-DPP-TPA based derivatives (4-6) owing to the presence of ferrocene unit(s). This was in addition to DPP and TPA redox peaks. Using spectral, electrochemical and computational studies, Gibbs free-energy calculations were performed to visualize excited state charge separation (ΔGCS ) in these donor-acceptor conjugates as a function of different number of Fc-DPP entities. Formation of Fc+ -DPP.- -TPA charge separated states (CSS) in the case of 4-6 was evident. Using spectroelectrochemical studies, spectrum of CSS was deduced. Finally, femtosecond transient absorption spectral studies were performed to gather information on excited state charge separation. Increasing the number of Fc-DPP entities in 4-6 improved charge separation rates. Surprisingly, lifetime of the charge separated state, Fc+ -DPP.- -TPA was found to persist longer with an increase in the number of Fc-DPP entities in 4-6 as compared to Fc-DPP-control and simple DPP derived donor-acceptor conjugates in literature. This unprecedented result has been attributed to subtle changes in ΔGCS and ΔGCR and the associated electron coupling between different entities.

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. Additionally, both SM2 and SM3 exhibited a distinct intramolecular charge-transfer (ICT) transition in the near-IR region more so for SM3. The electrochemical study revealed multi-redox processes due to the presence of redox-active phenothiazine, BODIPY, TCBD or DCNQ entities. Using data from spectral, electrochemical and computational studies, an energy-level diagram was established to witness excited-state electron-transfer events. Finally, evidence of electron transfer and their kinetic information was secured from studies involving a femtosecond transient absorption technique. The time constants for excited-state electron-transfer events in the case of SM2 and SM3 were less than 5 ps revealing ultrafast processes.

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

A new set of free-base and zinc(II)-metallated, ß-pyrrole-functionalized unsymmetrical push-pull porphyrins were designed and synthesized via ß-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 ß,ß'-pyrrole positions of porphyrin ring bearing triphenylamine push groups and naphthalimide pull groups. Systematic studies involving optical absorption, steady-state and time-resolved emission revealed existence of intramolecular type interactions both in the ground and excited states. The push-pull nature of the molecular systems was supported by frontier orbitals generated on optimized structures, wherein delocalization of HOMO over the push group and LUMO over the pull group connecting the porphyrin π-system was witnessed. Electrochemical studies were performed to visualize the effect of push and pull groups on the overall redox potentials of the porphyrins. Spectroelectrochemical studies combined with frontier orbitals helped in characterizing the one-electron oxidized and reduced porphyrins. Finally, by performing transient absorption studies in polar benzonitrile, the ability of push-pull porphyrins to produce charge-separated states upon photoexcitation was confirmed and the measured rates were in the range of 109  s-1 . The lifetime of the final charge separated state was around 5 ns. This study ascertains the importance of push-pull porphyrins in solar energy conversion and diverse optoelectronic applications, for which high-potential charge-separated states are warranted.

Excited-State Charge Transfer in Covalently Functionalized MoS2 with a Zinc Phthalocyanine Donor-Acceptor Hybrid.

The functionalization of MoS2 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 MoS2 at defect sites located at the edges. The structure of ZnPc-MoS2 was fully assessed by complementary spectroscopic, thermal, and microscopy imaging techniques. An energy-level diagram visualizing different photochemical events in ZnPc-MoS2 was established and revealed a bidirectional electron transfer leading to a charge separated state ZnPc.+ -MoS2 .- . Markedly, evidence of the charge transfer in the hybrid material was demonstrated using fluorescence spectroelectrochemistry. Systematic studies performed by femtosecond transient absorption revealed the involvement of excitons generated in MoS2 in promoting the charge transfer, while the transfer was also possible when ZnPc was excited, signifying their potential in light-energy-harvesting devices.

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

Exfoliated semiconducting MoS2 and WS2 were covalently functionalized with 1,2-dithiolane-modified carbon nanodots (CNDs). The newly synthesized CND-MoS2 and CND-WS2 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. Electrochemical studies revealed facile oxidation of MoS2 over WS2 in the examined hybrids, suggesting it to be better electron donor. Excited state events, investigated by femtosecond transient absorption spectroscopic studies, revealed ultrafast energy transfer from photoexcited CNDs to both MoS2 and WS2. Interestingly, upon MoS2 photoexcitation, charge transfer from an exciton dissociation path of MoS2 to CNDs, within CND-MoS2, was observed. However, such a process in CND-WS2 was found to be absent due to energetic reasons. The present study highlights the importance of TMD-derived donor-acceptor hybrids in light energy harvesting and optoelectronic applications. Furthermore, the fundamental information obtained from the current results will benefit design strategies and impact the development of additional TMD-based hybrid materials to efficiently manage and perform in electron-transfer processes.

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. A 15×10 mm sized subepithelial lesion was found 30 cm from the upper incisors on esophagogastroduodenoscopy. We diagnosed the lesion as a submucosal tumor, and performed endoscopic ultrasonography-guided fine needle aspiration for a pathologic diagnosis. The histologic examination revealed granulomatous inflammation consistent with tuberculosis. We suggest that the use of endoscopic ultrasonography and fine needle aspiration may be helpful in making an early diagnosis and planning for an optimal treatment.

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. After surgical excision of primary tumor with microscopic residual disease followed by concurrent chemoradiotherapy with docetaxel, the patient showed durable response of progression free survival of 12 months. DISCUSSION AND EVALUATION: This case shows benefit of concurrent chemoradiotherapy with taxane. Further investigation of aggressive multimodal treatment strategy is warranted for primary cardiac angiosarcoma with pauci-metastasis even when achievement of complete resection seems unlikely.