Guest-Regulated Generation of Reactive Oxygen Species from Porphyrin-Based Multicomponent Metallacages for Selective Photocatalysis.

The development of novel materials for highly efficient and selective photocatalysis is crucial for their practical applications. Herein, we employ the host-guest chemistry of porphyrin-based metallacages to regulate the generation of reactive oxygen species and further use them for the selective photocatalytic oxidation of benzyl alcohols. Upon irradiation, the sole metallacage (6) can generate singlet oxygen (1O2) effectively via excited energy transfer, while its complex with C70 (6⊃C70) opens a pathway for electron transfer to promote the formation of superoxide anion (O2⋅-), producing both 1O2 and O2⋅-. The addition of 4,4'-bipyridine (BPY) to complex 6⊃C70 forms a more stable complex (6⊃BPY) via the coordination of the Zn-porphyrin faces of 6 and BPY, which drives fullerenes out of the cavities and restores the ability of 1O2 generation. Therefore, benzyl alcohols are oxidized into benzyl aldehydes upon irradiation in the presence of 6 or 6⊃BPY, while they are oxidized into benzoic acids when 6⊃C70 is employed as the photosensitizing agent. This study demonstrates a highly efficient strategy that utilizes the host-guest chemistry of metallacages to regulate the generation of reactive oxygen species for selective photooxidation reactions, which could promote the utilization of metallacages and their related host-guest complexes for photocatalytic applications.

Halogen Bonding Tetraphenylethene Anion Receptors: Anion-Induced Emissive Aggregates and Photoswitchable Recognition.

A series of tetraphenylethene (TPE) derivatives functionalized with highly potent electron-deficient perfluoroaryl iodo-triazole halogen bond (XB) donors for anion recognition are reported. 1 H NMR titration experiments, fluorescence spectroscopy, dynamic light scattering measurements, TEM imaging and X-ray crystal structure analysis reveal that the tetra-substituted halogen bonding receptor forms luminescent nanoscale aggregates, the formation of which is driven by XB-mediated anion coordination. This anion-coordination-induced aggregation effect serves as a powerful sensory mechanism, capable of luminescence chloride sensing at parts per billion concentration. Furthermore, the doubly substituted geometric isomers act as unprecedented photoswitchable XB donor anion receptors, where the composition of the photostationary state can be modulated by the presence of a coordinating halide anion.

Bay-Substitution Effect of Perylene Diimides on Supramolecular Chirality and Optoelectronic Properties of Their Self-Assembled Nanostructures.

One-dimensional (1D) organic chiral supramolecules have received a great deal of attention for their promising applications in chiral recognition systems, chemical sensors, catalysts, and optoelectronics. Compared to modifications at the imide position of a perylene diimide (PDI), few studies have explored bay substitution of chiral PDIs and their self-assemblies into 1D nanomaterials. Herein, we describe the synthesis of three bay-substituted PDIs and explore the effects of bay substitution on supramolecular chirality by examining circular dichroism spectra and the optoelectronic performance of chiral PDI nanomaterials in phototransistors. Among the three fabricated self-assemblies, nanomaterials based on (R)-CN-CPDI-Ph exhibited the highest electron mobility of 0.17 cm2 V-1 s-1, a low threshold voltage of -1 V, and enhanced optoelectronic performance. For example, the photoresponsivity and external quantum efficiency of (R)-CN-CPDI-Ph assemblies were 4-fold higher than those of (R)-2Br-CPDI-Ph and (R)-2F-CPDI-Ph. All three nanomaterials exhibited fast switching speeds compared with previously reported N-substituted PDIs, suggesting that bay substitution can be an effective means of achieving rapid photoswitching. A comprehensive study using density functional theory calculations and crystal analyses revealed that the enhanced optoelectronic performance of (R)-CN-CPDI-Ph nanomaterials is related to the substitution of CN at the bay position of PDI. This minor change provides simultaneous improvements in electron injectability and structural order. Our findings demonstrate that bay substitution can significantly impact the self-assembly, supramolecular chirality, and optoelectronic properties of PDI nanomaterials.

Surface-Doped Quasi-2D Chiral Organic Single Crystals for Chiroptical Sensing.

Chiral organic optoelectronics using circularly polarized light (CPL) as the key element in the photonic signal has recently emerged as a next-generation photonic technology. However, it remains challenging to simultaneously achieve high polarization selectivity and superior optoelectronic performance. Supramolecular two-dimensional (2D) chiral organic single crystals may be good candidates for this purpose due to their defect-free nature, molecular diversity, and morphologies. Here, quasi-2D single crystals of chiral perylene diimides with parallelogram and triangle/hexagon morphologies have been selectively fabricated via self-assembly using different cosolvent systems. These materials exhibit amplified circular dichroism (CD) spectral signals, due to their molecular packing modes and supramolecular chirality. Through molecular surface n-doping using hydrazine, chiral single crystals exhibit electron mobility surpassing 1.0 cm2 V-1 s-1, which is one of the highest among chiral organic semiconductors, and excellent optoelectronic functions. Theoretical calculations reveal that the radical anions formed by n-doping increase the electron affinity and/or reduce the energy gap, thus facilitating electron transport. More importantly, the doped organic chiral crystals selectively discriminate CPL handedness with a high anisotropy factor of photoresponsivity (∼0.12). These results demonstrate that surface-doped quasi-2D chiral organic single crystals are highly promising for chiral optoelectronics.

Optoelectronic Property Modulation in Chiral Organic Semiconductor/Polymer Blends.

Organic phototransistors (OPTs) have been widely used in biomedical sensing, optical communications, and imaging. Charge-trapping effect has been utilized as an effective strategy for enhancing their photoresponsivity by effectively decreasing the dark current. The combination of organic semiconductors (OSCs), especially chiral OSCs, with insulating polymers has rarely been carried out for optoelectronic applications. Here, we fabricated OPTs containing both enantiopure and racemic air-stable n-type perylene diimide derivatives, CPDI-CN2-C6, and insulating biopolymer polylactide (PLA) and evaluated their photoresponsive properties. The PLA-blended systems exhibited greatly enhanced optoelectronic performances owing to the intense charge-trapping effect. Interestingly, the racemic system showed 3 times higher electron mobility and 12 times higher specific detectivity (1.3 × 1013 jones) compared with the enantiopure systems due to the more aggregated morphologies and larger grains, indicating that chiral composition can be used as a tuning parameter in optoelectronic devices. Our systematic study provides a feasible and effective method for producing high-performance n-type OPTs under ambient conditions.

Heterochiral Doped Supramolecular Coordination Networks for High-Performance Optoelectronics.

Chiral self-sorting has great potential for constructing new complex structures and determining chirality-dependent properties in multicomponent mixtures. However, it is still of great challenge to achieve high fidelity chiral self-discrimination. Besides, the researches on the coordination polymers or metal-organic frameworks for micro/nanooptoelectronics are still rare due to their low conductivity and difficulty in developing a rapid and simple scale-up synthetic method. Here, heterochiral supramolecular coordination networks (SCNs) were synthesized by the solvothermal reaction of naphthalene diimide enantiomers and cadmium iodide, using the chirality as a synthetic tuning parameter to control the morphologies. Intriguingly, heterochiral micro/nanocrystals exhibited photochromic and photodetecting properties. Furthermore, we also developed a simple and efficient doping method to enhance the conductivity and photoresponsivity of micro/nanocrystals using hydrazine. From experimental and theoretical studies, the mechanism was suggested as follows: the radicals in the singly occupied molecular orbital level of the ligands provide charge carriers that can undergo "through-space" transport between π-π stacked ligands and the electron transfer from adsorbed hydrazine to the SCNs results in reduction of energy gap, leading to increased conductivity. Our findings demonstrate a simple and powerful strategy for implementing coordination networks with redox ligands for micro/nanooptoelectronic applications.

Chronic active EBV infection associated with NK cell lymphoma and hemophagocytic lymphohistiocytosis in a 27-year-old woman: A case report.

RATIONALE: Chronic active Epstein-Barr virus infection (CAEBV) is a common infectious disease that often affects multiple organs or systems. However, it is liable to be neglected and misdiagnosed owing to its insidious onset, lack of specific findings in the early phase, and a general lack of awareness among clinicians. PATIENT CONCERNS:: a 27-year-old woman case has been described who was initially misdiagnosed as drug-induced liver injury due to onset presentation of mild splenomegaly, recurrent liver dysfunction, and disputable pathological evidence of liver biopsy. DIAGNOSES: CAEBV complicated with natural killer (NK) cell lymphoma and hemophagocytic lymphohistiocytosis (HLH) was diagnosed by in situ hybridization of liver tissue section with EBV-encoded RNA -1 probe and flow cytometry of bone marrow. INTERVENTIONS: After admission, the patient received symptomatic treatment and antiviral therapy (combination of acyclovir and foscarnet sodium) as well as adjuvant treatment (thymosin alpha 1 and methylprednisolone); later, the patient received etoposide and dexamethasone for diagnosis of EBV associated HLH. Subsequently, the disease progressed to NK cell lymphoma and the patient received the revised EPOCH chemotherapy regimen [etoposide (100 mg/d, d1-5), dexamethasone (7.5 mg/d, d1-5; 5 mg/d, d6-14), cyclophosphamide (0.8 g/d, d1-2), and pegaspargase (3750 u/d, tid, d1-2)]. OUTCOMES: Although the patient received a series of therapies and other comprehensive measures, finally she died of gastrointestinal hemorrhage and multiple organ failure. LESSONS: Liver is one of the main target organs of EBV infection. In the clinical setting of unexplained fever and liver injury, it is necessary to be aware of CAEBV, as well as its fatal complication such as EBV associated NK cell lymphoma and HLH.

Highly Enantioselective Graphene-Based Chemical Sensors Prepared by Chiral Noncovalent Functionalization.

As a basic characteristic of the natural environment and living matter, chirality has been used in various scientific and technological fields. Chiral discrimination is of particular interest owing to its importance in catalysis, organic synthesis, biomedicine, and pharmaceutics. However, it is still very challenging to effectively and selectively sense and separate different enantiomers. Here, enantio-differentiating chemosensor systems have been developed through spontaneous chiral functionalization of the surface of graphene field-effect transistors (GFETs). GFET sensors functionalized using noncovalent interactions between graphene and a newly synthesized chiral-functionalized pyrene material, Boc-l-Phe-Pyrene, exhibit highly enantioselective detection of natural acryclic monoterpenoid enantiomers, that is, ( R)-(+)- and ( S)-(-)-ß-citronellol. On the basis of a computational study, the origin of enantio-differentiation is assigned to the discriminable charge transfer from ( R)-(+)- or ( S)-(-)-ß-citronellol into graphene with a significant difference in binding strength depending on surface morphology. The chemosensor system developed herein has great potential to be applied in miniaturized and rapid enantioselective sensing with high sensitivity and selectivity.

Chiral self-sorted multifunctional supramolecular biocoordination polymers and their applications in sensors.

Chiral supramolecules have great potential for use in chiral recognition, sensing, and catalysis. Particularly, chiral supramolecular biocoordination polymers (SBCPs) provide a versatile platform for characterizing biorelated processes such as chirality transcription. Here, we selectively synthesize homochiral and heterochiral SBCPs, composed of chiral naphthalene diimide ligands and Zn ions, from enantiomeric and mixed R-ligands and S-ligands, respectively. Notably, we find that the chiral self-sorted SBCPs exhibit multifunctional properties, including photochromic, photoluminescent, photoconductive, and chemiresistive characteristics, thus can be used for various sensors. Specifically, these materials can be used for detecting hazardous amine materials due to the electron transfer from the amine to the SBCP surface and for enantioselectively sensing a chiral species naproxen due to the different binding energies with regard to their chirality. These results provide guidelines for the synthesis of chiral SBCPs and demonstrate their versatility and feasibility for use in various sensors covering photoactive, chemiresistive, and chiral sensors.

High-Performance Visible-Blind UV Phototransistors Based on n-Type Naphthalene Diimide Nanomaterials.

This study investigates the performance of single-crystalline nanomaterials of wide-band gap naphthalene diimide (NDI) derivatives with methylene-bridged aromatic side chains. Such materials are found to be easily used as high-performance, visible-blind near-UV light detectors. NDI single-crystalline nanoribbons are assembled using a simple solution-based process (without solvent-inclusion problems), which is then applied to organic phototransistors (OPTs). Such OPTs exhibit excellent n-channel transistor characteristics, including an average electron mobility of 1.7 cm2 V-1 s-1, sensitive UV detection properties with a detection limit of ∼1 µW cm-2, millisecond-level responses, and detectivity as high as 1015 Jones, demonstrating the highly sensitive organic visible-blind UV detectors. The high performance of our OPTs originates from the large face-to-face π-π stacking area between the NDI semiconducting cores, which is facilitated by methylene-bridged aromatic side chains. Interestingly, NDI-based nanoribbon OPTs exhibit a distinct visible-blind near-UV detection with an identical detection limit, even under intense visible light illumination (for example, 104 times higher intensity than UV light intensity). Our findings demonstrate that wide-band gap NDI-based nanomaterials are highly promising for developing high-performance visible-blind UV photodetectors. Such photodetectors could potentially be used for various applications including environmental and health-monitoring systems.

Morphogenesis and Optoelectronic Properties of Supramolecular Assemblies of Chiral Perylene Diimides in a Binary Solvent System.

Chiral supramolecular structures are attracting great attention due to their specific properties and high potential in chiral sensing and separation. Herein, supramolecular assembling behaviors of chiral perylene diimides have been systematically investigated in a mixed solution of tetrahydrofuran and water. They exhibit remarkably different morphologies and chiral aggregation behaviors depending on the mixing ratio of the solvents, i.e., the fraction of water. The morphogenesis and optoelectronic properties of chiral supramolecular structures have been thoroughly studied using a range of experimental and theoretical methods to investigate the morphological effects of chiral supramolecular assemblies on the electrical performances and photogenerated charge-carrier behaviors. In addition, chiral perylene diimides have been discriminated by combining vibrational circular dichroism with theoretical calculations, for the first time. The chiral supramolecular nanostructures developed herein strongly absorb visible spectral region and exhibit high photoresponsivity and detectivity, opening up new opportunities for practical applications in optoelectronics.

Supramolecular Nanostructures of Chiral Perylene Diimides with Amplified Chirality for High-Performance Chiroptical Sensing.

Chiral supramolecular nanostructures with optoelectronic functions are expected to play a central role in many scientific and technological fields but their practical use remains in its infancy. Here, this paper reports photoconductive chiral organic semiconductors (OSCs) based on perylene diimides with the highest electron mobility among the chiral OSCs and investigates the structure and optoelectronic properties of their homochiral and heterochiral supramolecular assemblies from bottom-up self-assembly. Owing to the well-ordered supramolecular packing, the homochiral nanomaterials exhibit superior charge transport with significantly higher photoresponsivity and dissymmetry factor compared with those of their thin film and monomeric equivalents, which enables highly selective detection of circularly polarized light, for the first time, in visible spectral range. Interestingly, the heterochiral nanostructures assembled from co-self-assembly of racemic mixtures show extraordinary chiral self-discrimination phenomenon, where opposite enantiomeric molecules are packed alternately into heterochiral architectures, leading to completely different optoelectrical performances. In addition, the crystal structures of homochiral and heterochiral nanostructures have first been studied by ab initio X-ray powder diffraction analysis. These findings give insights into the structure-chiroptical property relationships of chiral supramolecular self-assemblies and demonstrate the feasibility of supramolecular chirality for high-performance chiroptical sensing.

NKG2D modulates aggravation of liver inflammation by activating NK cells in HBV infection.

Hepatitis B virus (HBV) infection is thought to be an immune-mediated liver disease. The mechanisms underlying natural killer (NK) cell group 2D receptor (NKG2D) that activates NK cells and participates in anti-HBV immunity and immunopathology has not been thoroughly elucidated. Peripheral NKG2D+ and IFN-γ+ NK cells frequencies and intrahepatic NKG2D and IFN-γ mRNA and protein expressions were determined in HBV-infected patients. Levels of NKG2D and IFN-γ mRNA and protein in NK cells, co-cultured with HBV-replicating HepG2 cells with or without NKG2D blockade, were analyzed. Serum and supernatant IFN-γ, TNF-α, perforin and granzyme B were measured. In results, peripheral NKG2D+ and IFN-γ+ NK cells frequencies, intrahepatic NKG2D and IFN-γ mRNA and protein levels, and serum IFN-γ, TNF-α, perforin and granzyme B levels were all highest in HBV-related acute-on-chronic liver failure group, followed by chronic hepatitis B and chronic HBV carrier groups. In vitro, NKG2D and IFN-γ mRNA and protein levels were higher in NK cells with IFN-α stimulation than without stimulation. Supernatant IFN-γ, TNF-α, perforin and granzyme B levels were increased under co-culture or IFN-α stimulating conditions, but were partially blocked by NKG2DmAb. In conclusion, NKG2D regulates immune inflammation and anti-viral response partly through activation of NK cells during HBV infection.

Copper-catalyzed cascade cyclization reaction of 2-haloaryltriazenes and sodium azide: selective synthesis of 2H-benzotriazoles in water.

A new approach to the synthesis of 2H-benzotriazoles is described. This strategy is based on the copper-catalyzed C-N coupling of 2-haloaryltriazenes or 2-haloazo compounds with sodium azide and the intramolecular addition of nitrene to N=N bonds. This approach allows the synthesis of various N-amino- and N-aryl-2H-benzotriazoles in water, in good to excellent yields. The procedure is simple and the starting materials and catalyst are easily available, offering a practical and convenient synthetic route to 2-substituted benzotriazoles.