The Association Between Stress and Symptomatic Tinnitus: A Preliminary Study.

Background: Tinnitus can severely impair people's quality of life. Stress has been involved in the pathogenesis of multiform mental disorders. Tinnitus-related annoying symptoms have a negative effect on the life quality of tinnitus sufferers. Objectives: The aim of this study is to explore the association between stress and the symptomatic tinnitus. Methods: A total of 183 participants were categorized into 3 groups, depending on the presence of tinnitus-related symptoms. All participants underwent audiological examination, and their demographic data were collected via a questionnaire. Furthermore, the Social Readjustment Rating Scale (SRRS), the Tinnitus Handicapped Inventory (THI), and Tinnitus Questionnaire were filled by tinnitus patients. Results: The mean SRRS score in symptomatic (tinnitus-related symptoms) group was higher than that in asymptomatic group and the control group (P < .001), meanwhile no difference in this score was reported between asymptomatic group and control group. SRRS score (Grade 2) is an independent risk factor for symptomatic tinnitus. The SRRS score were positively correlated with THI scores. Conclusions and Significance: Stress is related to the occurrence of symptomatic tinnitus.

The effect of cognitive rehabilitation on daily functioning of patients with Alzheimer's disease: a systematic review and meta-analysis of clinical trials.

Background: Alzheimer's disease (AD) is the most prevalent type of dementia and represents 60-80% of dementia cases. AD affects over 32 million people globally, and 8.1% of affected females and 5.4% of affected males were older than 65 years. Cognitive rehabilitation focuses on helping patients develop individualized strategies to obtain or maintain optimal functioning. As of now, there is no complete and systematic meta-analysis on the effects of cognitive rehabilitation on cognitive functioning in AD patients. Objectives: To provide the most recent and extensive pooled analysis and evidence and explore the influence of cognitive rehabilitation on overall cognitive functioning in patients with AD. Methods: We searched articles through several databases such as PubMed, Cochrane Library, Embase, and Web of Science, from the inception to June 2023. Studies on cognitive stimulation, cognitive training, and cognitive interventions, and non-English articles were excluded. The outcome measures encompassed the effects of cognitive rehabilitation on the overall cognitive functioning of people with AD (e.g., verbal fluency, behavioral memory, neuropsychiatric status and occupational performance levels). Results: A total of 14 clinical trials were included in this analysis. The meta-analysis showed that cognitive rehabilitation significantly improved quality of life (WMD: 2.87; 95% CI: 0.79, 4.95; p = 0.007) and occupational performance levels (WMD: 1.53; 95% CI: 0.43, 2.63; p = 0.007) in patients with AD. However, it did not show a significant effect on other domains of specific cognitive functions in patients with AD. Conclusion: Cognitive rehabilitation exhibited a moderate to large impact on both quality of life and occupational performance levels in people with AD. Future studies are required to explore the potential of various cognitive interventions across specific domains, so as to provide more insights into the management of AD. Systematic review registration: https://www.crd.york.ac.uk/prospero/, identifier CRD42023444390.

X-ray-triggered through-space charge transfer and photochromism in silver nanoclusters.

Materials exhibiting X-ray-induced photochromism have consistently piqued the interest of researchers. Exploring the photochromic properties of such materials is valuable for understanding the structural changes and electron transfer processes that occur under high energy radiation, such as X-ray irradiation. Here, a crystalline silver(I) nanocluster synthesized from tert-butylacetylene silver was found to have the ability to exhibit color and photoluminescence changes upon exposure to X-ray radiation. The responsive behavior was observed across a wide temperature range of 100-300 K, with the ability to respond particularly well to soft X-rays (λ > 1 Å) and exhibit light responsiveness to hard X-rays (λ < 1 Å). By combining experimental findings including X-ray diffraction, X-ray photoelectron spectroscopy, electron spin resonance, etc. with theoretical calculations, we have proposed that X-ray irradiation induces electron transfer from chloride (Cl-) located in the center of the silver(I) nanocluster to the surrounding Ag14 in the skeleton. This represents the first documented example in which electron transfer induced by X-ray excitation has been observed, accompanied by a photochromism process, in silver nanoclusters. This study contributes to our understanding of X-ray-induced photochromism and the electron transfer process in silver cluster compounds. It also provides valuable insights and potential design strategies for applications such as photochromism, photoluminescence color change, and photoenergy conversion.

Transformation of SBUs and Synergy of MOF Host-Guest in Single Crystalline State: Ingenious Strategies for Modulating Third-Order NLO Signals.

Central metal exchange can innovatively open the cavity of metal-organic frameworks (MOFs) by alternating the framework topology. Here, the single-crystal-to-single-crystal (SC-SC) transformation is reported from a Co-based MOF {[Co1.25 (HL)0.5 (Pz-NH2 )0.25 (µ3 -O)0.25 (µ2 -OH)0.25 (H2 O)]·0.125 Co·0.125 L·10.25H2 O}n (Co-MOF, L = 5,5'-(1H-2,3,5-triazole-1,4-diyl)diisophthalic acid) into two novel MOF materials, {[Cu1.75 L0.75 (Pz-NH2 )0.125 (µ3 -O)0.125 (µ2 -OH)0.25 (H2 O)0.375 ]•3CH3 CN}n (Cu-MOF) and {[Zn1.75 L0.625 (Pz-NH2 )0.25 (µ3 -O)0.25 (µ2 -O)0.25 (H2 O)1.25 ]•4CH3 CN}n (Zn-MOF), through exchanging the Co2+ in the MOF into Cu2+ or Zn2+ , respectively. The free Co2+ and L4- in the Co-MOF channels fuse with the skeleton during the Co→Cu and Co→Zn exchange processes, leading to the expansion of the channel space and the transformation of the secondary building units (SBUs) to form an adjustable skeleton. The nonlinear optical response results show that the MOFs generated by the exchange of the central metal exhibit different saturable absorption and the self-focusing effect. In addition, loading polypyrrole (PPy) into the MOFs can not only improve the stability of the MOFs but also further optimize the nonlinear optical behavior. This work suggests that SC-SC central metal exchange and the introduction of polymer molecules can tune the nonlinear optical response, which provides a new perspective for the future study of nonlinear optical materials.

A trispecific antibody induces potent tumor-directed T-cell activation and antitumor activity by CD3/CD28 co-engagement.

Aim: A novel CD19xCD3xCD28 trispecific antibody with a tandem single-chain variable fragments (scFv) structure was developed for the treatment of B-cell malignancies. Methods: The trispecific antibody in inducing tumor-directed T-cell activation and cytotoxicity was evaluated in vitro and in vivo and compared with its bispecific counterpart BiTE-CD19xCD3 lacking a CD28-targeting domain. Results: The trispecific antibody with a co-stimulatory domain exhibited augmented T-cell activation and memory T-cell differentiation capability and it induced faster tumor cell lysis than the bispecific antibody. RNAseq analysis revealed that the trispecific antibody modulates CD3/TCR complex-derived signal and upregulates antiapoptotic factors to influence the survival of T cells. Conclusion: By CD3/CD28 co-engagement, the trispecific antibody demonstrated its advantages in T-cell immunity and potential use as a more powerful and long-lasting T-cell engager.

T-cell based immunotherapies are a type of treatment that stimulates the body's own immune system to fight cancer. They have grown in popularity in recent years and have had impressive results in cancer treatment. One type of T-cell immunotherapy is a T-cell engager antibody. This is a type of molecule that redirects the body's immune cells to recognise and kill cancer cells. In this study, we developed a new type of T-cell engager antibody to treat two types of blood and bone marrow cancer. The antibody works by joining immune cells and cancer cells close together, to help activate the immune cells for cancer killing. This new type of T-cell engager antibody worked better than previous versions. It helped the immune cells survive longer and kill cancer more effectively. This means the new antibody might be better at treating people who have these types of cancers, but more testing in humans needs to be done.

High-Efficiency Pure Blue Circularly Polarized Phosphorescence from Chiral N-Heterocyclic-Carbene-Stabilized Copper(I) Clusters.

Circularly polarized luminescence (CPL) materials have attracted considerable attention for their promising applications in encryption, chiral sensing, and three-dimensional (3D) displays. However, the preparation of high-efficiency, pure blue CPL materials remains challenging. In this study, we reported an enantiomeric pair of triangle copper(I) clusters (R/S-Cu3) rigidified by employing chiral N-heterocyclic carbene (NHC) ligands with two pyridine-functionalized wingtips. These chiral clusters emitted pure blue phosphorescence that overlapped with that of the commercial blue phosphor having Commission Internationale de l'Eclairage (CIE) chromaticity coordinates of (0.14, 0.10), and the films exhibited an unprecedented photoluminescence quantum yield (PLQY) of ∼70.0%. Additionally, the solutions showed very bright circularly polarized phosphorescence (CPP) with a dissymmetry factor of ±2.1 × 10-3. The excellent solubility and photostability endowed these pure-blue-emitting chiral clusters with promising applications as pure blue CPP inks for 3D printing white objects, such as precise-atomic-enlarged models of metal clusters and a lovely white stereoscopic "rabbit". The intricate mechanism underlying blue phosphorescence in this small cluster and across various states is elucidated through a comprehensive approach that integrates thorough analysis of luminescence properties, controlled experiments, and theoretical calculations. For the first time, we propose that the dominant high-energy emission center is constituted by delocalized hybrid orbitals over multiple atomic centers, encompassing both the metal and the coordinated atoms. This challenges stereotypical assumptions that the cluster center solely supports low-energy emissions. This work expands the currently limited range of CPP functional materials and provides a new direction for CPP applications involving NHC-stabilized metal clusters.

Halogen bonds regulating structures and optical properties of hybrid iodobismuthate perovskites.

Successive structural transformations were observed in a methanolic solution containing 4-iodo-1-methylpyridin-1-ium iodide (IPyMe·I) and bismuth iodide (BiI3). When kept in the solution, the amorphous solid (P_1) obtained immediately on mixing would transform to needle crystals (C_1) in hours, which would convert to prismatic crystals (C_2) in around 2 days. In the presence of hydroiodic acid, the hydrothermal reaction of IPyMe·I and BiI3 also gave rise to C_2, and crystals of C_2 in this solution would transform to a third crystalline product C_3 in ca. 3 days. X-ray single crystal diffraction experiments show C_1 containing one-dimensional {BiI4-}n chains, C_2 as a binuclear Bi2I93- structure, and C_3 consisting of a monomeric BiI63- unit, all with IPyMe+ as counter cations. Halogen bonds exist between IPyMe+ and the iodobismuthate, which may play key roles in the structural transformation. By introducing halogen bonding, the hybrids demonstrate excellent water-resistance. A thermal-induced reversible colour change from yellow to dark red occurred from 100 K to 450 K for all three hybrids, in which lattice expansion over the temperature range may be a reason for the thermochromism. The bandgaps derived from the UV-vis diffusion reflectance for the three complexes were 1.80 eV for C_1, 1.84 eV for C_2 and 2.00 eV for C_3. DTF computations followed by electron density topological analysis were applied to explain the structure-optical property relationship for complexes of diverse iodobismuthate types but the same counter cation. It was found that the nature of the Bi-I bonds rather than the dimensionality of the inorganic iodobismuthates is mainly responsible for the light absorption of the materials.

Water-Soluble Metallo-Supramolecular Nanoreactors for Mediating Visible-Light-Promoted Cross-Dehydrogenative Coupling Reactions.

Water-soluble metallo-supramolecular cages with well-defined nanosized cavities have a wide range of functions and applications. Herein, we design and synthesize two series of metallo-supramolecular octahedral cages based on the self-assembly of two congeneric truxene-derived tripyridyl ligands modified with two polyethylene glycol (PEG) chains, i.e., monodispersed tetraethylene glycol (TEG) and polydispersed PEG-1000, with four divalent transition metals (i.e., Pd, Cu, Ni, and Zn). The resulting monodispersed cages C1-C4 are fully characterized by electrospray ionization mass spectrometry (ESI-MS), nuclear magnetic resonance (NMR) spectroscopy, and single-crystal X-ray diffraction. The polydispersed cages C5-C8 display good water solubilities and can act as nanoreactors to mediate visible-light-promoted C(sp3)-C(sp2) cross-dehydrogenative coupling reactions in an aqueous phase. In particular, the most robust Pd(II)-linked water-soluble polydispersed nanoreactor C5 is characterized by ESI-MS and capable of mediating the reactions with the highest efficiencies. Detailed host-guest binding studies in conjunction with control studies suggest that these cages could encapsulate the substrates simultaneously inside its hydrophobic cavity while interacting with the photosensitizer (i.e., eosin Y).

The Interaction between Oxidative Stress Biomarkers and Gut Microbiota in the Antioxidant Effects of Extracts from Sonchus brachyotus DC. in Oxazolone-Induced Intestinal Oxidative Stress in Adult Zebrafish.

Oxidative stress is a phenomenon caused by an imbalance between the production and accumulation of reactive oxygen species in cells and tissues that eventually leads to the production of various diseases. Here, we investigated the antioxidant effects of the extract from Sonchus brachyotus DC. (SBE) based on the 0.2% oxazolone-induced intestinal oxidative stress model of zebrafish. Compared to the model group, the treatment group alleviated oxazolone-induced intestinal tissue damage and reduced the contents of malondialdehyde, reactive oxygen species, IL-1ß, and TNF-α and then increased the contents of superoxide dismutase, glutathione peroxidase, and IL-10. The 16s rDNA gene sequencing findings demonstrated that SBE could increase the relative abundance of Fusobacteriota, Actinobacteriota, and Firmicutes and decrease the relative abundance of Proteobacteria. Based on the correlation analysis between the oxidative stress biomarkers and intestinal flora, we found that the trends of oxidative stress biomarkers were significantly correlated with intestinal microorganisms, especially at the genus level. The correlations of MDA, IL-1ß, and TNF-α were significantly negative with Shewanella, while SOD, GSH-Px, and IL-10 were significantly positive with Cetobacterium, Gemmobacter, and Flavobacterium. Consequently, we concluded that the antioxidant effect of SBE was realized through the interaction between oxidative stress biomarkers and gut microbiota.

Facial Nerve Schwannoma Extending to Jugular Foramen: A Case Report.

Facial nerve schwannoma (FNS) is a benign, slow-growing schwannoma that originates from Schwann cells. Facial nerve schwannoma is the most common tumor of the facial nerve but rare and only accounts for 0.15% to 0.8% of intracranial neurinomas. It may be manifested as asymmetric hearing loss, facial palsy, and hemifacial spasm. A 56-year-old woman was transferred to our department, because of pain behind the right ear and spasm of the right lateral muscle for more than 2 years and pulsatile tinnitus for half a year. Based on the preoperative medical history, physical signs, and auxiliary examination, it was diagnosed with jugular foramen (JF) space-occupying lesion. We removed the tumor through the infratemporal fossa type A approach and found that the tumor originated from the facial nerve. After the tumor resection, sural nerve transplantation was performed. The patient demonstrated postoperative facial palsy (House-Brackman grade VI) and was smoothly discharged after good recovery. Facial nerve schwannoma rarely invades the JF, and the most common tumor in the JF is the glomus jugular tumor, followed by the posterior cranial schwannoma. They have common symptoms, making it difficult to obtain a correct diagnosis. Clinical data, medical history, and auxiliary examinations should be carefully analyzed to avoid misdiagnosis or mistreatment. Infratemporal fossa type A approach is an effective method for treating FNS of JF.

A study of impurities in the repurposed COVID-19 drug hydroxychloroquine sulfate using ultra-high-performance liquid chromatography-quadrupole/time-of-flight mass spectrometry and liquid chromatography-solid-phase extraction-nuclear magnetic resonance.

RATIONALE: Hydroxychloroquine sulfate is effective in the treatment of malaria and autoimmune diseases and as an antiviral drug. However, unreported impurities are often detected in this drug, which pose a health risk. In this study, the structures of hydroxychloroquine and six unknown impurities were analyzed using ultra-high-performance liquid chromatography-quadrupole/time-of-flight-tandem mass spectrometry (UHPLC-Q/TOF/MS/MS), and the structures were characterized using liquid chromatography-solid-phase extraction-nuclear magnetic resonance (LC-SPE-NMR) spectroscopy. METHODS: An Agilent InfinityLad Poroshell HPH-C18 column (100 × 4.6 mm, 2.7 µm) was used. For the analysis of hydroxychloroquine and six unknown impurities, the mobile phase was 20 mM ammonium formate aqueous solution and methanol/acetonitrile (80:20, v/v) using gradient elution. Full-scan MS and MS2 were performed to obtain as much structural information as possible. In addition, six unknown impurities were separated by semi-preparative liquid chromatography and characterized using LC-SPE-NMR. RESULTS: The MS2 fragmentation patterns of the impurities were investigated, leading to more structural information and an understanding of the fragmentation pathways of the impurities. The structures of the unknown impurities were confirmed using NMR. In addition, some possible pathways of the formation of the impurities in the drugs were outlined, and these impurities were found to be process impurities. CONCLUSIONS: Based on the identification and characterization of these impurities, this study also describes the cause of the production of the impurities and provides insights for companies to improve their production processes and a scientific basis for the improvement of the related pharmacopoeias.

Small symmetry-breaking triggering large chiroptical responses of Ag70 nanoclusters.

The origins of the chiroptical activities of inorganic nanostructures have perplexed scientists, and deracemization of high-nuclearity metal nanoclusters (NCs) remains challenging. Here, we report a single-crystal structure of Rac-Ag70 that contains enantiomeric pairs of 70-nuclearity silver clusters with 20 free valence electrons (Ag70), and each of these clusters is a doubly truncated tetrahedron with pseudo-T symmetry. A deracemization method using a chiral metal precursor not only stabilizes Ag70 in solution but also enables monitoring of the gradual enlargement of the electronic circular dichroism (CD) responses and anisotropy factor gabs. The chiral crystals of R/S-Ag70 in space group P21 containing a pseudo-T-symmetric enantiomeric NC show significant kernel-based and shell-based CD responses. The small symmetry breaking of Td symmetry arising from local distortion of Ag-S motifs and rotation of the apical Ag3 trigons results in large chiroptical responses. This work opens an avenue to construct chiral medium/large-sized NCs and nanoparticles, which are promising for asymmetric catalysis, nonlinear optics, chiral sensing, and biomedicine.

A TRP Family Based Signature for Prognosis Prediction in Head and Neck Squamous Cell Carcinoma.

PURPOSE: Head and neck squamous cell carcinoma (HNSCC) is a classical type of head and neck cancers, with heterogeneous clinical outcome. This project is set out to create a robust risk signature based on TRP family genes (TFGs) for prognosis evaluation in HNSCC. METHODS: Based on the HNSCC sample data from the TCGA website, we integrated expression profile of TFGs for 490 HNSCC cases. We explore the interactions among TFGs using STRING tool. The TFGs-based signature (TFBS) was created by Cox relative analyses. In addition, we conducted GSEA to identify the underlying signaling pathways of the specific TFGs in HNSCC. The immune landscape of HNSCC patients was analyzed by CIBERSORT and ssGSEA algorithms. RESULTS: A total of 6 TFGs (TRPC1, TRPC3, TRPC6, TRPV2, TRPV4, and TRPM8) closely associated with prognosis of HNSCC cases were screened to create TFBS. TFBS predicted that the TFBS-high group presented dismal patient outcome. Cox regression revealed the favorable independent value of TFBS. ROC analysis showed the robust power of TFBS for prognosis forecasting. GSEA determined several crucial pathways related with HNSCC, which are the p53 pathway, TNF-alpha signaling via NFKB, and hypoxia. Moreover, immune-related analysis showed that patients in the TFBS-high group were more likely in immunosuppressive status. CONCLUSION: Our proposed TFBS could serve as a favorable indicator to forecast the survival outcome of HNSCC cases and offer prominent therapy guidance.

Self-Assembly of [3]Catenane and [4]Catenane Based on Neutral Organometallic Scaffolds.

Transition metal-mediated templating and self-assembly have shown great potential to construct mechanically interlocked molecules. Herein, we describe the formation of the bimetallic [3]catenane and [4]catenane based on neutral organometallic scaffolds via the orthogonality of platinum-to-oxygen coordination-driven self-assembly and copper(I) template-directed strategy of a [2]pseudorotaxane. The structures of these bimetallic [3]catenane and [4]catenane were characterized by multinuclear NMR {1H and 31P} spectroscopy, electrospray ionization time-of-flight mass spectrometry (ESI-TOF-MS), and PM6 semiempirical molecular orbital theoretical calculations. In addition, single-crystal X-ray analyses of the [3]catenane revealed two asymmetric [2]pseudorotaxane units inside the metallacycle. It was discovered that tubular structures were formed through the stacking of individual [3]catenane molecules driven by the strong π-π interactions.

Rapid Detection of Fatty Acids in Edible Oils Using Vis-NIR Reflectance Spectroscopy with Multivariate Methods.

The composition and content of fatty acids are critical indicators to identify the quality of edible oils. This study was undertaken to establish a rapid determination method for quality detection of edible oils based on quantitative analysis of palmitic acid, stearic acid, arachidic acid, and behenic acid. Seven kinds of oils were measured to obtain Vis-NIR spectra. Multivariate methods combined with pretreatment methods were adopted to establish quantitative analysis models for the four fatty acids. The model of support vector machine (SVM) with standard normal variate (SNV) pretreatment showed the best predictive performance for the four fatty acids. For the palmitic acid, the determination coefficient of prediction (RP2) was 0.9504 and the root mean square error of prediction (RMSEP) was 0.8181. For the stearic acid, RP2 and RMSEP were 0.9636 and 0.2965. In the prediction of arachidic acid, RP2 and RMSEP were 0.9576 and 0.0577. In the prediction of behenic acid, the RP2 and RMSEP were 0.9521 and 0.1486. Furthermore, the effective wavelengths selected by successive projections algorithm (SPA) were useful for establishing simplified prediction models. The results demonstrate that Vis-NIR spectroscopy combined with multivariate methods can provide a rapid and accurate approach for fatty acids detection of edible oils.

Azo-Enhanced Raman Scattering for Enhancing the Sensitivity and Tuning the Frequency of Molecular Vibrations.

Raman scattering provides stable narrow-banded signals that potentially allow for multicolor microscopic imaging. The major obstacle for the applications of Raman spectroscopy and microscopy is the small cross section of Raman scattering that results in low sensitivity. Here, we report a new concept of azo-enhanced Raman scattering (AERS) by designing the intrinsic molecular structures using resonance Raman and concomitant fluorescence quenching strategies. Based on the selection of vibrational modes and the enhancing unit of azobenzenes, we obtained a library of AERS molecules with specific Raman signals in the fingerprint and silent frequency regions. The spectral characterization and molecular simulation revealed that the azobenzene unit conjugated to the vibrational modes significantly enhanced Raman signals due to the mechanism of extending the conjugation system, coupling the electronic-vibrational transitions, and improving the symmetry of vibrational modes. The nonradiative decay of azobenzene from the excited state quenched the commitment fluorescence, thus providing a clean background for identifying Raman scattering. The most sensitive AERS molecules produced Raman signals of more than 4 orders of magnitude compared to 5-ethynyl-2'-deoxyuridine (EdU). In addition, a frequency tunability of 10 distinct Raman bands was achieved by selecting different types of vibrational modes. This methodology of AERS allows for designing small-molecule Raman probes to visualize various entities in complex systems by multicolor spontaneous Raman imaging. It will open new prospects to explore innovative applications of AERS in interdisciplinary research fields.

Crystal structure and Hirshfeld surface analysis of bis-(6,7,8,9-tetra-hydro-11H-pyrido[2,1-b]quinazolin-5-ium) tetra-chlorido-zincate.

The title compound, (C12H15N2)2[ZnCl4], is a salt with two symmetrically independent, essentially planar heterocyclic cations and a slightly distorted tetra-hedral chloro-zincate dianion. N-H⋯Cl hydrogen bonds link these ionic constituents into a discrete aggregate, which comprises one formula unit. The effect of hydrogen bonding is reflected in the minor distortions of the [ZnCl4]2- moiety: distances between the cation and chlorido ligands engaged in classical hydrogen bonds are significantly longer than the others. Secondary inter-actions comprise C-H⋯π hydrogen bonding and weak π-π stacking. A Hirshfeld surface analysis indicates that the most abundant contacts in packing stem from H⋯H (47.8%) and Cl⋯H/H⋯Cl (29.3%) inter-actions.

Base-assisted synthesis of 4-pyridinate gold(I) metallaligands: a study of their use in self-assembly reactions.

The synthesis of di- and tritopic gold(i) metallaligands of the type [(Au4-py)2(µ2-diphosphane)] (diphosphane = bis(diphenylphosphanyl)isopropane or dppip (1), 1,2-bis(diphenylphosphanyl)ethane or dppe (2), 1,3-bis(diphenylphosphanyl)propane or dppp (3) and 1,4-bis(diphenylphosphanyl)butane or dppb (4)) and [(Au4-py)3(µ3-triphosphane)] (triphosphane = 1,1,1-tris(diphenylphosphanylmethyl)ethane or triphos (5) and 1,3,5-tris(diphenylphosphanyl)benzene or triphosph (6)) from [(AuCl)2(µ2-diphosphane)] or [(AuCl)3(µ3-triphosphane)] and 4-pyridylboronic acid in the presence of Cs2CO3 has been conducted. Interestingly, when [(AuCl)2(µ2-dppm)] (dppm = bis(diphenylphosphanyl)methane) was used as a starting material, the cyclic tetranuclear gold(i) compound [(Au4-py)2(CH)2{µ2-Au(PPh2)2}2] (I) was obtained instead. All the products have been characterized by IR and multinuclear NMR spectroscopy, mass spectrometry and elemental analysis and in the case of 1, 3, 5 and I by X-ray crystallography, which showed the presence of aurophilic interactions in all of them. The obtained metallaligands have been used as building blocks in self-assembly reactions with cis-blocked palladium or platinum acceptor moieties producing [2 + 2] metallamacrocycles or trigonal bipyramidal (TBP) [2 + 3] metallacages in good yields. The photophysical properties of both the metallaligands and the corresponding assemblies have been investigated.

Confinement inside a Crystalline Sponge Induces Pyrrole To Form N-H⋠⋠⋠π Bonded Tetramers.

Based on the DFT-level-calculated molecular volume (Vmol ) of pyrrole and its liquid density, pyrrole manifests the highest liquid density coefficient LDc (defined as [Vmol ×density ×0.6023]/FW) value of 0.7. Normal liquids have LDc <0.63. This very high LDc is due to the strong N-H⋅⋅⋅π interactions in solution, and hence pyrrole can be considered to be a pseudo-crystalline liquid. When trapped inside the confined space of a crystalline sponge, a reorientation of the N-H⋅⋅⋅π interaction is observed leading to specific cyclic N-H⋅⋅⋅π tetramers and N-H⋅⋅⋅π dimers, as verified by single-crystal X-ray crystallographic and computational methods. These tetramers are of the same size as four pyrrole molecules in the solid-state of pyrrole, yet the cyclic N-H⋅⋅⋅π intermolecular interactions are circularly oriented instead of being in the linear zigzag structure found in the X-ray structure of a solid pyrrole. The confinement thus acts as an external driving force for tetramer formation.

Postsynthetic-Modified PANI/MOF Composites with Tunable Thermoelectric and Photoelectric Properties.

A 3D Co-based metal-organic framework (Co-MOF) with two kinds of large pores filled by free Co2+ ions and ligands was synthesized and characterized. To expand the MOF structure and conductivity, the free Co2+ ions and ligands were exchanged by conductive ionic liquid EtpyBr and photosensitive AgNO3 through single crystal-to-single crystal transformation, which produced structure-changed 3D MOFs Co-MOF-Br and Co-Ag-MOF, which were characterized by single-crystal X-ray diffraction. Incorporating small quantities of doped polyaniline (PANI) with redox activity into the pores could further tune the stability and conductivity of the three MOFs. The PANI/MOFs all show outstanding electrical conductivity (≈10-2  S cm-1 ), and PANI/Co-MOF-Br has the largest p-type Seebeck coefficient of 66.6 µV K-1 . PANI/Co-MOF-Br and PANI/Co-Ag-MOF have 4 and 15 times higher photocurrent density compared with PANI/Co-MOF, respectively. This work sheds light on the design of advanced electrically conductive 3D MOFs.