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A halogen-substituted cyclic disilene compound, bromocyclotrisilene, Si3Br(Eind)3 (3a), bearing fused-ring bulky Eind (a: R1 = R2 = Et) groups, has been synthesized as an extraordinarily air-stable compound by the reduction of 1,2-dibromodisilene, (Eind)BrSiâSiBr(Eind) (2a), or tribromosilane, (Eind)SiBr3 (1a), with the Mg or Li metal. The X-ray diffraction analysis of 3a showed that the disilene moiety has an almost planar, but slightly trans-bent structure. Even though 3a is quite air-stable both in solutions and in the solid state, its Si-Br bond is reactive under reducing conditions. The further treatment of 3a with the Li metal leads to the formation of room-temperature thermally stable silicon homologues of the cyclopropyl radical, i.e., the cyclotrisilanyl radicals (6a) [6a(syn) and 6a(anti)], via intramolecular C-H bond activation in a transient silicon homologue of the cyclopropenyl radical, i.e., the cyclotrisilenyl radical, [Si3(Eind)3]⢠(5a). The formation mechanism of 6a from 5a is discussed based on the theoretical calculations. The unique structural and electronic properties of these Si3 three-membered ring species incorporating the Eind groups have been experimentally and theoretically investigated.
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Transition metal atom (M)-encapsulating silicon cage nanoclusters (M@Si16) exhibit a superatomic nature, depending on the central M atom owing to the number of valence electrons and charge state on organic substrates. Since M@Si16 superatom featuring group 4 and 5 transition metal atoms exhibit rare-gas-like and alkali-like characteristics, respectively, group 6 transition metal atoms are expected to show alkaline earth-like behavior. In this study, M@Si16, comprising a central atom from group 6 (MVI = Cr, Mo, and W) were deposited on C60 substrates, and their electronic and chemical stabilities were investigated in terms of their charge state and chemical reactivity against oxygen exposures. In comparison to alkali-like Ta@Si16, the extent of charge transfer to the C60 substrate is approximately doubled, while the oxidative reactivity is subdued for MVI@Si16 on C60, especially for W@Si16. The results show that a divalent state of MVI@Si162+ appears on the C60 substrate, which is consistently calculated to be a symmetrical cage structure of W@Si162+ in C3v, revealing insights into the "periodic law" of M@Si16 superatoms pertaining to the characteristics of alkaline earth metals.
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In organic reactions, bond-forming and bond-cleaving processes are generally considered to be more important than other processes such as conformational isomerization. We report herein an example where a conformational isomerization process, propeller-like alkene rotation, is considered to determine the selectivity over the reaction pathways. The transition state with the highest energy barrier in some alkylpalladium isomerization (chain walking) events was theoretically indicated to correspond to alkene rotation, while transition states for bond-cleaving ß-hydride elimination and bond-forming migratory insertion were not even observed. It was also suggested both theoretically and experimentally that the palladium chain walking over internal carbons in alkyl chains proceeds via cis alkene intermediates rather than thermodynamically more stable trans alkene intermediates, due to their relative difficulty to undergo alkene rotation.
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Elemental substitution and doping validate the optimization of chemical and physical properties of functional materials, and the composition ratio of the substituting atoms generally determines their properties by changing their geometric and electronic structures. For atomically precise nanoclusters (NCs) consisting of countable atom aggregates, the composition can be controlled accurately to provide an ideal model to study the heteroatom substitution effects. Since aluminum (Al) and boron (B) both belong to group 13 in the periodic table, the effect of B atom substitution on Aln NCs can be investigated while maintaining the total number of valence electrons in AlnBm NCs. In this study, oxidative reactivities of small Al NCs with B atom substitution are studied for AlnBm NCs (m = 1, n = 6-14 and m = 2, n = 11) supported on organic surfaces by using X-ray photoelectron spectroscopy and oxygen molecule (O2) exposure measurements. Before completing the endohedral B@Al12- superatomic NC, one B atom substitution in Al NCs (AlnB) enhances oxidative reactivities 3-20 times compared to those of Aln+1, particularly for n ≤ 11. When one Al atom of Al12B is further substituted by a B atom to form Al11B2, the reactivity drastically increases (6.6 × 102 times), showing that the B atom substitution makes the NC chemically active or inactive geometrically depending on the exohedral or endohedral site for the B atom in the Al NC. In addition, density functional theory calculations show that the electronegative B atom contributes to forming a locally positive Al site to facilitate O2 adsorption except in Al12B, in which the B atom is geometrically shielded by the surface of the Al12 cage in B@Al12.
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Cyclometalated iridium(III) complexes have been used in various optical materials, including organic light-emitting diodes (OLEDs) and photocatalysts, and a deeper understanding and prediction of their luminescence quantum yields (LQYs) greatly aid in accelerating material design. In this study, we integrated density functional theory (DFT) calculations with machine learning (ML) techniques to extract factors controlling LQY. Although a substantial data set of Ir(III) complexes and their LQYs is indispensable for constructing accurate ML models to predict LQYs, generating this type of data set is challenging due to the complexities associated with ab initio calculations of LQYs. To address this issue, we investigated the nonradiative decay process of nine Ir(III) complexes emitting blue to green, each exhibiting varying experimental LQYs, by using DFT calculations. For all nine complexes, the quenching process was induced by the rotation of the single bond in one of the ligands, which converted the six-coordinate structure to the five-coordinate structure. Since the decay mechanism was common for the nine Ir(III) complexes, parameters correlated with LQYs could be used as objective variables instead of LQYs. Based on this idea, we collected a data set featuring Ir(III) complexes and the energy differences between their six- and five-coordinate triplet structures, which correlated with LQYs. We also constructed ML models using the calculated LQYs as the objective variables with the parameters from the ground-state calculations as explanatory variables. The analyses of the constructed model revealed that the LUMO energy of the ligand made the most significant negative contribution to LQY. This suggests that the potential energy surface of the metal-to-ligand charge transfer (MLCT) excited state, which stabilizes the six-coordinate structure, is reduced by decreasing the energy of the unoccupied orbitals.
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The structural and dynamical properties of water can be greatly altered by the anisotropic interfacial environment. Here, we study the intermolecular vibration and relaxation dynamics of a water film and a water droplet on a graphene surface based on low-frequency Raman spectra calculated from molecular dynamics simulations. The calculated Raman spectra of the interfacial water systems show a weakened libration peak and an enhanced intermolecular hydrogen bond (HB) stretching peak compared to the spectrum of bulk water, which are attributed to softened orientation motion. We also find that the collective polarizability relaxation in the droplet is much slower than that in the film and bulk, which is completely different from the collective dipole relaxation. The slow relaxation is due to a positive correlation between the induced polarizabilities of distinct molecules caused by the global and anisotropic structural fluctuations of the water droplet. Furthermore, we find that the two-dimensional HB network by the orientation-ordered interfacial water molecules leads to different intermolecular vibration dynamics between the parallel and perpendicular components. The present theoretical study demonstrates that low-frequency Raman spectroscopy can reveal the anisotropic and finite effects on the intermolecular dynamics of the water film and droplet.
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Fourier-transform infrared (FTIR) spectroscopy can detect the presence of functional groups and molecules directly from a mixed solution of organic molecules. Although it is quite useful to monitor chemical reactions, quantitative analysis of FTIR spectra becomes difficult when various peaks of different widths overlap. To overcome this difficulty, we propose a chemometrics approach to accurately predict the concentration of components in chemical reactions, yet interpretable by humans. The proposed method first decomposes a spectrum into peaks with various widths by the wavelet transform. Subsequently, a sparse linear regression model is built using the wavelet coefficients. Models by the method are interpretable using the regression coefficients shown on Gaussian distributions with various widths. The interpretation is expected to reveal the relation of broad regions in spectra to the model prediction. In this study, we conducted the prediction of monomer concentration in copolymerization reactions of five monomers against methyl methacrylate by various chemometric approaches including conventional methods. A rigorous validation scheme revealed that the proposed method overall showed better predictive ability than various linear and non-linear regression methods. The visualization results were consistent with the interpretation obtained by another chemometric approach and qualitative evaluation. The proposed method is found to be useful for calculating the concentrations of monomers in copolymerization reactions and for the interpretation of spectra.
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BACKGROUND: Schnitzler syndrome is a rare disorder with chronic urticaria, and there is no report summarizing the current status in Japan. METHODS: A nationwide survey of major dermatology departments in Japan was conducted in 2019. We further performed a systematic search of PubMed and Ichushi-Web, using the keywords "Schnitzler syndrome" and "Japan" then contacted the corresponding authors or physicians for further information. RESULTS: Excluding duplicates, a total of 36 clinically diagnosed cases were identified from 1994 through the spring of 2022, with a male to female ratio of 1:1. The median age of onset was 56.5 years. It took 3.3 years from the first symptom, mostly urticaria, to reach the final diagnosis. The current status of 30 cases was ascertained; two patients developed B-cell lymphoma. SchS treatment was generally effective with high doses of corticosteroids, but symptoms sometimes recurred after tapering. Colchicine was administered in 17 cases and was effective in 8, but showed no effect in the others. Tocilizumab, used in six cases, improved laboratory abnormalities and symptoms, but lost its efficacy after several years. Rituximab, used in five cases, was effective in reducing serum IgM levels or lymphoma mass, but not in inflammatory symptoms. Four cases were treated with IL-1 targeting therapy, either anakinra or canakinumab, and achieved complete remission, except one case with diffuse large B-cell lymphoma. CONCLUSIONS: Since Schnitzler syndrome is a rare disease, the continuous collection and long-term follow-up of clinical information is essential for its appropriate treatment and further understanding of its pathophysiology.
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Urticaria Crónica , Síndrome de Schnitzler , Urticaria , Humanos , Masculino , Femenino , Persona de Mediana Edad , Síndrome de Schnitzler/diagnóstico , Síndrome de Schnitzler/tratamiento farmacológico , Urticaria/diagnóstico , Proteína Antagonista del Receptor de Interleucina 1/uso terapéutico , Urticaria Crónica/tratamiento farmacológico , Japón/epidemiologíaRESUMEN
By means of an initial electrochemical carbon dioxide reduction reaction (eCO2RR), both the reaction current and Faradaic efficiency of the eCO2RR on boron-doped diamond (BDD) electrodes were significantly improved. Here, this effect is referred to as the self-activation of BDD. Generally, the generation of carbon dioxide radical anions (CO2 â¢-) is the most recognized pathway leading to the formation of hydrocarbons and oxygenated products. However, the self-activation process enabled the eCO2RR to take place at a low potential, that is, a low energy, where CO2 â¢- is hardly produced. In this work, we found that unidentate carbonate and carboxylic groups were identified as intermediates during self-activation. Increasing the amount of these intermediates via the self-activation process enhances the performance of eCO2RR. We further evaluated this effect in long-term experiments using a CO2 electrolyzer for formic acid production and found that the electrical-to-chemical energy conversion efficiency reached 50.2% after the BDD self-activation process.
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Pyoderma gangrenosum (PG), a chronic aseptic inflammatory skin disease characterized by skin ulcers with elevated and undermined borders, is resistant to conventional therapies. PG is elicited by activated neutrophils and macrophages and is often associated with systemic diseases such as inflammatory bowel disease, rheumatoid arthritis, aortitis syndrome, and hematopoietic disorders. This single-center study assessed the efficacy and safety of selectively depleting myeloid-lineage leukocytes in patients with PG. Patients with PG, aged 20 or over, received 5 or 10 treatment sessions of granulocyte and monocyte adsorption apheresis (GMA), once or twice a week. Treatment efficacy was assessed based on the rate of skin ulcer reduction, the visual analog scale of pain, and the physician's global assessment of the skin lesions. A complete response (CR) was obtained in eight patients, a nearly complete response (nCR) in three patients, and a partial response (PR) in two patients. In four of the other six, the disease remained stable (SD) and in two we observed disease progression (PD). No severe adverse events were recorded. Our results suggest that GMA is a useful and safe treatment modality for PG.
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Eliminación de Componentes Sanguíneos , Colitis Ulcerosa , Piodermia Gangrenosa , Adsorción , Adulto , Eliminación de Componentes Sanguíneos/métodos , Colitis Ulcerosa/terapia , Granulocitos , Humanos , Monocitos , Piodermia Gangrenosa/complicaciones , Piodermia Gangrenosa/terapia , Resultado del Tratamiento , Adulto JovenRESUMEN
BACKGROUND: Granulomatous amoebic encephalitis (GAE) is an infrequent and fatal infectious disease worldwide. Antemortem diagnosis in this condition is very difficult because clinical manifestations and neuroimaging are nonspecific. CASE PRESENTATION: A 60-year-old Japanese woman was admitted with a chief complaint of left homonymous hemianopsia. Brain-MRI showed extensive necrotizing lesions enhanced by gadolinium, in the right frontal lobe, right occipital lobe, and left parietal lobe. Epithelioid granulomas of unknown etiology were found in the biopsied brain specimens. Shotgun metagenomic sequencing using a next-generation sequencer detected DNA fragments of Balamuthia mandrillaris in the tissue specimens. The diagnosis of granulomatous amoebic encephalitis was confirmed using an amoeba-specific polymerase chain reaction and immunostaining on the biopsied tissues. CONCLUSIONS: Shotgun metagenomics is useful for the diagnosis of central nervous system infections such as GAE wherein the pathogens are difficult to identify.
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Amebiasis , Balamuthia mandrillaris , Encefalitis , Amebiasis/diagnóstico , Balamuthia mandrillaris/genética , Encefalitis/diagnóstico , Femenino , Granuloma/diagnóstico , Humanos , Metagenómica , Persona de Mediana EdadRESUMEN
Catalytic asymmetric Mannich reactions of imines with weakly acidic simple amides were developed using a chiral potassium hexamethyldisilazide (KHMDS)-bis(oxazoline) potassium salt (K-Box) catalyst system. The desired reactions proceeded to afford the target compounds in high yields with high diastereo- and enantioselectivities. It was suggested that a K enolate interacted with K-Box to form a chiral K enolate that reacted with imines efficiently. In this system, K-Box (potassium salt of Box) worked as a chiral ligand of the active potassium species.
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Inmunodeficiencia Variable Común , Dermatitis Herpetiforme , Impétigo , Antibacterianos/uso terapéutico , Inmunodeficiencia Variable Común/complicaciones , Inmunodeficiencia Variable Común/diagnóstico , Dermatitis Herpetiforme/tratamiento farmacológico , Humanos , Impétigo/diagnóstico , Impétigo/tratamiento farmacológico , RecurrenciaRESUMEN
Methods for direct functionalization of C-H bonds mediated by N-oxyl radicals constitute a powerful tool in modern organic synthesis. While several N-oxyl radicals have been developed to date, the lack of structural diversity for these species has hampered further progress in this field. Here we designed a novel class of N-oxyl radicals based on N-hydroxybenzimidazole, and applied them to the direct C-H functionalization reactions. The flexibly modifiable features of these structures enabled facile tuning of their catalytic performance. Moreover, with these organoradicals, we have developed a metal-free approach for the synthesis of acyl fluorides via direct C-H fluorination of aldehydes under mild conditions.
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Agammaglobulinemia/inmunología , Infecciones por Virus de Epstein-Barr/diagnóstico , Herpesvirus Humano 4/inmunología , Leucemia Linfocítica Crónica de Células B/complicaciones , Úlcera Cutánea/diagnóstico , Agammaglobulinemia/sangre , Agammaglobulinemia/diagnóstico , Agammaglobulinemia/tratamiento farmacológico , Anciano , Biopsia , Ciclofosfamida/uso terapéutico , Quimioterapia Combinada/métodos , Infecciones por Virus de Epstein-Barr/tratamiento farmacológico , Infecciones por Virus de Epstein-Barr/inmunología , Infecciones por Virus de Epstein-Barr/virología , Herpesvirus Humano 4/aislamiento & purificación , Humanos , Inmunosupresores/uso terapéutico , Leucemia Linfocítica Crónica de Células B/sangre , Leucemia Linfocítica Crónica de Células B/inmunología , Masculino , Prednisolona , Piel/inmunología , Piel/patología , Úlcera Cutánea/tratamiento farmacológico , Úlcera Cutánea/inmunología , Úlcera Cutánea/virología , Resultado del TratamientoRESUMEN
Nivolumab and pembrolizumab are humanized IgG4 monoclonal antibodies against programmed cell death 1 (PD-1). Although these agents are effective in treating advanced melanoma, non-small-cell lung carcinoma, and other types of cancers, various adverse events have been reported. Cutaneous adverse events are particularly prevalent and, while granulomatous/sarcoid-like reactions are uncommon, they are increasingly recognized as immune-related adverse events associated with immune checkpoint inhibitors. Herein, we report two cases of granulomatous/sarcoid-like reaction with foreign material, mimicking metastatic malignancy after PD-1 inhibitor treatment. Clinicians should be aware of the existence of cutaneous lesions and perform biopsy if needed to prevent misdiagnosis and unnecessary adjustments to immunotherapy.
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Erupciones por Medicamentos , Melanoma , Proteínas de Neoplasias/antagonistas & inhibidores , Nivolumab/efectos adversos , Receptor de Muerte Celular Programada 1/antagonistas & inhibidores , Neoplasias del Recto , Anciano , Erupciones por Medicamentos/diagnóstico , Erupciones por Medicamentos/metabolismo , Erupciones por Medicamentos/patología , Humanos , Masculino , Melanoma/diagnóstico , Melanoma/tratamiento farmacológico , Melanoma/metabolismo , Melanoma/patología , Metástasis de la Neoplasia , Proteínas de Neoplasias/metabolismo , Nivolumab/administración & dosificación , Receptor de Muerte Celular Programada 1/metabolismo , Neoplasias del Recto/diagnóstico , Neoplasias del Recto/tratamiento farmacológico , Neoplasias del Recto/metabolismo , Neoplasias del Recto/patologíaAsunto(s)
Liquen Plano Oral/tratamiento farmacológico , Triazinas/administración & dosificación , Anciano de 80 o más Años , Biopsia , Femenino , Uniones Comunicantes/efectos de los fármacos , Uniones Comunicantes/patología , Humanos , Liquen Plano Oral/diagnóstico , Liquen Plano Oral/patología , Mucosa Bucal/citología , Mucosa Bucal/patología , Resultado del TratamientoRESUMEN
A remarkably strained cyclopyrenylene trimer CP3 was synthesized and it underwent the first biaryl C-C σ-bond cleavage by direct oxygen insertion without the aid of any metal agents. A priori highly strained CP3 exhibits the longest wavelength emission among all pyrene-based fluorophores due to the intensive electronic interactions between pyrenes. The color of the emission drastically changes from orange to light blue upon oxidation. Theoretical studies revealed that the release of ring strain reasonably drives the reaction between two CP3 molecules and O2. This strain-induced transformation could be also applied for sulfur atom insertion into a biaryl σ-bond.