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Purpose: To examine the usefulness of semi-quantitative analysis using the standardized uptake value (SUV) of iodine-123 metaiodobenzylguanidine ([ 123 I]-MIBG) for predicting metastatic potential in patients with pheochromocytoma (PHEO) and paraganglioma (PGL)., Procedures: This study included 18 PHEO and 2 PGL patients. [ 123 I]-MIBG visibility and SUV-related parameters (SUVmax, SUVmean, tumor volume of [ 123 I]-MIBG uptake [TV&#95;MIBG], and total lesion [ 123 I]-MIBG uptake) were compared with the pathological grading obtained using the Pheochromocytoma of the Adrenal Gland Scaled Score (PASS) and the Grading System for Adrenal Pheochromocytoma and Paraganglioma (GAPP), which are used to predict metastatic potential. The PASS scores were categorized as < 4 and ≥ 4. Based on the GAPP scores, PHEOs/PGLs were categorized as follows: well, moderately, and poorly differentiated tumors. The Mann-Whitney U test or Spearman's rank correlation was used to assess differences or associations between two quantitative variables., Results: All PHEOs/PGLs were visualized on [ 123 I]-MIBG scintigraphy. There were 16 PASS < 4 and 4 PASS ≥ 4 tumors. Moreover, 11 and 9 tumors were well and moderately differentiated, respectively. The uptake scores and SUV-related parameters significantly differed between tumors with a PASS score of < 4 and those with a PASS score of ≥ 4 (each, p > 0.05). Moderately differentiated tumors had significantly higher uptake scores and SUV-related parameters except TV&#95;MIBG than well-differentiated tumors (each, p < 0.05). The GAPP score was positively correlated with the uptake scores and SUV-related parameters (each, p < 0.05) except TV&#95;MIBG., Conclusions: The primary tumor [ 123 I]-MIBG uptake assessed using SUV-related parameters can be an imaging tool for predicting metastatic potential in patients with PHEO/PGL., Competing Interests: Declarations. Conflict of Interest: The authors declare that they have no conflict interest. Ethical Approval: All procedures performed in studies involving human participants were in accordance with the ethical standards of the institutional and/or national research committee and with the 1964 Helsinki declaration and its later amendments or comparable ethical standards. This article does not contain any studies with animals performed by any of the authors. Informed Consent: Informed consent was waived by the institutional review board for this retrospective study., (© 2024. The Author(s).)

Self-assembled oligonuclear and polynuclear complexes have numerous functionalities and potential applications. Generally, such compounds have been constructed by thermal substitution reactions with bridging ligands. Herein, we report bottom-up and photochemical construction of functional coordination oligomers and polymers by photosubstitution-induced self-assembly. The photosubstitution reactions of a ruthenium precursor complex with bridging ligands having pyrazole moieties afford mono-, di-, tri-, tetra-, and pentanuclear ruthenium complexes, Ru 1 -Ru 5 , which have one-dimensional architectures. Intramolecular hydrogen bonding between each bridging ligand is a key to construct the molecular nanowires. All the complexes have been isolated and thoroughly characterized. The photochemically synthesized ruthenium complexes act as synthons for longer metal-complex-based nanowires with a length of the order of tens-of nanometers. The multinuclear complexes are generated by photoinduced self-assembly in the presence of a base, and they undergo photoinduced disassembly in the presence of acid., (© 2024 Wiley-VCH GmbH.)

Freshwater microalga Haematococcus lacustris rich in astaxanthin, as a supplemental live diet can directly supply natural astaxanthin to the aquaculture organisms, except marine aquaculture organisms, since H. lacustris cannot tolerate seawater salinity. The objective of the present study is to provide a salinity acclimation method that allows H. lacustris to survive and accumulate astaxanthin with the aim of developing a novel supplemental live diet for marine aquaculture organisms. H. lacustris cultured in freshwater was subjected to different stepwise salinity acclimation processes (two-, three-, and four-shift). As the controls, H. lacustris was exposed to five constant salinities conditions (0, 0.05, 0.075, 0.3, and 0.6 M NaCl, respectively). Among the controls, almost all cells in the 0.3 M and 0.6 M NaCl conditions died immediately. In contrast, H. lacustris in the stepwise salinity acclimation processes survived in 0.6 M NaCl (equivalent to seawater salinity of 35 psu), showing the highest living-cell proportion (50.0%) and astaxanthin yield (0.72 mg·L -1 ) in the four-shift. The present study first demonstrated that H. lacustris tolerated seawater salinity through a stepwise acclimation process, proving a new strategy to supply live microalgal diets rich in natural astaxanthin for marine aquaculture., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Objectives: To develop and identify machine learning (ML) models using pretreatment 2-deoxy-2-[ 18 F]fluoro-D-glucose ([ 18 F]-FDG)-positron emission tomography (PET)-based radiomic features to differentiate benign from malignant parotid gland diseases (PGDs)., Materials and Methods: This retrospective study included 62 patients with 63 PGDs who underwent pretreatment [ 18 F]-FDG-PET/computed tomography (CT). The lesions were assigned to the training (n = 44) and testing (n = 19) cohorts. In total, 49 [ 18 F]-FDG-PET-based radiomic features were utilized to differentiate benign from malignant PGDs using five different conventional ML algorithmic models (random forest, neural network, k-nearest neighbors, logistic regression, and support vector machine) and the deep learning (DL)-based ensemble ML model. In the training cohort, each conventional ML model was constructed using the five most important features selected by the recursive feature elimination method with the tenfold cross-validation and synthetic minority oversampling technique. The DL-based ensemble ML model was constructed using the five most important features of the bagging and multilayer stacking methods. The area under the receiver operating characteristic curves (AUCs) and accuracies were used to compare predictive performances., Results: In total, 24 benign and 39 malignant PGDs were identified. Metabolic tumor volume and four GLSZM features (GLSZM&#95;ZSE, GLSZM&#95;SZE, GLSZM&#95;GLNU, and GLSZM&#95;ZSNU) were the five most important radiomic features. All five features except GLSZM&#95;SZE were significantly higher in malignant PGDs than in benign ones (each p < 0.05). The DL-based ensemble ML model had the best performing classifier in the training and testing cohorts (AUC = 1.000, accuracy = 1.000 vs AUC = 0.976, accuracy = 0.947)., Conclusions: The DL-based ensemble ML model using [ 18 F]-FDG-PET-based radiomic features can be useful for differentiating benign from malignant PGDs. The DL-based ensemble ML model using [ 18 F]-FDG-PET-based radiomic features can overcome the previously reported limitation of [ 18 F]-FDG-PET/CT scan for differentiating benign from malignant PGDs. The DL-based ensemble ML approach using [ 18 F]-FDG-PET-based radiomic features can provide useful information for managing PGD., (© 2024. The Author(s).)

A polycyclic aromatic hydrocarbon displaying twelve edge nitrogen centers for a 42 π-electron system is reported. This compound was synthesized via Sonogashira coupling of pyrimidine precursors, [2+2+2] cycloaddition of bis(aryl) alkynes, and anionic cyclodehydrogenation. Spectroscopy, electrochemistry, and computational results suggest a narrowing of the HOMO-LUMO gap compared to the N -free analogue. Metal coordination affects the optical properties of the extended π system.

Objectives: To investigate the usefulness of machine learning (ML) models using pretreatment 18 F-FDG-PET-based radiomic features for predicting adverse clinical events (ACEs) in patients with cardiac sarcoidosis (CS)., Materials and Methods: This retrospective study included 47 patients with CS who underwent 18 F-FDG-PET/CT scan before treatment. The lesions were assigned to the training (n = 38) and testing (n = 9) cohorts. In total, 49 18 F-FDG-PET-based radiomic features and the visibility of right ventricle 18 F-FDG uptake were used to predict ACEs using seven different ML algorithms (namely, decision tree, random forest [RF], neural network, k-nearest neighbors, Naïve Bayes, logistic regression, and support vector machine [SVM]) with tenfold cross-validation and the synthetic minority over-sampling technique. The ML models were constructed using the top four features ranked by the decrease in Gini impurity. The AUCs and accuracies were used to compare predictive performances., Results: Patients who developed ACEs presented with a significantly higher surface area and gray level run length matrix run length non-uniformity (GLRLM&#95;RLNU), and lower neighborhood gray-tone difference matrix&#95;coarseness and sphericity than those without ACEs (each, p < 0.05). In the training cohort, all seven ML algorithms had a good classification performance with AUC values of > 0.80 (range: 0.841-0.944). In the testing cohort, the RF algorithm had the highest AUC and accuracy (88.9% [8/9]) with a similar classification performance between training and testing cohorts (AUC: 0.945 vs 0.889). GLRLM&#95;RLNU was the most important feature of the modeling process of this RF algorithm., Conclusion: ML analyses using 18 F-FDG-PET-based radiomic features may be useful for predicting ACEs in patients with CS., (© 2024. The Author(s).)

The budding of human immunodeficiency virus from an infected host cell is induced by the modification of structural proteins bearing long-chain fatty acids, followed by their anchoring to the cell membrane. Although many model budding systems using giant unilamellar vesicles (GUVs) induced by various stimuli have been developed, constructing an artificial viral budding system of GUVs using only synthesized molecules remains challenging. Herein, we report the construction of an artificial viral capsid budding system from a lipid bilayer of GUV. The C-terminus of the β-annulus peptide was modified using an octyl chain as an alkyl anchor via a disulfide bond. The self-assembly of the β-annulus peptide with an octyl chain formed an artificial viral capsid aggregate. The fluorescence imaging and transmission electron microscopy observations revealed that the addition of the tetramethylrhodamine (TMR)-labeled octyl chain-bearing β-annulus peptide to the outer aqueous phase of GUV induced the budding of the capsid-encapsulated daughter vesicle outside-to-inside the mother GUV. Conversely, the encapsulation of the TMR-labeled octyl chain-bearing β-annulus peptide in the inner aqueous phase of GUV induced the budding of the capsid-encapsulated daughter vesicle inside-to-outside the mother GUV. Contrarily, the addition of the TMR-labeled β-annulus peptide to GUV barely induced budding. It was demonstrated that the higher the membrane fluidity of GUV, the more likely budding would be induced by the addition of the alkyl anchor-modified artificial viral capsid. The simple virus-mimicking material developed in this study, which buds off through membrane anchoring, can provide physicochemical insights into the mechanisms of natural viral budding from cells., Competing Interests: No potential conflict of interest was reported by the author(s)., (© 2024 The Author(s). Published by National Institute for Materials Science in partnership with Taylor & Francis Group.)

Ruthenium complexes bearing bis pyrazole (pzH) ligands, cis -[Ru(bpy) 2 (R-pzH) 2 ] 2+ (bpy = 2,2'-bipyridine, R = -H, -Cl), were examined as photoactivated anticancer prodrugs. A dicationic pyrazole complex deprotonated to give monocationic pyrazole-pyrazolate complexes, cis- [Ru(bpy) 2 (R-pz - )(R-pzH)] + , in an aqueous solution with p K a values of 9.5 and 7.2 for R = H and R = Cl, respectively. Upon deprotonation, relative quantum yields of photosubstitution decreased while lipophilicity of the complexes increased according to the measurements of water-octanol coefficients. The ruthenium complex with 4-chloropyrazole ligands displayed high cytotoxicity upon light irradiation (IC 50 = 0.060 ± 0.016 μM) toward lung cancer cells, which was 7 times higher than that in the dark (IC 50 = 0.44 ± 0.07 μM). Additional experiments for the ruthenium R-pyrazole complexes indicated that (1) selective photodissociation of the 4-chloropyrazole ligand occurs from cis- [Ru(bpy) 2 (4-Clpz - )(4-ClpzH)] + , (2) photoinduced ligand dissociation is dominant rather than photoinduced generation of singlet oxygen ( 1 O 2 ), and (3) induction of cell death occurs via the intrinsic pathway of apoptosis.

Machine learning (ML) analyses using 18 F-fluorodeoxyglucose ( 18 F-FDG) positron emission tomography (PET)/computed tomography (CT) radiomics features have been applied in the field of oncology. The current review aimed to summarize the current clinical articles about 18 F-FDG PET/CT radiomics-based ML analyses to solve issues in classifying or constructing prediction models for several types of tumors. In these studies, lung and mediastinal tumors were the most commonly evaluated lesions, followed by lymphatic, abdominal, head and neck, breast, gynecological, and other types of tumors. Previous studies have commonly shown that 18 F-FDG PET radiomics-based ML analysis has good performance in differentiating benign from malignant tumors, predicting tumor characteristics and stage, therapeutic response, and prognosis by examining significant differences in the area under the receiver operating characteristic curves, accuracies, or concordance indices (> 0.70). However, these studies have reported several ML algorithms. Moreover, different ML models have been applied for the same purpose. Thus, various procedures were used in 18 F-FDG PET/CT radiomics-based ML analysis in oncology, and 18 F-FDG PET/CT radiomics-based ML models, which are easy and universally applied in clinical practice, would be expected to be established., (© 2023. The Author(s).)

distal -[Ru(EtOtpy)(pynp)Cl] + ( d - EtO1Cl ) (EtOtpy = 4'-ethoxy-2,2':6',2″-terpyridine, pynp = 2-(2-pyridyl)-1,8-naphthyridine), and distal / proximal -[Ru(EtOtpy)(pynp)OH 2 ] 2+ ( d / p - EtO1H 2 O ) complexes were newly synthesized to investigate the synergistic influence of the geometric configuration coupled with substituent introduction of an ethoxy (EtO) group on the physicochemical properties and reactions of the Ru(II) complexes. Configurationally nonselective aquation of d - EtO1Cl was uniquely observed to form d / p - EtO1H 2 O isomers in water, in contrast to configurationally selective aquation of distal -[Ru(tpy)(pynp)Cl] + ( d - 1Cl , tpy = 2,2':6',2″-terpyridine) without the EtO group [Yamazaki, H. . J. Am. Chem. Soc. 2011, 133, 8846-8849].The kinetic profiles of the aquation reactions of d - EtO1Cl were well analyzed using a sequential reversible reaction model assuming the reversible interconversion between d / p - EtO1H 2 O isomers via d - EtO1Cl . The observed equilibrium constant ( K iso ) of isomerization between p / d - EtO1H 2 O was calculated from the kinetic analysis as K iso = 0.45, which is consistent with the final concentration ratio (1:0.43) of p / d - EtO1H 2 O generated in the aquation reaction of d - EtO1Cl . The irreversible photoisomerization from d - EtO1H 2 O to p - EtO1H 2 O was observed in water with an internal quantum yield (Φ) of 0.44% at 520 nm. Electrochemical measurements showed that d - EtO1H 2 O undergoes a 2-step oxidation reaction of 1H + -coupled 1e - processes of Ru II -OH 2 /Ru III -OH and Ru III -OH/Ru IV ═O at pH 1.3-9.7, whereas p - EtO1H 2 O undergoes a 1-step oxidation reaction of a 2H + -coupled 2e - process of Ru II -OH 2 /Ru IV ═O in the pH range of 1.8-11.5. Any redox potential of d / p - EtO1H 2 O isomers was decreased by the electro-donating EtO substitution, compared with distal / proximal -[Ru(tpy)(pynp)OH 2 ] 2+ ( d / p - 1H 2 O ). The turnover frequency ( k O 2 = 1.7 × 10 -2 s -1 ) of d - EtO1H 2 O for water oxidation catalysis is higher than that (3.5 × 10 -4 s -1 ) of p - EtO1H 2 O by a factor of 48.6. The k O 2 value (1.7 × 10 -2 s -1 ) for d - EtO1H 2 O is 4.5-fold higher than those of d - 1H 2 O (3.8 × 10 -3 s -1 ). The higher k O 2 value of d - EtO1H 2 O compared with d - 1H 2 O could be explained by the fast oxidation rate from Ru IV ═O to Ru V ═O involved in the rate-determining step due to the electron-donating EtO group.

Stimuli-responsive ruthenium complexes proximal - and distal -[Ru(C 10 tpy)(C 10 pyqu) OH 2 ] 2+ ( proximal - 1 and distal - 1 ; C 10 tpy = 4'-decyloxy-2,2':6',2″-terpyridine and C 10 pyqu = 2-[2'-(6'-decyloxy)-pyridyl]quinoline) were experimentally studied for adduct formation with a model DNA base. At 303 K, proximal - 1 exhibited 1:1 adduct formation with 9-ethylguanine (9-EtG) to yield proximal -[Ru(C 10 tpy)(C 10 pyqu)(9-EtG)] 2+ ( proximal - RuEtG ). Rotation of the guanine ligand on the ruthenium center was sterically hindered by the presence of an adjacent quinoline moiety at 303 K. Results from 1 H NMR measurements indicated that photoirradiation of a proximal - RuEtG solution caused photoisomerization to distal - RuEtG , whereas heating of proximal - RuEtG caused ligand substitution to proximal - 1 . The distal isomer of the aqua complex, distal - 1 , was observed to slowly revert to proximal - 1 at 303 K. In the presence of 9-EtG, distal - 1 underwent thermal back-isomerization to proximal - 1 and adduct formation to distal - RuEtG . Kinetic analysis of 1 H NMR measurements showed that adduct formation between proximal - 1 and 9-EtG was 8-fold faster than that between distal - 1 and 9-EtG. This difference may be attributed to intramolecular hydrogen bonding and steric repulsion between the aqua ligand and the pendant moiety of the bidentate ligand.., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

A new chemiluminescence (CL) method based on the chemiluminescent reaction between sulfide and an acidic permanganate solution was used to quantify sulfide in seawater. A terbium-pipemidic acid complex was used as CL enhancer. The method was used to determine sulfide in the concentration range of 1-30 μmol/L in artificial seawater samples. The limit of detection of the method was 21 nmol/L sulfide. The sensitivity of the CL method was eight times higher than that of the CL method reported previously. Br - ions, which are conservative ions, interfered with sulfide. We investigated the effects of salinity, water temperature, and interfering chemicals,such asheavy-metal ions and organic matter, on the performance of the CL method. In addition, sulfite-spiked natural seawater samples were analyzed. The results demonstrate that the CL method can be used to develop a deep-sea sulfide analyzer., (© 2023. The Author(s), under exclusive licence to The Japan Society for Analytical Chemistry.)

Geometric isomers of mononuclear ruthenium(II) complexes, distal- / proximal -[Ru(tpy)(dpda)Cl] + ( d- / p - RuCl , tpy = 2,2':6',2″-terpyridine, dpda = 2,7-bis(2-pyridyl)-1,8-diazaanthracene), were newly synthesized to comprehensively investigate the geometric and electronic structures and distinctive aspects in various reactions between isomers. The ultraviolet (UV)-visible absorption spectra of d- / p - RuCl isomers show intense bands for metal-to-ligand charge transfer (MLCT) at close wavelengths of 576 and 573 nm, respectively. However, time-dependent density functional theory (TD-DFT) calculations suggest that the MLCT transition of d - RuCl involves mainly single transitions to the π* orbital of the dpda ligand in contrast to mixing of the π* orbitals of the dpda and tpy ligands for p - RuCl . The aquation reaction (1.5 × 10 -3 s -1 ) of p - RuCl to yield proximal -[Ru(tpy)(dpda)(OH 2 )] 2+ ( p - RuH 2 O ) is faster than that (5.3 × 10 -6 s -1 ) of d - RuCl in D 2 O/CD 3 OD (4:1 v/v) by three orders of magnitude, which resulted from the longer Ru-Cl bond by 0.017 Å and the distorted angle (100.2(3)°) of Cl-Ru-N (a nitrogen of dpda, being on a tpy plane) due to the steric repulsion between Cl and dpda for p - RuCl . Electrochemical measurements showed that d - RuH 2 O undergoes a 2-step oxidation reaction of 1H + -coupled 1e - processes of Ru II -OH 2 /Ru III -OH and Ru III -OH/Ru IV ═O at pH 1-9, whereas p - RuH 2 O undergoes a 1-step oxidation reaction of a 2H + -coupled 2e - process of Ru II -OH 2 /Ru IV ═O in the pH range of pH 1-10. The irreversible photoisomerization from d - RuH 2 O to p - RuH 2 O was observed in aqueous solution with an internal quantum yield (Φ) of 5.4 × 10 -3 % at 520 nm, which is lower compared with Φ = 1.1-2.1% of mononuclear Ru(II) aquo complexes with similar bidentate ligands instead of dpda by three orders of magnitude. This is possibly ascribed to the faster nonradiative decay rate from the excited 3 MLCT state to the ground state for d - RuH 2 O due to the lower π* level of dpda ligands according to the energy-gap law: the rate decreases exponentially with the increasing energy gap.

Electrochemical water splitting is a key technology for the conversion of renewable energy into chemical resources such as hydrogen. However, the oxygen evolution reaction (OER), a half-reaction of water splitting, is so slow that various effective catalysts for the OER have been explored. In this study, we demonstrate a simple and direct process for the synthesis of OER-active NiFe catalysts over electrodes. A NiFe/C catalyst layer was formed on a glassy carbon electrode by simply dropping the catalyst ink containing only metal nitrates and carbon black. The catalyst layer exhibited higher OER performance than the state-of-the-art Ir/C catalyst. The presence of carbon black is essential to enhance the OER activity of NiFe because carbon black helps to disperse the NiFe active sites. Cyclic voltammetry indicated that Ni and Fe are adjacent to each other on the surface of carbon black, resulting in significantly higher activity of NiFe/C compared to those of Ni/C and Fe/C. The effects of the Ni/Fe ratio, amount of carbon black, and type of carbon black on the OER activity of NiFe/C were examined in detail. Furthermore, we discuss the factors that determine the OER performance of NiFe/C.

In the present study, we investigated the visible-light- and thermal-stimuli-responsive properties of a host-guest system based on proximal - and distal -[Ru(C 10 tpy)(C 10 pyqu)OH 2 ] 2+ complexes ( proximal and distal -1; C 10 tpy = 4'-decyloxy-2,2':6',2''-terpyridine and C 10 pyqu = 2-[2'-(6'-decyloxy)-pyridyl]quinoline). The analogs of such ruthenium aqua complexes are well-known as metallodrugs and catalysts. The proximal isomer has a dicationic ruthenium center and hydrophobic alkyl chains on both ligands, with the two alkyl chains located close together. According to titration experiments, proximal -1 binds to γ-cyclodextrin (γ-CD) in aqueous media with a binding constant of K = 520 ± 60 M 1:1 = 520 ± 60 M -1 , which is much higher than the corresponding values for α-CD and β-CD. Additional experiments indicated that the two alkyl chains were incorporated into the cavity of γ-CD. The photoisomerized complex, distal -1, exhibits thermal isomerization back to proximal -1 in the dark with a k obs = 7.26 ± 0.01 × 10 -6 s -1 . In the presence of γ-CD, the corresponding rate constant is 1.3 times higher, which is attributed to the steric repulsion of cyclodextrin and the aqua ligand by the inclusion complex formation between distal -1 and the cyclodextrins. The distal isomer has a lower affinity for CDs because the two alkyl chains are more separated. The repeated application of external stimuli to a mixture of proximal -1 and γ-CD resulted in a reproducible and reversible host-guest complex formation.

Perovskite-type oxides have impacted various research fields, including materials and energy science. Despite their vast potential in various applications, general and simple synthesis methods for nano-perovskites remain limited. Herein, various nano-perovskites were synthesized by a facile approach involving the use of nanocarbons. The calcination of the nanocarbon deposited with metal salts yielded nano-perovskites, emulating the morphology of nanocarbons. The accumulation of precursors ( i.e. , metal salts) on the surface of the nanocarbon during the evaporation of the solvent is the key step in which the precursors are homogeneously mixed prior to calcination. The homogeneity of the precursors facilitated low-temperature calcination that resulted in the formation of nano-perovskites. Various nano-perovskites, including LaMnO 3 , LaCoO 3 , LaFeO 3 , LaNiO 3 , LaAlO 3 , LaGaO 3 , CaMnO 3 , BaMnO 3 , SrMnO 3 , La 0.7 Sr 0.3 FeO 3 , La 2 CuO 4 , and Ca 2 Fe 2 O 5 , were successfully synthesized, demonstrating the simplicity and novelty of the method for the general synthesis of nano-perovskites., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The understanding of O-O bond formation is of great importance for revealing the mechanism of water oxidation in photosynthesis and for developing efficient catalysts for water oxidation in artificial photosynthesis. The chemical oxidation of the Ru II 2 (OH)(OH 2 ) core with the vicinal OH and OH 2 ligands was spectroscopically and theoretically investigated to provide a mechanistic insight into the O-O bond formation in the core. We demonstrate O-O bond formation at the low-valent Ru III 2 (OH) core with the vicinal OH ligands to form the Ru II 2 (μ-OOH) core with a μ-OOH bridge. The O-O bond formation is induced by deprotonation of one of the OH ligands of Ru III 2 (OH) 2 via intramolecular coupling of the OH and deprotonated O - ligands, conjugated with two-electron transfer from two Ru III centers to their ligands. The intersystem crossing between singlet and triple states of Ru II 2 (μ-OOH) is easily switched by exchange of H + between the μ-OOH bridge and the auxiliary backbone ligand., Competing Interests: The authors declare no competing interest.

Photosubstitution reactions of cis -[Ru(bpy) 2 (MeCN) 2 ] 2+ with a pyrazole ligand (pzH) were studied under various conditions toward the development of a photochemical synthetic route to polypyridyl ruthenium complexes (bpy = 2,2'-bipyridine). In the absence of a base, light irradiation of an acetonitrile solution of pyrazole and cis -[Ru(bpy) 2 (MeCN) 2 ] 2+ gave a mixture of the reactant and cis -[Ru(bpy) 2 (pzH)(MeCN)] 2+ . In the presence of a mild base such as N , N -dimethylaminopyridine, a second photosubstitution from cis -[Ru(bpy) 2 (pzH)(MeCN)] 2+ to cis -[Ru(bpy) 2 (pz)(pzH)] + ( 1b ) was greatly enhanced, as confirmed by UV-vis and 1 H nuclear magnetic resonance spectroscopy. The yields of 1b were increased in solvents with moderate coordinating properties, such as acetone. The successive photosubstitution reaction was observed using a stoichiometric amount of pyrazole.

Oxygen evolution reaction (OER) is a key step in energy storage devices. Lanthanum cobaltite (LaCoO 3 ) perovskite is an active catalyst for OER in alkaline solutions, and it is expected to be a low-cost alternative to the state-of-the-art catalysts (IrO 2 and RuO 2 ) because transition metals are abundant and inexpensive. For efficient catalysis with LaCoO 3 , nanosized LaCoO 3 with a high surface area is desirable for increasing the number of catalytically active sites. In this study, we developed a novel synthetic route for LaCoO 3 nanoparticles by accumulating the precursor molecules over nanocarbons. This precursor accumulation (PA) method for LaCoO 3 nanoparticle synthesis is simple and involves the following steps: (1) a commercially available carbon powder is soaked in a solution of the nitrate salts of lanthanum and cobalt and (2) the sample is dried and calcined in air. The LaCoO 3 nanoparticles prepared by the PA method have a high specific surface area (12 m 2 g -1 ), comparable to that of conventional LaCoO 3 nanoparticles. The morphology of the LaCoO 3 nanoparticles is affected by the nanocarbon type, and LaCoO 3 nanoparticles with diameters of less than 100 nm were obtained when carbon black (Ketjen black) was used as the support. Further, the sulfur impurities in nanocarbons significantly influence the formation of the perovskite structure. The prepared LaCoO 3 nanoparticles show excellent OER activity owing to their high surface area and perovskite structure. The Tafel slope of these LaCoO 3 nanoparticles is as low as that of the previously reported active LaCoO 3 catalyst. The results strongly suggest that the PA method provides nanosized LaCoO 3 without requiring the precise control of chemical reactions, harsh conditions, and/or special apparatus, indicating that it is promising for producing active OER catalysts at a large scale., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The ionosphere is one of the important sources for magnetospheric plasma, particularly for heavy ions with low charge states. We investigate the effect of solar illumination on the number flux of ion outflow using data obtained by the Fast Auroral SnapshoT (FAST) satellite at 3000-4150 km altitude from 7 January 1998 to 5 February 1999. We derive empirical formulas between energy inputs and outflowing ion number fluxes for various solar zenith angle ranges. We found that the outflowing ion number flux under sunlit conditions increases more steeply with increasing electron density in the loss cone or with increasing precipitating electron density (> 50 eV), compared to the ion flux under dark conditions. Under ionospheric dark conditions, weak electron precipitation can drive ion outflow with small averaged fluxes (~ 10 7  cm -2  s -1 ). The slopes of relations between the Poynting fluxes and outflowing ion number fluxes show no clear dependence on the solar zenith angle. Intense ion outflow events (> 10 8  cm -2  s -1 ) occur mostly under sunlit conditions (solar zenith angle < 90°). Thus, it is presumably difficult to drive intense ion outflows under dark conditions, because of a lack of the solar illumination (low ionospheric density and/or small scale height owing to low plasma temperature)., Competing Interests: Competing interestsThe authors declare that they have no competing interests., (© The Author(s) 2021.)

Significantly high eicosapentaenoic acid (EPA) and fucoxanthin contents with high production rate were achieved in semi continuous culture of marine diatom. Effects of dilution rate on the production of biomass and high value biocompounds such as EPA and fucoxanthin were evaluated in semi-continuous cultures of Chaetoceros gracilis under high light condition. Cellular dry weight increased at lower dilution rate and higher light intensity conditions, and cell size strongly affected EPA and fucoxanthin contents. The smaller microalgae cells showed significantly higher ( p < 0.05) value of 17.1 mg g-dw -1 fucoxanthin and 41.5% EPA content per total fatty acid compared to those observed in the larger cells. Chaetoceros gracilis can accumulate relatively higher EPA and fucoxanthin than those reported previously. In addition, maintenance of small cell size by supplying sufficient nutrients and light energy can be the key for the increase production of valuable biocompounds in C. gracilis ., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2020 Tachihana, Nagao, Katayama, Hirahara, Yusoff, Banerjee, Shariff, Kurosawa, Toda and Furuya.)

A ruthenium complex showing multi-stimuli-responsive isomerization was synthesized. The catalytic activity of this complex toward water oxidation showed responses to visible-light irradiation and heat due to photoisomerization and thermal back-isomerization, respectively. DFT calculations suggested that a pendant moiety in the complex was key to controlling the catalytic activity.

Photosubstitution reactions of ruthenium complexes with pyrazole ligands, cis- [Ru(bpy) 2 (pzH) 2 ] 2+ ( 1a ), cis- [Ru(bpy) 2 (pz)(pzH)] + ( 1b ), and cis- [Ru(bpy) 2 (pz) 2 ] 0 ( 1c ) (pzH = pyrazole, bpy = 2,2'-bipyridine), were investigated. Dicationic complex 1a was deprotonated to 1b using moderate base (p K a = 15.2, MeCN), while the second deprotonation to give 1c required more severe conditions (p K a = 26.9). Monocationic complex 1b possessed an N-H···N-type intramolecular hydrogen bond between the pyrazole and pyrazolate ligands, as corroborated by the solid-state crystal structure. The photosubstitution quantum yield of 1a (Φ = 0.26) was comparable to that of cis- [Ru(bpy) 2 (pyridine) 2 ] 2+ (Φ = 0.24) in acetonitrile solution. In contrast, the photodissociation of a pzH ligand was strongly suppressed by the deprotonation of a pyrazole ligand N-H group. In the presence of 10 000 equiv of 4,4'-dimethylaminopyridine, the quantum yield dropped to ∼2 × 10 -6 in acetonitrile. The photosubstitution quantum yield of 1b was even smaller than that of neutral complex 1c , although 1c had a smaller HOMO-LUMO energy gap than monocationic complex 1b . The small quantum yield of 1b was attributed to intramolecular hydrogen bonding between pyrazole and pyrazolate ligands. The apparent rate constants for the photosubstitution of 1b were highly solvent-dependent. The photosubstitution of 1b was suppressed in aprotic solvents, while the reaction was accelerated by 2 orders of magnitude in protic solvents with strong proton donor abilities.

To achieve precise control of sulfonated polymer structures, a series of poly( p -phenylene)-based ionomers with well-controlled ion exchange capacities (IECs) were synthesised via a three-step technique: (1) preceding sulfonation of the monomer with a protecting group, (2) nickel(0) catalysed coupling polymerisation, and (3) cleavage of the protecting group of the polymers. 2,2-Dimethylpropyl-4-[4-(2,5-dichlorobenzoyl)phenoxy]benzenesulfonate (NS-DPBP) was synthesised as the preceding sulfonated monomer by treatment with chlorosulfuric acid and neopentyl alcohol. NS-DPBP was readily soluble in various organic solvents and stable during the nickel(0) catalysed coupling reaction. Sulfonated poly(4-phenoxybenzoyl-1,4-phenylene) (S-PPBP) homopolymer and seven types of random copolymers (S-PPBP- co -PPBP) with different IECs were obtained by varying the stoichiometry of NS-DPBP. The IECs and weight average molecular weights ( M w s) of ionomers were in the range of 0.41-2.84 meq. g -1 and 143 000-465 000 g mol -1 , respectively. The water uptake, proton conductivities, and water diffusion properties of ionomers exhibited a strong IEC dependence. Upon increasing the IEC of S-PPBP- co -PPBPs from 0.86 to 2.40 meq. g -1 , the conductivities increased from 6.9 × 10 -6 S cm -1 to 1.8 × 10 -1 S cm -1 at 90% RH. S-PPBP and S-PPBP- co -PPBP (4 : 1) with IEC values >2.40 meq. g -1 exhibited fast water diffusion (1.6 × 10 -11 m -10 m 2 s -1 ), and were comparable to commercial perfluorosulfuric acid polymers. When fully hydrated, the maximum power density and the limiting current density of membrane electrode assemblies (MEAs) prepared with S-PPBP- co -PPBP (4 : 1) were 712 mW cm -2 and 1840 mA cm -2 , respectively., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Surface modification of nanocarbons, for example, by coating with oxide nanolayers, is a research topic of significant interest because of the drastic changes in the physicochemical properties of the modified nanocarbons. One simple method of creating these oxide nanolayer coatings on nanocarbons is the precursor accumulation (PA) technique, which entails the following: (1) a precursor solution is added dropwise onto nanocarbon powder; (2) the solvent is dried, leaving the accumulated precursor on the nanocarbon surface; and (3) hydrolysis or decomposition of the precursor in air leads to the formation of oxide nanolayers on the nanocarbons. In this study, tetraethoxysilane (TEOS) was used as a precursor for coating silica nanolayers onto carbon nanofibers (CNFs). TEOS is so stable that it hardly undergoes hydrolysis on the surface of pristine CNFs. By treating CNFs with H 2 SO 4 /HNO 3 , acidic functional groups were introduced onto the CNF surfaces. Silica nanolayers were successfully synthesized on these acid-treated CNFs via PA coating because the acidic functional groups catalyzed the hydrolysis of TEOS accumulated on the CNF surfaces. Scanning transmission electron microscopy indicated that the thickness of silica layer is approximately several nanometers. Pore size distribution analysis for the silica nanolayer suggested the presence of nanopores with 3-5 nm. The TEOS molecules could have accessed the functional groups through the nanopore; therefore, the number of silica nanolayers formed increased with the number of PA coatings. Finally, we compared the PA coating with conventional sol-gel and atomic layer deposition techniques.

[Ru(Rtpy)(bpy)(H 2 O)] 2+ ( 1R ; bpy = 2,2'-bipyridine, and Rtpy = 2,2':6',2″-terpyridine derivatives) complexes with a variety of 4'-substituent groups on Rtpy were synthesized and characterized to reveal the effects of substituents on their structures, physicochemical properties, and catalytic activities for water oxidation. The geometric structures of 1R are not considerably influenced by the electron-donating ability of the 4'-substituent groups on Rtpy. Similar multistep proton-coupled electron transfer reactions were observed for 1R , and the redox potentials for each oxidation step tended to decrease with an increase in the electron-donating ability of the substituent, which is explained by the increased electron density on the Ru center by electron-donating groups, stabilizing the positive charge that builds up upon oxidation. This is consistent with the red-shift of the absorption bands around 480 nm assigned to the metal-to-ligand charge transfer transition for 1R due to the increased d orbital energy level of the Ru center. The turnover frequency ( k O 2 ) of 1R for water oxidation catalysis, however, depended greatly on the Rtpy ligands, varying from 0.05 × 10 -2 to 44 × 10 -2 s -1 (as the highest k O 2 was observed for R = ethoxy) by a factor of 880. A critical electron-donating ability of the 4'-substituent groups with a narrow range of Hammett constants (σ p = -0.27 to -0.24) found for the highest k O 2 values is valuable for understanding the great difficulty in the search for efficient water oxidation catalysts. On another front, the k O 2 values increased with a decrease in the redox potentials of Ru IV ═O/Ru V ═O for 1R , indicating that the potential of formation of Ru V ═O species for 1R is crucial for water oxidation catalysis under the employed conditions.

Purpose: The purpose of this case series was to describe computed tomography (CT) and magnetic resonance imaging (MRI) features of undifferentiated carcinoma with osteoclast-like giant cells of the pancreas., Methods: Institutional ethics review board approval was obtained, and informed consent was waived for this case series. We reviewed CT and MRI of patients with pathologically confirmed undifferentiated carcinoma with osteoclast-like giant cells of the pancreas found in the medical records of our hospital between 2006 and 2016., Results: Seven patients (3 males and 4 females; age, 59-82 years (mean, 71)) with confirmation by surgical resection (n = 3) or biopsy (n = 4) were identified. They underwent CT (n = 7) and MRI (n = 6). The tumors 26-83 mm in diameter (mean, 44 mm) were located in the head (n = 4) or body (n = 3) of the pancreas. They were demonstrated as lower attenuation areas relative to the adjacent pancreas on CT images obtained in both pancreatic and portal vein phases (n = 7) with a well-defined smooth margin (n = 5). They were demonstrated as hypointense areas relative to the pancreas on T2-weighted images (n = 4) and T2*-weighted images (n = 4) and diffusion-weighted images (n = 3). They contained hemosiderin deposits on histology (n = 7)., Conclusions: Undifferentiated carcinoma with osteoclast-like giant cells of the pancreas might be present as low attenuation areas with a well-defined smooth margin on CT images obtained in pancreatic and portal vein phases, and hypointense areas on T2-, T2*-, and diffusion-weighted images caused by hemosiderin deposits.

A series of ruthenium complexes with chloro-substituted bidentate ligands, proximal-[Ru(tpy)(Cl-pyqu)L] n + [ n = 1 for L = Cl, and n = 2 for L = OH 2 , tpy = 2,2';6',2''-terpyridine, pyqu = 2-(2'-pyridyl)quinoline] were synthesized and their reversible photoisomerizations and thermal isomerizations were investigated experimentally. The crystal structures of the complexes indicated that introduction of a chloro substituent at the 4- or 4'-position of the pyqu ligand did not change the structure around the metal center from that of the non-substituted complex, proximal-[Ru(tpy)(pyqu)L] n + . In contrast, the 6'-substituted complexes had sterically hindered environments around the metal center. The ruthenium aqua complexes showed reversible photoisomerization between the proximal and distal isomers. The quantum yield for photoisomerization of the 6'-substituted ruthenium aqua complex was almost twice as large as those of the other derivatives. This is explained by weakening of the ligand field on the ruthenium center by introduction of a chloro substituent at the 6'-position. Thermal back isomerization from the distal isomer to the proximal one was observed for the 6'-substituted complex, but such reactions were not observed for the other derivatives. The steric hindrance in the 6'-substituted aqua complex enhanced both thermal isomerization and photoisomerization., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

A new series of low-valent dinuclear molybdenum complexes bearing phosphido or phosphinidene bridging ligands was synthesized as a structural model of heterogeneous metal phosphide catalysts. Addition of acid to a monocationic Mo 2 -μ-P complex results in phosphide protonation, affording a dicationic Mo 2 -μ-PH species. Alternatively, reaction of an isoelectronic Mo 2 -μ-P precursor with LiBEt 3 H gives a Mo 2 H-μ-P complex. Mixing these species, one bearing a Mo-H and the other a P-H bond, results in facile H 2 production at room temperature., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

An axial-substituted silicon phthalocyanine derivative, SiPc(OR) 2 (R = C 4 H 9 ), that is soluble in organic solvent is conveniently synthesized. This silicon phthalocyanine derivative reacts with a hydroxyl group on a substrate and then with another phthalocyanine derivative under mild conditions. The accumulation number of the phthalocyanine molecules on the substrates is easily controlled by the immersion time. On the basis of AFM (atomic force microscopy) images, the surface of the phthalocyanine-modified glass substrate has uneven structures on the nanometer scale. ITO electrodes modified with the composition of the phthalocyanine derivative and PCBM show stable cathodic photocurrent generation upon light irradiation.

Possible complications of nasotracheal intubation include injury to the nasal or pharyngeal mucosa. Dissection of the retropharyngeal tissue by the endotracheal tube is one of the rarer of the more severe complications. Previous studies have indicated that the Parker Flex-Tip (PFT) tracheal tube (Parker Medical, Highlands Ranch, Colo) reduces the incidence of mucosal injury. We experienced a case involving inadvertent retropharyngeal placement of a PFT tube in a 29-year-old patient during nasotracheal intubation under general anesthesia for elective dental treatment. Despite thermosoftening the PFT tube, expanding the nasal meatus, and ensuring gentle maneuvering, the tube intruded into the left retropharyngeal mucosa. However, the injury was not severe, and the only required treatment was the administration of antibiotics and corticosteroids. Even when a PFT tube is utilized, pharyngeal dissection is possible. When resistance is felt during passing of the PFT tube through the nasopharynx, an alternative method to overcome this resistance should be utilized.

proximal,proximal-(p,p)-[Ru II 2 (tpy) 2 LXY] n+ (tpy = 2,2';6',2″-terpyridine, L = 5-phenyl-2,8-di-2-pyridyl-1,9,10-anthyridine, and X and Y = other coordination sites) yields the structurally and functionally unusual Ru II (μ-OH)Ru II core, which is capable of catalyzing water oxidation with key water insertion to the core (Inorg. Chem. 2015, 54, 7627). Herein, we studied a sequence of bridging-ligand substitution among p,p-[Ru 2 (tpy) 2 L(μ-Cl)] 3+ (Ru 2 (μ-Cl)), p,p-[Ru 2 (tpy) 2 L(μ-OH)] 3+ (Ru 2 (μ-OH)), p,p-[Ru 2 (tpy) 2 L(OH)(OH 2 )] 3+ (Ru 2 (OH)(OH 2 )), and p,p-[Ru 2 (tpy) 2 L(OH) 2 ] 2+ (Ru 2 (OH) 2 ) in aqueous solution. Ru 2 (μ-Cl) converted slowly (10 -4 s -1 ) to Ru 2 (μ-OH), and further Ru 2 (μ-OH) converted very slowly (10 -6 s -1 ) to Ru 2 (OH)(OH 2 ) by the insertion of water to reach equilibrium at pH 8.5-12.3. On the basis of density functional theory (DFT) calculations, Ru 2 (OH)(OH 2 ) was predicted to be thermodynamically stable by 13.3 kJ mol -1 in water compared to Ru 2 (μ-OH) because of the specially stabilized core structure by multiple hydrogen-bonding interactions involving aquo, hydroxo, and L backbone ligands. The observed rate from Ru 2 (μ-OH) to Ru 2 (OH) 2 by the insertion of an OH - ion increased linearly with an increase in the OH - concentration from 10 to 100 mM. The water insertion to the core is very slow (∼10 -6 s -1 ) in aqueous solution at pH 8.5-12.3, whereas the insertion of OH - ions is accelerated (10 -5 -10 -4 s -1 ) above pH 13.4 by 2 orders of magnitude. The kinetic data including activation parameters suggest that the associative mechanism for the insertion of water to the Ru II (μ-OH)Ru II core of Ru 2 (μ-OH) at pH 8.5-12.3 alters the interchange mechanism for the insertion of an OH - ion to the core above pH 13.4 because of relatively stronger nucleophilic attack of OH - ions. The hypothesized p,p-[Ru 2 (tpy) 2 L(μ-OH 2 )] 4+ and p,p-[Ru 2 (tpy) 2 L(OH 2 ) 2 ] 4+ formed by protonation from Ru 2 (μ-OH) and Ru 2 (OH)(OH 2 ) were predicted to be unstable by 71.3 and 112.4 kJ mol -1 compared to Ru 2 (μ-OH) and Ru 2 (OH)(OH 2 ), respectively. The reverse reactions of Ru 2 (μ-OH), Ru 2 (OH)(OH 2 ), and Ru 2 (OH) 2 to Ru 2 (μ-Cl) below pH 5 could be caused by lowering the core charge by protonation of the μ-OH - or OH - ligand.

Background: The trigeminal subnucleus caudalis (Vc) plays a critical role in transmission and modulation of nociceptive afferent inputs, and exhibits a similar layer construction to the spinal dorsal horn. However, afferent inputs enter the brainstem and project to a separately located nucleus. It has previously been difficult to record responses of the Vc to afferent fiber activation in a brainstem slice preparation. The aim of the present study was to establish a novel brainstem slice preparation method to study trigeminal nociceptive transmission mechanisms., New Method: Thirty adult 6-7-week-old C57/BL6J male mice were included in the study. Obliquely sliced brainstem sections at a thickness of 600μm, which included the Vc and the root entry zone to the brainstem, were prepared. The Vc response to electrical stimulation of afferent fibers was observed as a change in intracellular calcium concentration by fluorescence intensity response., Results: Electrical stimulation of afferent inputs to the trigeminal nerve increased fluorescent intensity in the Vc, which was completely diminished by tetrodotoxin and significantly suppressed by the AMPA/kainate antagonist CNQX (paired t-test, P<0.001), although the non-competitive NMDA antagonist (+)-MK801 maleate resulted in no changes. These results suggested a glutamate receptor-mediated response., Comparison With Existing Methods/conclusion: This brainstem slice preparation will be useful for investigating nociceptive transmission mechanisms of the trigeminal nerve., (Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.)

Ruthenium(ii) complexes with polypyridyl ligands have been extensively studied as promising functional molecules due to their unique photochemical and photophysical properties as well as redox properties. In this context, we report the photoisomerization of distal-[Ru(tpy)(pynp)OH 2 ] 2+ (d-1) (tpy = 2,2';6',2''-terpyridine, pynp = 2-(2-pyridyl)-1,8-naphthyridine) to proximal-[Ru(tpy)(pynp)OH 2 ] 2+ (p-1), which has not been previously characterized for polypyridyl ruthenium(ii) aquo complexes. Herein, we review recent progress made by our group on the mechanistic insights and application developments related to the photoisomerization of polypyridyl ruthenium(ii) aquo complexes. We report a new strategic synthesis of dinuclear ruthenium(ii) complexes that can act as an active water oxidation catalyst, as well as the development of unique visible-light-responsive giant vesicles, both of which were achieved based on photoisomerization.

Objective: Washing the hands using cleansers with antiseptic materials is the most popular method for hand hygiene and helps maintain health by preventing food poisoning and bacterial infections. However, repeated hand washing tends to induce eczema of the hand, such as dryness, cracking and erythema. Moreover, eczema on the hand leads to increased levels in Staphylococcus aureus (S. aureus) on the skin surface in contrast to expectations. Thus, mild hand cleansers which induce less eczema even with repeated washings are desired. Here, we evaluated the efficacy of a hand cleanser formulated with alkyl ether sulphate (AES), alkyl ether carboxylic acid (AEC) and alkyl glucoside (AG) that contains isopropyl methylphenol (IPMP) on skin symptoms and S. aureus levels., Methods: Eczema of the hand and the presence of S. aureus on the skin surface were analysed prior to and following 4 weeks of usage of the hand cleanser. A soap-based hand cleanser with IPMP was used as a reference cleanser. Eczema and cutaneous conditions were evaluated by visual grading, transepidermal water loss (TEWL), stratum corneum moisture-retention ability (MRA) and skin surface pH., Results: The repeated use of the soap-based hand cleanser significantly worsened the hand dryness, scaling and cracks on the tips of the fingers and significantly increased the TEWL and decreased the MRA. In contrast, usage of the test cleanser only induced a significant increase in skin dryness but did not induce skin scaling or cracking and did not increase TEWL or decrease the MRA. Corresponding to these changes in skin symptoms, the presence of S. aureus increased the following use of the reference cleanser but not the test cleanser. There was no significant difference in skin surface pH between the two cleansers. Moreover, the increase in S. aureus was significantly correlated to the worsening of skin dryness and scaling., Conclusion: These results suggest that not only antimicrobial activity but also the mildness, which minimizes cutaneous effects, are important for hand cleansers to prevent the growth of S. aureus. The cleanser formulated with AES, AEC and AG containing IPMP is mild and is effective to promote hand hygiene., (© 2016 Society of Cosmetic Scientists and the Société Française de Cosmétologie.)

Visible- and red-light responsive vesicles were prepared by incorporating a ruthenium aqua complex having two alkyl chains on tridentate and asymmetrical bidentate ligands (proximal-2: [Ru(C10 tpy)(C10 pyqu)OH2 ](2+) , C10 tpy=4'-decyloxy-2,2';6',2"-terpyridine, C10 pyqu=2-[2'-(6'-decyloxy)-pyridyl]quinoline). The ruthenium complex of proximal-2 with closed alkyl chain geometry and a cylinder-like molecular shape exhibited photoisomerization to distal-2 with an open alkyl chain geometry and a cone-like shape, both in an aqueous solution and in vesicle dispersions. We observed that light irradiation of giant vesicles containing proximal-2 induced diverse morphological changes., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Nanopillars composed of a photoresponsive phthalocyanine derivative have been conveniently fabricated using a continuous silane coupling reaction on a substrate. The chemical potentials of phthalocyanine nanopillars (PNs) are precisely controlled by changing the number of phthalocyanine derivatives on the substrate. In addition, photocurrent generation efficiencies have been strongly influenced by the number of phthalocyanine derivatives. High photocurrent conversion cells in a solid state have been obtained by the combination of PNs and a fullerene derivative.

In an aqueous clay mineral (montmorillonite) dispersion at a low concentration, isolated clay nanosheets with negative charges were suspended. When a solution of amphiphilic octadecylammonium chloride (ODAH(+)Cl(-)) was spread on an air-dispersion interface, the clay nanosheets were adsorbed on the ODAH(+) cations at the interface to form a stable ultrathin floating film. The floating film was transferred onto a substrate by the Schaefer method, and then the film was immersed in a [Ru(dpp)3]Cl2 (dpp = 4,7-diphenyl-1,10-phenanthroline) solution. The Ru(II) complex cations were adsorbed on the film surface because the film surface possessed a cation-exchange ability. The layers of ODAH(+), clay nanosheets, and [Ru(dpp)3](2+) were deposited in this order. By repeating these procedures, three-layer-component films were fabricated (OCR films). In a similar way, three-layer-component films in which the layers of [Ru(dpp)3](2+), clay nanosheets, and ODAH(+) were deposited in the reverse order (RCO films) were prepared by spreading a [Ru(dpp)3](ClO4)2 solution and immersing the films in an ODAH(+)Cl(-) solution. Both OCR and RCO films were characterized by surface pressure-molecular area (π-A) curve measurements, IR and visible spectroscopy, and the XRD method. The OCR and RCO film systems possessed nearly the same properties in the densities of ODAH(+) and [Ru(dpp)3](2+) and the tilt angle of the Ru(II) complex cation, although the layer distance for the RCO film was a little longer than that for the OCR film and the layered structure for the RCO film was less ordered than that for the OCR film. Pyroelectric currents for the films were measured by a noncontact method using an (241)Am radioactive electrode. When the films were heated, the pyroelectric currents were observed and the current directions for the OCR and RCO films were different. This was clear evidence that the layer order in the OCR film was reverse of that in the RCO film.

A new series of proximal,proximal-[Ru2(tpy)2(L)XY](n+) (p,p-Ru2XY, tpy = 2,2':6',2″-terpyridine, L = 5-phenyl-2,8-di(2-pyridyl)-1,9,10-anthyridine, X and Y = other coordination sites) were synthesized using photoisomerization of a mononuclear complex. The p,p-Ru2XY complexes undergo unusual reversible bridge-exchange reactions to generate p,p-Ru2(μ-Cl), p,p-Ru2(μ-OH), and p,p-Ru2(OH)(OH2) with μ-Cl, μ-OH, as well as hydroxo and aquo ligands at X and Y sites of p,p-Ru2XY, respectively. The geometric and electronic structures of these complexes were characterized based on UV-vis and (1)H NMR spectra, X-ray crystallography, and density functional theory (DFT) calculations. (1)H NMR data showed C2 symmetry of p,p-Ru2(OH)(OH2) with the distorted L chelate and nonequivalence of two tpy ligands, in contrast to the C2v symmetry of p,p-Ru2(μ-Cl) and p,p-Ru2(μ-OH). However, irrespective of the lower symmetry, p,p-Ru2(OH)(OH2) is predominantly formed in neutral and weakly basic conditions due to the specially stabilized core structure by multiple hydrogen-bond interactions among aquo, hydroxo, and backbone L ligands. The electrochemical data suggested that p,p-Ru2(OH)(OH2) (Ru(II)-OH:Ru(II)-OH2) is oxidized to the Ru(III)-OH:Ru(III)-OH state at 0.64 V vs saturated calomel electrode (SCE) and further to Ru(IV)═O:Ru(IV)-OH at 0.79 V by successive 1-proton-coupled 2-electron processes at pH 7.0. The cyclic voltammogram data exhibited that the p,p-Ru2(OH)(OH2) complex works more efficiently for electrocatalytic water oxidation, compared with a similar mononuclear complex distal-[Ru(tpy)(L)OH2](2+) (d-RuOH2) and p,p-Ru2(μ-Cl) and p,p-Ru2(μ-OH), showing that the p,p-Ru2 core structure with aquo and hydroxo ligands is important for efficient electrocatalytic water oxidation. Bulk electrolysis of the p,p-Ru2(OH)(OH2) solution corroborated the electrocatalytic cycle involving the Ru(III)-OH:Ru(III)-OH state species as a resting state. The mechanistic insight into O-O bond formation for O2 production was provided by the isotope effect on electrocatalytic water oxidation by p,p-Ru2(OH)(OH2) and d-RuOH2 in H2O and D2O media.

N-terminal domain of HIV-1 p24 capsid protein is a globular fold composed of seven helices and two β-strands with a flexible structure including the α4-5 loop and both N- and C-terminal ends. However, the protein shows a high tendency (48%) for an intrinsically disordered structure based on the PONDR VL-XT prediction from the primary sequence. To assess the possibility of marginally stabilized structure under physiological conditions, the N-terminal domain of p24 was destabilized by the addition of an artificial flexible tag to either N- or C-terminal ends, and it was analyzed using T1, T2, hetero-nuclear NOE, and amide-proton exchange experiments. When the C-terminal tag (12 residues) was attached, the regions of the α3-4 loop and helix 6 as well as the α4-5 loop attained the flexible structures. Furthermore, in the protein containing the N-terminal tag (27 residues), helix 4 in addition to the above-mentioned area including α3-4 and α4-5 loops as well as helix 6 exhibited highly disordered structures. Thus, the long-range effects of the existence of tag sequence was observed in the stepwise manner of the appearance of disordered structures (step 1: α4-5 loop, step 2: α3-4 loop and helix 6, and step 3: helix 4). Furthermore, the disordered regions in tagged proteins were consistent with the PONDR VL-XT disordered prediction. The dynamic structure located in the middle part (α3-4 loop to helix 6) of the protein shown in this study may be related to the assembly of the viral particle., (Copyright © 2014 Elsevier B.V. All rights reserved.)

A ligation of Ru(tpy)Cl3 (tpy = 2,2':6',2"-terpyridine) with 2-(2-pyridyl)-1,8-naphthyridine) (pynp) in the presence of LiCl gave distal-[Ru(tpy)(pynp)Cl](+) (d-1Cl) selectively, whereas the ligation gave proximal-[Ru(tpy)(pynp)OH2](2+) (p-1H2O) selectively in the absence of halide ions. (The proximal/distal isomers were defined by the structural configuration between the 1,8-naphthyridine moiety and the aquo or chloro ligand.) An aquation reaction of d-1Cl quantitatively afforded distal-[Ru(tpy)(pynp)OH2](2+) (d-1H2O) in water, and d-1H2O is quantitatively photoisomerized to p-1H2O. The mechanism of the photoisomerization was investigated by transient absorption spectroscopy and quantum chemical calculations. The temperature dependence of the transient absorption spectral change suggests existence of the thermally activated process from the (3)MLCT state with the activation energy (ΔE = 49 kJ mol(-1)), which is close to that (41.7 kJ mol(-1)) of the overall photoisomerization reaction. However, quantum chemical calculations suggest another activation process involving the conformational change of the pentacoordinated distal structure to the proximal structure. Quantum chemical calculations provide redox potentials and pK(a) values for proton-coupled electron transfer reactions from Ru(II)-OH2 to Ru(IV)═O in good agreement with experiments and provide an explanation for mechanistic differences between d-1H2O and p-1H2O with respect to water oxidation. The calculations show that water nucleophilic attack (WNA) on d-[Ru(V)-O](3+) (the ruthenyl oxo species derived from d-1H2O, calculated ΔG(‡) of 87.9 kJ/mol) is favored over p-[Ru(V)-O](3+) (calculated ΔG(‡) of 104.6 kJ/mol) for O-O bond formation. Examination of the lowest unoccupied molecular orbitals in d- and p-[Ru(V)-O](3+) indicates that more orbital amplitude is concentrated on the [Ru-O] unit in the case of d-[Ru(V)-O](3+) than in the case of p-[Ru(V)-O](3+), where some of the amplitude is instead delocalized over the pynp ligand, making this isomer less electrophilic.

Although the transcription factors are required for expression of the proinflammatory cytokines and immune proteins which are involved in airway hyperresponsiveness and inflammation of bronchial asthma, the antigen-induced alterations of the transcription factors in bronchi have not yet been revealed. Therefore, in order to profile the alteration pattern of the transcription factors after antigen challenge in bronchi, we used protein/DNA arrays. Rats were sensitized and repeatedly challenged with 2,4-dinitrophenylated Ascaris suum antigen. Half, 1, 2 and 4 h after the last antigen challenge, protein/DNA array was performed with nuclear extract of bronchial tissue. Twenty-one the transcription factors exhibited an activation after the last antigen challenge in rat bronchial tissue. Among them, upstream transcription factor-1 (USF-1) and CAAT box general (CBF) were markedly activated after the last antigen challenge. Conversely, 4 transcription factors were inactivated after the last challenge. In development of bronchial asthma, some of the transcription factors may have an ability to modulate the transcription of inflammatory proteins such as cytokines, inflammatory enzymes, etc. Furthermore, the transcription factors, such as USF-1 and CBF, which have not been taken notice so far are also presumed to play an important role in the development of bronchial asthma., (Copyright © 2011 Elsevier B.V. All rights reserved.)

Amidate-bridged diplatinum(II) entities [Pt(2)(bpy)(2)(μ-amidato)(2)](2+) (amidate = pivalamidate and/or benzamidate; bpy = 2,2'-bipyridine) were covalently linked to one or two Ru(bpy)(3)(2+)-type derivatives. An amide group was introduced at the periphery of Ru(bpy)(3)(2+) derivatives to give metalloamide precursors [Ru(bpy)(2)(BnH)](2+) (abbreviated as RuBnH, n = 1 and 2), where deprotonation of amide BnH affords the corresponding amidate Bn, B1H = 4-(4-carbamoylphenyl)-2,2'-bipyridine, and B2H = ethyl 4'-[N-(4-carbamoylphenyl)carbamoyl]-2,2'-bipyridine-4-carboxylate. From a 1:1:1 reaction of [Pt(2)(bpy)(2)(μ-OH)(2)](NO(3))(2), RuBnH, and pivalamide, trinuclear complexes [Pt(2)(bpy)(2)(μ-RuBn)(μ-pivalamidato)](4+) (abbreviated as RuBn-Pt(2)) were isolated and characterized. Tetranuclear complexes [Pt(2)(bpy)(2)(μ-RuBn)(2)](6+) (abbreviated as (RuBn)(2)-Pt(2)) were separately prepared and characterized in detail. The quenching of the triplet excited state of the Ru(bpy)(3)(2+) derivative (i.e., Ru*(bpy)(3)(2+)) upon tethering the Pt(2)(bpy)(2)(μ-amidato)(2)(2+) moiety is strongly enhanced in RuB1-Pt(2) and (RuB1)(2)-Pt(2), while it is only slightly enhanced in RuB2-Pt(2) and (RuB2)(2)-Pt(2). These are partly explained by the driving forces for the electron transfer from the Ru*(bpy)(3)(2+) moiety to the Pt(2)(bpy)(2)(μ-amidato)(2)(2+) moiety (ΔG°(ET)); the ΔG°(ET) values for RuB1-Pt(2), (RuB1)(2)-Pt(2), RuB2-Pt(2), and (RuB2)(2)-Pt(2) are estimated as -0.01, 0.00, +0.22, and +0.28 eV, respectively. The considerable difference in the photochemical properties of the B1- and B2-bridged systems were further examined based on the emission decay and transient absorption measurements, which gave results consistent with the above conclusions.

In the title compound, [Ru(C(10)H(8)N(2))(2)(C(21)H(18)N(4)O(4))](PF(6))(2), the Ru(II) complex cation reveals a slightly distorted octa-hedral coordination. The coordination bonds of the 4,4'-substituted bipyridyl donors [Ru-N = 2.038 (3) and 2.051 (3) Å] are shorter than those of the 2,2'-bipyridyl donors [Ru-N1 = 2.065 (3)-2.077 (3) Å], due to the electron-withdrawing effects of the substituents at the 4,4'-positions. The angles between the pyridyl planes of the three bipyridyl ligands are 1.5 (2), 6.3 (3) and 8.7 (2)°, respectively. The cations are connected by anions via N-H⋯F inter-actions.

To determine the mechanism(s) of the inhibitory effect of glucocorticoids on airway hyperresponsiveness in allergic bronchial asthma, the effects of systemic treatment with glucocorticoids on bronchial smooth muscle hyperresponsiveness and RhoA upregulation were investigated in rats with allergic bronchial asthma. Rats were sensitized and repeatedly challenged with 2,4-dinitrophenylated Ascaris suum antigen. Animals were also treated with prednisolone or beclomethasone (each 10 mg/kg, i.p.) once a day during the antigen inhalation period. Repeated antigen inhalation caused a marked bronchial smooth muscle hyperresponsiveness to acetylcholine with an upregulation of RhoA. Augmented acetylcholine-induced activation of RhoA and phosphorylation of myosin light chain were observed in bronchial smooth muscles of the antigen-exposed animals. Systemic treatment with either glucocorticoid used inhibited the bronchial smooth muscle hypercontraction until the level of the sensitized control rats that received saline inhalation instead of antigen challenge. Interestingly, both glucocorticoids also inhibited the upregulation of RhoA and augmented acetylcholine-induced activation of RhoA and phosphorylation of myosin light chain. In conclusion, glucocorticoids ameliorated the augmented bronchial smooth muscle contraction by inhibiting upregulation of RhoA. These effects of glucocorticoids may account for, in part, their beneficial effects in the treatment of asthma.

When a stimulus of equally spaced parallel lines is displaced slightly in a direction perpendicular to the lines, low-speed motion toward the displacement direction can be perceived. Such a stimulus embodies both a low-speed and a high-speed component in opposite directions. The dominance of the former would result in the perception of low-speed motion. To see how the unperceived high-speed component is processed by the visual system, I measured coherence thresholds for random-dot test-motion with and without prior adaptation to the low-speed motion of the equally spaced parallel lines. The results depended on the test speeds. At low speeds, the coherence thresholds for the same direction as that perceived during the adaptation phase increased and the coherence thresholds for the opposite direction decreased. At high speeds, the same adaptation resulted in an opposite effect. The threshold reduction for high-speed motion in the same direction as that perceived during the adaptation phase and the threshold elevation in the opposite direction might be due to adaptation of a high-speed processing channel to the high-speed component that was not perceived but was nevertheless detected.

We propose a general model for detection of both first-order motion and second-order motion. In this model an input stimulus is divided into a number of partially overlapping spatiotemporal local regions. Spatiotemporal frequency analysis is done for every local region using Gabor filters, then the input stimulus (original spatiotemporal signal) is replaced by the outputs of Gabor filters. Local motion is detected by applying Gabor motion detectors to each local spatiotemporal pattern depicted by each local feature value. Outputs of all the detectors are integrated to give the final output for global motion of the input stimulus. The model was simulated on a computer and was confirmed to correctly detect second-order motion as well as first-order motion.

Most visible matter in the Universe exists as plasma. How this plasma is heated, and especially how the initial non-equilibrium plasma distributions relax to thermal equilibrium (as predicted by Maxwell-Boltzman statistics), is a fundamental question in studies of astrophysical and laboratory plasmas. Astrophysical plasmas are often so tenuous that binary collisions can be ignored, and it is not clear how thermal equilibrium develops for these 'collisionless' plasmas. One example of a collisionless plasma is the Earth's plasma sheet, where thermalized hot plasma with ion temperatures of about 5 x 10(7) K has been observed. Here we report direct observations of a plasma distribution function during a solar eclipse, revealing cold ions in the Earth's plasma sheet in coexistence with thermalized hot ions. This cold component cannot be detected by plasma sensors on satellites that are positively charged in sunlight, but our observations in the Earth's shadow show that the density of the cold ions is comparable to that of hot ions. This high density is difficult to explain within existing theories, as it requires a mechanism that permits half of the source plasma to remain cold upon entry into the hot turbulent plasma sheet.

In Earth's environment, the observed polar outflow rate for O(+) ions, the main source of oxygen above gravitational escape energy, corresponds to the loss of approximately 18% of the present-day atmospheric oxygen over 3 billion years. However, part of this apparent loss can actually be returned to the atmosphere. Examining loss rates of four escape routes with high-altitude spacecraft observations, we show that the total oxygen loss rate inferred from current knowledge is about one order of magnitude smaller than the polar O(+) outflow rate. This disagreement suggests that there may be a substantial return flux from the magnetosphere to the low-latitude ionosphere. Then the net oxygen loss over 3 billion years drops to approximately 2% of the current atmospheric oxygen content.

In conventional models for storing hierarchically correlated patterns, correlations between ancestors (first-level patterns) and their descendants (second-level ones) are assumed to be uniform, so that the descendants are distributed around their ancestors with equal distances. However, this assumption might be unnatural. We believe that objects are encoded into patterns by preserving the similarity between them. In this case, descendants are distributed around their ancestors with various distances, so that the assumption is invalid and the conventional models become inapplicable. To overcome this, we propose a model CASM3 for storing hierarchically correlated patterns with various correlations. In CASM3, critical load levels vary with the descendants, and become higher with increasing correlations. Increase in load level successively destroys the memories of the descendants in descending order of their correlations. The size of the basins of attraction depends on the range of the correlations, and becomes larger as the correlation range is shifted toward lower levels.