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Neoadjuvant therapy with nivolumab improves event-free survival (EFS) in patients with resectable non-small cell lung cancer, and a pathological complete response is a predictor of longer EFS. We assessed metabolic responses using 18F-fluorodeoxyglucose-positron emission tomography (FDG-PET) before and after neoadjuvant treatment to explore its surrogacy for pathological complete response (pCR). We describe three patients with squamous cell lung carcinoma who underwent neoadjuvant therapy with nivolumab plus chemotherapy, followed by surgery. In Cases 1 and 2, preoperative tumour response were PR per RECIST and demonstrated marked metabolic response on FDG-PET after neoadjuvant therapy, with both resected tumours showing a pCR. On the other hand, Case 3 showed a tumour response before surgery (PR per RECIST), however, the tumour, maintained FDG uptake (19.5 → 15.1), and the resected tumour remained residual cells (RVT, 15%). Thus, reduction of FDG uptake on FDG-PET can predict the pathological response to neoadjuvant therapy with nivolumab., Competing Interests: Hiroaki Akamatsu, Honoraria; Amgen Inc, AstraZeneca K.K., Boehringer Ingelheim Japan Inc., Bristol‐Myers Squibb, Chugai Pharmaceutical Co. Ltd., Eli Lilly Japan K.K., MSD K.K., Nippon Kayaku. Co. Ltd., Novartis Pharma K.K., Ono Pharmaceutical Co. Ltd., Pfizer Inc, Takeda Pharmaceutical Co. Ltd. and Taiho Pharmaceutical Co. Ltd. Advisory role; Amgen Inc, and Janssen Pharmaceutical K.K., Sandoz. Research funding; Amgen Inc, Chugai Pharmaceutical Co. Ltd. and MSD K.K. Nobuyuki Yamamoto, Honoraria; AbbVie Inc., Accuray Japan K.K., Amgen K.K., AstraZeneca K.K., Boehringer Ingelheim Japan Inc., Chugai Pharmaceutical Co. Ltd., Daiichi Sankyo Co., Ltd., Eli Lilly Japan K.K., Guardant Health Japan Corp., Janssen Pharmaceutical K.K., Merck Biopharma Co., Ltd., Miyarisan Pharmaceutical Co., Ltd., MSD K.K., Kyorin Pharmaceutical Co., Ltd., Novartis Pharma K.K., Ono Pharmaceutical Co. Ltd., Pfizer Inc, Takeda Pharmaceutical Co. Ltd. and Taiho Pharmaceutical Co. Ltd., Terumo Corp., Tsumura & Co.. Advisory role; Amgen K.K., AstraZeneca K.K., Chugai Pharmaceutical Co. Ltd., Eli Lilly Japan K.K., MSD K.K., Novartis Pharma K.K., Ono Pharmaceutical Co. Ltd. Research funding; AbbVie Inc., Amgen K.K., Asahi Kasei Corporation, AstraZeneca K.K., A2 Healthcare Corporation, Boehringer Ingelheim Japan Inc., Bristol‐Myers Squibb K.K., Chugai Pharmaceutical Co. Ltd., EPS Holdings, Inc., IQVIA Services Japan K.K., Janssen Pharmaceutical K.K., Mebix, Inc., MSD K.K., Novartis Pharma K.K., Ono Pharmaceutical Co. Ltd., Taiho Pharmaceutical Co. Ltd.. Data safety Monitoring Board: AstraZeneca K.K. All other authors declare no conflict of interest., (© 2024 The Author(s). Respirology Case Reports published by John Wiley & Sons Australia, Ltd on behalf of The Asian Pacific Society of Respirology.)

The Ca 2+ -dependent activator protein for secretion (CAPS/CADPS) family protein facilitates catecholamine release through the dense-core vesicle exocytosis in model neuroendocrine cell lines. However, it remains unclear if it induces dopamine release in the central neurons. This study aimed to examine the expression and function of CADPS2, one of the two CADPS paralogs, in dopamine neurons of the mouse midbrain. This study shows that CADPS2 was expressed in tyrosine hydroxylase and the vesicular monoamine transporter 2 (VMAT2)-positive dopaminergic neurons of the midbrain samples and primary mesencephalic cell cultures. Subcellular fractions rich in dopamine were collected using immunoaffinity for CADPS2 from midbrain protein extracts. Cell imaging using fluorescent false neurotransmitter FFN511 as a substrate for VMAT2 showed decreased activity-dependent dopamine release in Cadps2 -deficient cultures, compared to that in wild-type cultures. These results suggest that CADPS2 is involved in dopamine release from the central neurons, indicating its involvement in the central dopamine pathway., Competing Interests: The authors declare that the research was conducted without any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2024 Iguchi, Katsuzawa, Saruta, Sadakata, Kobayashi, Sato, Sato, Sano, Maezawa, Shinoda and Furuichi.)

Significant effort has been devoted to the development of materials that combine high electrical conductivity and permanent porosity. This paper discloses a diazaporphyrin-based hydrogen-bonded organic framework (HOF) with porosity and n-type semiconductivity. A 5,15-diazaporphyrin Ni(ii) complex with carboxyphenyl groups at the meso positions afforded a HOF due to hydrogen-bonding interactions between the carboxy groups and meso -nitrogen atoms. The thermal and chemical stabilities of the HOF were examined using powder X-ray diffraction analysis, and the charge-carrier mobility was determined to be 2.0 × 10 -7 m 2 V -1 s -1 using the flash-photolysis time-resolved microwave conductivity (FP-TRMC) method. An analogous diazaporphyrin, which does not form a HOF, exhibited mobility that was 20 times lower. The results presented herein highlight the crucial role of hydrogen-bonding networks in achieving conductive pathways that can tolerate thermal perturbation., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

This research focuses on enhancing H 2 adsorption by using the [Mo(PCy 3 ) 2 (CO) 3 ] complex supported on porous materials such as silica gel and mesoporous carbon. The study reports a significant increase in hydrogen adsorption capacity, reaching up to 9.3 times that of the bulk complex. This improvement suggests that using mesoporous materials as supports for the [Mo(PCy 3 ) 2 (CO) 3 ] complex enhances the accessibility of H 2 gas to its open-metal sites., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The aim of this study was to estimate the administered dosage of 81mKr noble gas as calculated by the radioactivity of 81Rb-rubidium hydroxide (81RbOH). The administered dosage was regarded as the total amount of 81mKr noble gas. The radioactivity of 81mKr was calculated using the radioactivity of 81RbOH at the examination, the beginning of inhalation, the inhalation duration and the attenuation volume from the generator to the patient for 81mKr noble gas. In addition, we created an Internet survey and asked National University Hospital in Japan to respond to questions regarding the parameters of concern. Survey responses were provided by 38 hospitals (response rate was 90.5%). Twenty-seven hospitals (64.3%) examined lung ventilation scintigraphy using 81mKr noble gas. The mean administered dosage and the effective dose of lung ventilation scintigraphy using 81mKr noble gas were 35.8 ± 22.1 GBq and 0.97 ± 0.60 mSv, respectively., (© The Author(s) 2023. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.)

Background Aims: Monocytes, derived from hematopoietic stem cells (HSCs), play a pivotal role in the immune response to cancer. Although they are an attractive source of cell therapy for cancer, a method for ex vivo expansion has not yet been established. Monocytes differentiated from pluripotent stem cells (PSCs), including induced pluripotent stem cells (iPSCs), can be an alternative source of HSC-derived monocytes because of their self-renewal and pluripotency. To develop a standardized method for the generation of iPSC-derived monocytes for future clinical applications, we aim to control the size of the iPSC colony., Methods: To this end, we developed a plate with multiple dots containing a chemical substrate for the iPSC scaffold. iPSCs placed in the plate expanded only on the dots and created colonies of the same size. The cells were then differentiated into monocytes by adding cytokines to the colonies., Results: The dot plate substantially reduced variability in monocyte-like cell generation when compared with cultivating cells on a plate with the substrate covering the entire surface area. Furthermore, more monocyte-like cells were obtained by adjusting the dot size and the distance between the dots. The iPSC-derived monocyte-like cells phagocytosed cancer cells and secreted proinflammatory cytokines. The cells also expressed Fc receptors and exerted immunoglobulin G-mediated killing of cancer cells with the corresponding antibodies., Conclusions: The dot plate enabled the control of iPSC colony size in two-dimensional culture, which resulted in a reduction in the generation-variation of functional monocyte-like cells. This standardized method for generating iPSC-derived monocyte-like cells using the dot plate could also facilitate the development of an automated closed system on a large scale for clinical applications., Competing Interests: Declaration of Competing Interest NS, ES, AU and MU collaborate with Sekisui Chemical Co. YN, HI and SH are employees of Sekisui Chemical Co. HI and SH are coinventors of a patent WO2021/024943 issued on a technology of the chemical scaffold. OM has no commercial, proprietary or financial interest in the products or companies described in this article., (Copyright © 2023 International Society for Cell & Gene Therapy. Published by Elsevier Inc. All rights reserved.)

The electronic states of iodo-bridged platinum nanowire complexes have been studied using polarized FT-IR spectroscopy. The N-H symmetrical stretching mode was found to be highly sensitive to the electronic states, distinguishing mixed-valence (MV) and averaged-valence (AV) states. The first Pt(III) nanowire complexes have been realized by the chemical pressures of the counter-anions.

New Magnus' green salt (MGS) analogues, [M(dabdOH) 2 ][MCl 4 ]·2H 2 O (dabdOH = (2 S ,3 S )-2,3-diaminobutane-1,4-diol; M = Pd (1) and M = Pt(2)), in which [M(dabdOH) 2 ] 2+ and [MCl 4 ] 2- are stacked alternately to form linear chains, were obtained as hexagonal plate crystals. The hexagonal shape and large crystal size are unprecedented features as MGS analogues. An unusual trigonal grade separation of chain complexes has been revealed by the structural analysis. 1 and 2 exhibited remarkable yellow and pink colours, respectively, which are derived from weak M⋯M interactions. The dabdOH ligand, which has an additional hydrogen donor group (hydroxy group), produces a multiple-hydrogen-bond network. The combination of intrachain and interchain hydrogen bonds gives a two-dimensional (2D) hydrogen-bond sheet, and each 2D sheet is indirectly connected by hydrogen bonds via lattice water molecules. The OH-functionalised ligand greatly increases the hydrophilicity of the MGS analogues and yields the largest single crystals of all MGS analogues reported so far. The trigonal grade-separated chain structure is likely due to the geometric matching between the periodicity of chains and the short axis width of the chain. This strategy opens up new insight for preparing large crystals of MGS analogues and for constructing trigonal grade-separated nanowires in molecular crystals.

Background: Bone modifying agents (BMAs) have been used to prevent skeletal-related events (SRE) in cancer patients with bone metastases. In this meta-analysis, efficacy and adverse events (AEs) were studied based on a de-escalation strategy in which the BMA dosing interval was prolonged from 4 to 12 weeks., Methods: PubMed, Cochrane, ICHUSHI, and CINAHL were searched for articles on BMA dosing intervals from outcomes measured were the incidence of SRE and related various AEs. A quantitative meta-analysis was performed using a random-effects model to calculate relative risk ratios (RRs) and 95% confidence intervals (CIs)., Result: The meta-analysis included three randomized controlled studies (RCTs) of Zoledronic acid hydrate (ZA) ( n = 2663) and six RCTs ( n = 141) on BMA other than ZA. There was no difference in the incidence of SREs when comparing the dosing frequency of 12 versus 4 weeks for BMA (RR = 1.21, 95% CI [0.82-1.78], p = 0.33). Further, AEs related to treatment discontinuation were significantly less frequent with ZA given every 12 weeks than when given every 4 weeks (RR = 0.51 [0.30-0.89], p = 0.02). In particular, renal dysfunction leading to grade ≥3 or discontinuation of treatment with ZA occurred significantly less frequently with every 12-week dosing (RR = 0.33 [0.12-0.91], p = 0.33)., Conclusion: This meta-analysis showed no influence of BMA de-escalation on the incidence of SRE; nevertheless, AEs appeared to reduce with the de-escalated usage of ZA., Competing Interests: Declaration of Conflicting InterestsThe author(s) declared no potential conflicts of interest with respect to the research, authorship, and/or publication of this article.

Purpose: Atrial fibrillation (AF) frequently occurs after pulmonary resection and is commonly referred to as postoperative atrial fibrillation (POAF). This study explored whether or not POAF is related to the recurrence of AF in the chronic phase., Methods: A total of 1311 consecutive patients without a history of AF who underwent lung resection based on a diagnosis of lung tumor were retrospectively analyzed., Results: POAF occurred in 46 patients (3.5%), and a logistic regression analysis revealed that the age (p < 0.05), history of hyperthyroidism (p < 0.05), and major lung resection (p < 0.05) were independent predictors of POAF. AF events in the chronic phase were observed in 15 (32.6%) and 45 (3.6%) patients with and without POAF, respectively. A Cox regression analysis revealed that POAF was the only independent predictor of AF development in the chronic phase (p < 0.01). The Kaplan-Meier curve and log-rank test revealed that the cumulative incidence of AF in the chronic phase was significantly higher in patients with POAF than in those without POAF (p < 0.01)., Conclusion: POAF was an independent predictor for AF in the chronic phase after lung resection. Further investigations including cases of catheter ablation and optimal medical therapy for patients with POAF after lung resection are needed., (© 2023. The Author(s) under exclusive licence to Springer Nature Singapore Pte Ltd.)

Objectives  Descending necrotizing mediastinitis (DNM) is a poor prognosis disease. This study aims to examine the patient background and treatment of DNM and to identify more effective treatments for DNM. Methods  The patient background and treatment of 11 patients who underwent surgery for DNM between November 2010 and June 2021 were studied. The patients were divided into six patients who underwent continuous saline irrigation (group I) and five patients who did not (group N). The differences in the drainage duration and length of hospital stay between the two groups were retrospectively investigated. Results  Eleven patients were treated for DNM: six male and five female, with a median age of 61 years (35-79). Comorbidities included diabetes mellitus in three cases; one patient was administered steroids. The pathways of occurrence were anterior tracheal gap/vascular visceral gap/posterior visceral gap in group I (2/1/2) and group N (0/2/4). Progression was I/IIA/IIB according to Endo's classification in group I (1/1/4) and group N (3/1/1). The mean duration of irrigation was 9.0 ± 3.7 days, and the drainage duration in group I was 17.5 ± 8.2 days, which was significantly shorter than 31 ± 13.6 days in group N ( p  < 0.048). The hospital stays in group I was 29.3 ± 8.4 days, which was significantly shorter than that in group N (68 ± 27.1 days; p  < 0.015). Conclusions  Irrigation therapy significantly shortened the drainage duration and hospital stay. Irrigation is a useful treatment for DNM., Competing Interests: Conflict of Interest None declared., (The Author(s). This is an open access article published by Thieme under the terms of the Creative Commons Attribution License, permitting unrestricted use, distribution, and reproduction so long as the original work is properly cited. ( https://creativecommons.org/licenses/by/4.0/ ).)

The rate of cell proliferation is a crucial factor in cell production under good manufacturing practice (GMP) control. In this study, we identified a culture system for induced pluripotent cells (iPSCs) that supports cell proliferation and viability and maintains the cells in an undifferentiated state even at 8 days after seeding. This system involves the use of dot pattern culture plates that have been coated with a chemically defined scaffold which has high biocompatibility. Under cell starvation conditions, where medium exchange was not performed for 7 days or where the amount of medium exchange was reduced to half or a quarter, iPSC viability and lack of differentiation were maintained. The rate of cell viability in this culture system was greater than generally obtained by standard culture methods. The cells in this compartmentalized culture system could be induced to differentiate in a controlled and consistent manner: differentiation of endoderm occurred in a controlled and consistent manner: endoderm, mesoderm, and ectoderm could be consistently induced to differentiate in the cultures. In conclusion, we have developed a culture system that supports high viability in iPSCs and allows their controlled differentiation. This system has the potential for use in GMP-based production of iPSCs for clinical purposes.

Objective: This study was aimed at determining the minimum acquisition count to provide diagnosable image quality (DIQ) and investigating the usefulness of preset count acquisition (PCA) for planar images of pediatric 99m Tc-dimercaptosuccinic acid (DMSA) scintigraphy., Methods: First, we calculated a coefficient of variation (CV) for DIQ with the shortest acquisition time through visual evaluation in 12 pediatric patients who underwent 99m Tc-DMSA scintigraphy. Second, a minimum acquisition count to achieve the CV for DIQ was determined with the single regression analysis using CV as an explanatory variable and the total acquisition count as an objective variable in 81 pediatric patients. Finally, we compared PCA images based on the minimum acquisition count and preset time acquisition (PTA) images for 5 min in terms of the acquisition time, CV, and renal uptake ratio in another 23 pediatric patients., Results: The visual evaluation showed that the CV corresponding to DIQ with the shortest acquisition time was 27.1%. The total acquisition count corresponding to DIQ was revealed to be 299,764 in the single regression analysis and was determined to be 300,000 after rounding. The CV and its standard deviation in PCA at 300,000 counts and PTA for 5 min were 26.4 ± 0.6% and 24.8 ± 1.3%, respectively. The standard deviation of CV in PCA at 300,000 counts was smaller than that in PTA for 5 min, indicating little variation in image quality between cases. The acquisition time in PCA at 300,000 counts (3.1 ± 0.7 min) was shorter than that in PTA for 5 min (5.0 ± 0.0 min). The intraclass correlation coefficient between renal uptake ratios for PCA and PTA was 0.98, indicating an extremely high concordance., Conclusions: The minimum acquisition count required for the DIQ was 300,000. In addition, PCA at 300,000 counts was demonstrated to be useful by providing stable image quality at the shortest acquisition time., (© 2023. The Author(s) under exclusive licence to The Japanese Society of Nuclear Medicine.)

Oligothiols are useful as building blocks in the construction of disulfide-based macrocycles and polymers or as ligands for coordination polymers. Above all, benzenehexathiol ( BHT ) is a particularly important molecule, as it is used to construct conductive two-dimensional MOFs. Despite the desire to clarify its structure and isolate it to high purity, the chemical instability of BHT has hampered single-crystal X-ray structure analysis of intact BHT . In addition, the synthesis of discrete disulfide molecules of BHT has not been reported. Here, we succeed in obtaining the single crystals of intact BHT , which is analyzed by single crystal X-ray structure analysis. Furthermore, the structures of a group of molecules with intermolecular disulfide bonds ( BHT·4im and BHT 2 ·2TBA , im = imidazole, TBA = tetrabutylammonium cation) obtained by processing BHT in the presence of bases are determined.

N,N'-dihydroxy-1,4,5,8-naphthalenetetracarboxdiimide (NDI-(OH) 2 ) has attracted much attention in recent years, because its doubly deprotonated state, (O-NDI-O) 2- , has metal-coordination ability and characteristic electronic transition useful for designing electronic and optical functions. In contrast, a molecular crystal with the mono-deprotonated (HO-NDI-O) - ion remains unknown. We herein report an organic crystal containing non-disproportionated (HO-NDI-O) - ions, which are connected by very strong O-H-O hydrogen bonds. Its lowest energy absorption band (450 to 650 nm) is observed in between that of NDI-(OH) 2 (380 nm) and isolated (O-NDI-O) 2- (500 to 850 nm) species, consistent with the molecular orbital calculations. This absorption originates from the electronic transition from deprotonated imide-based orbitals to NDI-core orbitals, which can be influenced by the hydrogen bonds around imide group. Consequently, the optical properties of NDI-(OH) 2 can be modulated by the stepwise deprotonation and hydrogen-bonding interactions., (© 2023 Wiley-VCH GmbH.)

Topochemical reactions provide selective products based on the molecular position; however, they generally require molecules to be placed in strictly limited orientations and distances, making them less versatile. In this study, we found that by confining trans -4-styrylpyridine (4-spy) as a reactive substrate in a flexible metal-organic framework (MOF) nanospace, [2+2] cycloadducts can be selectively obtained, even when the distance between two C═C bonds of 4-spy in the crystal is 5.9 Å, which is much larger than the conventionally observed upper limit (4.2 Å). Such an unusual cyclization reaction is suggested to occur due to the transient proximity of the 4-spy due to the "swing" motion in the nanospace. The MOF nanospace, with its high degree of molecular structural freedom, can be applied to different platforms that do not require the fine constraints of reactive distances for solid-phase reactions.

We report the synthesis, characterization, and electronic properties of the quinoid-based three-dimensional metal-organic framework [Fe 2 (dhbq) 3 ]. The MOF was synthesized without using cations as a template, unlike other reported X 2 dhbq 3 -based coordination polymers, and the crystal structure was determined by using single-crystal X-ray diffraction. The crystal structure was entirely different from the other reported [Fe 2 (X 2 dhbq 3 )] 2- ; three independent 3D polymers were interpenetrated to give the overall structure. The absence of cations led to a microporous structure, investigated by N 2 adsorption isotherms. Temperature dependence of electrical conductivity data revealed that it exhibited a relatively high electrical conductivity of 1.2 × 10 -2 S cm -1 ( E a = 212 meV) due to extended d-π conjugation in a three-dimensional network. Thermoelectromotive force measurement revealed that it is an n-type semiconductor with electrons as the majority of charge carriers. Structural characterization and spectroscopic analyses, including SXRD, Mössbauer, UV-vis-NIR, IR, and XANES measurements, evidenced the occurrence of no mixed valency based on the metal and the ligand. [Fe 2 (dhbq) 3 ] upon incorporating as a cathode material for lithium-ion batteries engendered an initial discharge capacity of 322 mAh/g.

Here we report the development of an equimolar conjugate of a metal-organic cage (MOC) and DNA (MOC-DNA). Several MOC-DNA conjugates were assembled into a programmed structure by coordinating with a template DNA having a complementary base sequence. Moreover, conjugation with the MOC drastically enhanced the permeability of DNA through the lipid bilayer, presenting great potential as a drug delivery system.

The use of molecular spins as quantum bits is fascinating because it offers a wide range of strategies through chemical modifications. In this regard, it is very interesting to search for organic radical ions that have small spin-orbit coupling values. On the other hand, the feature of the magnetic relaxation of π-organic radical ions is rarely exploited due to the difficulty of spin dilution, and π-stacking interaction. In this study, we focus on N , N ', N ''-tris(2,6-dimethylphenyl)benzenetriimide (BTI-xy), where three xylene moieties connected to the imide groups cover the π-plane of the BTI core. As a result, BTI-xy radical anions without π-stacking interaction were obtained. This led to the slow magnetization relaxation, which is reported for the first time in organic radicals. Furthermore, the relaxation times in a solution state revealed the importance of spin interaction.

We report the water adsorption/desorption behavior and dynamic magnetic properties of the Pt-Cl chain complex [{[Pt(en) 2 ][PtCl 2 (en) 2 ]} 3 ][{(MnCl 5 )Cl 3 } 2 ] ⋅ 12H 2 O (1). Upon heating 1 in a vacuum, we obtained the dehydrated form [{[Pt(en) 2 ][PtCl 2 (en) 2 ]} 3 ][{(MnCl 5 )Cl 3 } 2 ] (1DH). The framework structures of 1 and 1DH are identical, and both complexes underwent slow magnetic relaxation. However, the magnetic relaxation times for 1DH were shorter than those for 1, meaning that the dynamic magnetic properties were controlled upon water vapor adsorption/desorption. From detailed analyses of the dynamic magnetic behavior, a phonon-bottleneck effect contributes to the magnetic relaxation processes. We discuss the mechanism for the changes in the magnetic relaxation processes upon dehydration in terms of the heat capacity and thermal conductivity., (© 2022 Wiley-VCH GmbH.)

α-Alkylation reactions between amides and alcohols, with dimethylacetamide-stabilized Ru nanoparticles (NPs) as the catalyst, were investigated. The reactions proceeded with low catalyst loadings compared to metal complexes. Characterizations of the Ru NPs were performed by X-ray photoelectron spectroscopy, X-ray absorption fine structure spectroscopy, and various techniques. Control experiments revealed the reaction mechanisms, which proceeded via hydrogen autotransfer with alcohols.

Benzenetriimide (BTI) is a promising building block for materials chemistry due to its characteristic 3-fold symmetry and redox properties, whereas little is known about its conductive and magnetic properties. In this study, we synthesized three charge-transfer complexes based on N,N',N''-trimethylbenzenetriimide (BTI-Me). One of the complexes contains isolated dimers of BTI-Me radical anion (BTI-Me⋅ - ), while the other two have the infinite π-stacked array of BTI-Me with the formal charge of -0.5. The latter two complexes did not show metallic behavior but showed semiconducting behavior probably due to the characteristic insulation in one-dimensional electron system, so-called charge ordering and dimer-Mott insulation. The magnetic susceptibility of the complex in dimer-Mott state exhibits an unusual transition from antiferromagnetic to ferromagnetic spin states with the hysteresis loop of 15 K derived from the structural phase transition around 130 K. These properties were also supported by DFT calculations., (© 2022 Wiley-VCH GmbH.)

In condensed matter, phase separation is strongly related to ferroelasticity, ferroelectricity, ferromagnetism, electron correlation, and crystallography. These ferroics are important for nano-electronic devices such as non-volatile memory. However, the quantitative information regarding the lattice (atomic) structure at the border of phase separation is unclear in many cases. Thus, to design electronic devices at the molecular level, a quantitative electron-lattice relationship must be established. Herein, we elucidated a Pd II -Pd IV /Pd III -Pd III phase transition and phase separation mechanism for [Pd(cptn) 2 Br]Br 2 (cptn = 1 R ,2 R -diaminocyclopentane), propagated through a hydrogen-bonding network. Although the Pd···Pd distance was used to determine the electronic state, the differences in the Pd···Pd distance and the optical gap between Mott-Hubbard (MH) and charge-density-wave (CDW) states were only 0.012 Å and 0.17 eV, respectively. The N-H···Br···H-N hydrogen-bonding network functioned as a jack, adjusting the structural difference dynamically, and allowing visible ferroelastic phase transition/separation in a fluctuating N 2 gas flow. Additionally, the effect of the phase separation on the spin susceptibility and electrical conductivity were clarified to represent the quasi-epitaxial crystals among CDW-MH states. These results indicate that the phase transitions and separations could be controlled via atomic and molecular level modifications, such as the addition of hydrogen bonding.

Halogen-bridged linear chain metal complexes (MX-Chains) are fascinating compounds that have a quasi-one-dimensional (1D) electronic system. In this study, we synthesized the first Ni-based MX-Chain compound having hydroxy groups, i.e., [Ni(dabdOH) 2 Br]Br 2 ·[Ni(dabdOH x ) 2 Br] 0.5 ·(2-PrOH) 0.25 ·(MeOH) 0.25 ( 1 ·solvent, x = ∼0.6, dabdOH = (2 S ,3 S )-2,3-diaminobutane-1,4-diol). Single-crystal X-ray diffraction revealed that the MX-Chains in 1 ·solvent formed sheets and single-chain structures in the superlattice. It suggested an MH-like state, whereas the polarized reflection and Raman spectra suggested a CDW-like state. Magnetic and electron spin resonance measurements revealed that both high-spin Ni(II) (∼15%) and low-spin Ni(III) (∼85%) sites are present in the chain structures, i.e., the metal sites show mixed valency. Therefore, we concluded that 1 ·solvent adopts an intermediate state between the MH and CDW states. Moreover, a single crystal of 1 ·solvent exhibited semiconductive characteristics along the chain direction. This finding represents a new structural and electronic state of 1D electronic systems as well as MX-Chains.

The coordination polymers (CPs) with binary ligands, including 2,5-dihydroxy-1,4-benzoquinone (H2DHBQ) and 4,4'-bipyridyl (bpy), were synthesized using in situ hydrolysis of 2,5-dimethoxy-1,4-benzoquinone (DMBQ). Three kinds of CPs were obtained depending on the metal ions. For M = Mn and Zn, a 1D zigzag chain structure with cis conformation ( cis -1D-M ) was obtained, whereas Co, Ni, and Cu compounds afforded a 2D net structure with trans conformation ( trans -2D-M ) with a 1D pore. A linear chain structure was also obtained for M = Cu. Magnetic susceptibility (χ M T ) at 300 K in cis -1D-Mn and trans -2D-Co was evaluated to be 4.421 and 2.950 cm 3 K mol -1 , respectively, indicating that both compounds are in the high-spin state. According to the N 2 adsorption isotherms at 77 K, trans -2D-Ni showed microporosity with the BET surface area of 177 m 2 g -1 , whereas the isomorphic trans -2D-Co rarely adsorbed N 2 at 77 K. This phenomenon was explained by the difference of diffusion kinetics of the adsorbent molecules, which was supported by the CO 2 adsorption isotherms at 195 K. The optical band gaps of cis -1D-Mn , cis -1D-Zn , trans -2D-Co , and trans -2D-Ni were estimated to be 1.6, 1.8, 1.0, and 1.1 eV, respectively, by using UV-vis-NIR spectroscopy., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Electrical conduction among metallocycles has been unexplored because of the difficulty in creating electronic transport pathways. In this work, we present an electrocrystallization strategy for synthesizing an intrinsically electron-conductive metallocycle, [Ni 6 (NDI-Hpz) 6 (dma) 12 (NO 3 ) 6 ]·5DMA· n H 2 O (PMC-hexagon) (NDI-Hpz = N , N '-di(1 H -pyrazol-4-yl)-1,4,5,8-naphthalenetetracarboxdiimide). The hexagonal metallocycle units are assembled into a densely packed ABCABC… sequence (like the fcc geometry) to construct one-dimensional (1D) helical π-stacked columns and 1D pore channels, which were maintained under the liberation of H 2 O molecules. The NDI cores were partially reduced to form radicals as charge carriers, resulting in a room-temperature conductivity of (1.2-2.1) × 10 -4 S cm -1 (pressed pellet), which is superior to that of most NDI-based conductors including metal-organic frameworks and organic crystals. These findings open up the use of metallocycles as building blocks for fabricating conductive porous molecular materials., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Current-voltage characteristics and dielectric properties were studied in bromo-bridged one-dimensional compounds, [Pd(en) 2 Br](Suc-C 5 ) 2 ·H 2 O, exhibiting mixed-valence and averaged valence (MV-AV) phase transition. In the AV phase, clear nonlinear current-voltage characteristics were observed. This phenomenon was explained by the thermally induced electron-hole separation assisted by an electric field. This mechanism was supported by the dielectric properties of [Pd(en) 2 Br](Suc-C n ) 2 ·H 2 O ( n = 5 and 6).

The front cover artwork is provided by Prof. Masahiro Yamashita's group at Tohoku University and designed by Dr. Laurent Guérin at University of Rennes 1. The image illustrates that the atomic structure of a 2D charge density wave can be revealed although the planes associated to this local 2D order are randomly stacked preventing the use of conventional structure determination techniques. Read the full text of the Research Article at 10.1002/cphc.202100857., (© 2022 Wiley-VCH GmbH.)

Many solids, particularly low-dimensional systems, exhibit charge density waves (CDWs). In one dimension, charge density waves are well understood, but in two dimensions, their structure and their origin are difficult to reveal. Herein, the 2D charge-density-wave atomic structure and stabilization mechanism in the bromide-bridged Pd compound [Pd(cptn) 2 Br]Br 2 (cptn=1R,2R-diaminocyclopentane) is investigated by means of single-crystal X-ray diffraction employing the 3D-Δpair distribution function (3D-ΔPDF) method. Analysis of the diffuse scattering using 3D-ΔPDF shows that a 2D-CDW is stabilized by a hydrogen-bonding network between Br - counteranion and the amine (NH 2 ) group of the cptn in-plane ligand, and that 3D ordering is prevented due to a weak plane to plane correlation. We extract the effective displacements of the atoms describing the atomic structure quantitatively and discuss the stabilization mechanism of the 2D-CDW. Our study provides a method to identify and measure the key interaction responsible for the dimensionality and stability of the CDW that can help further progress of rational design., (© 2022 Wiley-VCH GmbH.)

Guest-promoted modulation of the electronic states in metal-organic frameworks (MOFs) has brought about a new field of interdisciplinary research, including host-guest chemistry and solid-state physics. Although there are dozens of studies on guest-promoted enhancement of the electrical conductivity properties, including stoichiometry, conductive carriers and structure-property relationships have been scarcely studied in detail. Herein, we studied the effects of continuous and controlled bromine vapor doping on structural, optical, thermoelectric, and semiconducting properties of Cu[Cu(pdt) 2 ] (pdt = 2,3-pyrazinedithiolate) as a function of bromine stoichiometry. We demonstrated that the same material could act as both p- and n-type semiconductors by tuning the stoichiometry of Br doped in Br x @Cu[Cu(pdt) 2 ], and a change in the charge-carrier type from holes in pristine MOF to electrons upon bromine vapor doping was observed. Bromine molecules acted as an oxidant, causing the selective oxidation of [Cu II (pdt) 2 ] in the host framework. In addition, a redox hopping pathway between the partially oxidized Cu II /Cu III center contributed to the enhancement of the electrical conductivity of the MOF.

The creation of low-dimensional heterostructures for intelligent devices is a challenging research topic; however, macro- and atomic-scale connections in one-dimensional (1D) electronic systems have not been achieved yet. Herein, we synthesize a heterostructure comprising a 1D Mott insulator [Ni(chxn) 2 Br]Br 2 (1; chxn = 1R-2R-diaminocyclohexane) and a 1D Peierls or charge-density-wave insulator [Pd(chxn) 2 Br]Br 2 (2) using stepwise electrochemical growth. It can be considered as the first example of electrochemical liquid-phase epitaxy applied to molecular-based heterostructures with a macroscopic scale. Moreover, atomic-resolution scanning tunneling microscopy images reveal a modulation of the electronic state in the heterojunction region with a length of five metal atoms (~ 2.5 nm), that is a direct evidence for the atomic-scale connection of 1 and 2. This is the first time that the heterojunction in the 1D chains has been shown and examined experimentally at macro- and atomic-scale. This study thus serves as proof of concept for heterojunctions in 1D electronic systems., (© 2022. The Author(s).)

Objective: With the increased frequency of small lung tumor detection, there has been a similar increase in limited surgery, such as wedge resection. To identify such small lung tumors, we use a computed tomography (CT)-guided intraoperative marking method using the O-arm Surgical Imaging System. We retrospectively investigated its usefulness. Methods: Of 1,043 cases of thoracic surgery performed at our department between May 2017 and June 2021, O-arm System marking was used in 30 cases (2.9%), totaling 39 lesions. Tumor location was predicted preoperatively based on 3-dimensional CT and anatomic positioning. Visceral pleura near the tumor was marked with a metal clip, and the O-arm System was brought to the surgical site. CT was taken after the tumor side lung was fully re-expanded and clamped. After confirming the tumor and the clip locations, the clip was repositioned as necessary and marked in the same way. If the marking was successful, the clips were used as markers when performing lung resection. Results: Marking was successful in all cases. The average number of targets was 1.3, the average number of O-arm insertions was 1.3, and the average total number of marking clips was 2.6. In all cases, we checked the specimens, and if the tumor was palpable, the resection margin was also checked. No intraoperative or postoperative complications were observed in any patients. Conclusions: If the O-arm System is available, this technique is a noninvasive, simple, and useful method that could be widely used in clinical practice with a low dose of radiation.

Clinical use of human pluripotent stem cells (hPSCs) is hampered by the technical limitations of their expansion. Here, we developed a chemically synthetic culture substrate for human pluripotent stem cell attachment and maintenance. The substrate comprises a hydrophobic polyvinyl butyral-based polymer (PVB) and a short peptide that enables easy and uniform coating of various types of cell culture ware. The coated ware exhibited thermotolerance, underwater stability and could be stored at room temperature. The substrate supported hPSC expansion in combination with most commercial culture media with an efficiency similar to that of commercial substrates. It supported not only the long-term expansion of examined iPS and ES cell lines with normal karyotypes during their undifferentiated state but also directed differentiation of three germ layers. This substrate resolves major concerns associated with currently used recombinant protein substrates and could be applied in large-scale automated manufacturing; it is suitable for affordable and stable production of clinical-grade hPSCs and hPSC-derived products., (© 2022. The Author(s).)

Introduction: Microsoft Kinect V2 ® (Kinect) is a peripheral device of Xbox ® and acquires information such as depth, posture, and skeleton definition. In this study, we investigated whether Kinect can be used for human gait analysis., Methods: Ten healthy volunteers walked 20 trials, and each walk was recorded by a Kinect and infrared- and marker-based-motion capture system. Pearson's correlation and overall agreement with a method of meta-analysis of Pearson's correlation coefficient were used to assess the reliability of each parameter, including gait velocity, gait cycle time, step length, hip and knee joint angle, ground contact time of foot, and max ankle velocity. Hip and knee angles in one gait cycle were calculated in Kinect and motion capture groups., Results: The coefficients of correlation for gait velocity (r = 0.92), step length (r = 0.81) were regarded as strong reliability. Gait cycle time (r = 0.65), minimum flexion angle of hip joint (r = 0.68) were regarded as moderate reliability. The maximum flexion angle of the hip joint (r = 0.43) and maximum flexion angle of the knee joint (r = 0.54) were regarded as fair reliability. Minimum flexion angle of knee joint (r = 0.23), ground contact time of foot (r = 0.23), and maximum ankle velocity (r = 0.22) were regarded as poor reliability. The method of meta-analysis revealed that participants with small hip and knee flexion angles tended to have poor correlations in maximum flexion angle of hip and knee joints. Similar trajectories of hip and knee angles were observed in Kinect and motion capture groups., Conclusions: Our results strongly suggest that Kinect could be a reliable device for evaluating gait parameters, including gait velocity, gait cycle time, step length, minimum flexion angle of the hip joint, and maximum flexion angle of the knee joint., (© The Authors, published by EDP Sciences, 2022.)

We reported in 2018 that among several extracellular matrices, fibronectin, type I collagen, type IV collagen, laminin I, fibrinogen, and bovine serum albumin, fibronectin is particularly useful for adhesion of porcine pancreatic tissue. Subsequently, we developed a technology that enables the chemical coating of the constituent motifs of fibronectin onto cell culture dishes. In this experiment, we used islets (purity ≥ 90%), duct epithelial cells (purity ≥ 60%), and acinar cells (purity ≥ 99%) isolated from human pancreas according to the Edmonton protocol published in 2000 and achieved adhesion to the constituent motifs of fibronectin. A solution including cGMP Prodo Islet Media was used as the assay solution. In islets, adhesion was enhanced with the constitutive motifs of fibronectin compared with uncoated islets. In the functional evaluation of islets, insulin mRNA expression and insulin secretion were enhanced by the constitutive motif of fibronectin compared with non-coated islets. The stimulation index was comparable between non-coated islets and fibronectin motifs. In duct epithelial cells, adhesion was mildly promoted by the fibronectin component compared with non-coated component, while in acinar cells, adhesion was inhibited by the fibronectin component compared with the non-coated component. These data suggest that the constitutive motifs of fibronectin are useful for the adhesion of islets and duct epithelial cells.

The first interdigitated MX-type chain complex with infinite π-stacked arrays was synthesized. The synchronization between a Pt-Br⋯ chain and π-stacking periodicities led to the longest M-X-M distance (6.6978(15) Å) and nil or negligible intervalence charge transfer, which is essential to realize the Robin-Day class I mixed valence state in MX chains.

Ohmic contacts are of critical importance to improve the performance of semiconductor devices as well as those of low-dimensional materials. Halogen-bridged metal complexes (MX-Chains) are fascinating quasi-one-dimensional (1D) electronic materials. However, reports on the electrical characteristics of MX-Chains remain elusive. Herein, we report the electrical characteristics of single crystals of [Ni(chxn) 2 Br]Br 2 (chxn: (1R,2R)-(-)-1,2-cyclohexanediamine), which is a 1D Mott insulator, using different probe arrangements. [Ni(chxn) 2 Br]Br 2 was shown for the first time to exhibit Ohmic characteristics on the crystal surface, albeit that the conductivity behavior of the interior of the crystal is nonlinear due to the Joule heating effect. The current flow on the surface is shallow (a few micrometers in depth) despite the millimeter-scale crystal size; this phenomenon is strongly connected to its structural anisotropy. The Ohmic contact revealed in this work should be valuable for the application of MX-Chains as electronic devices in the near future., (© 2021 Wiley-VCH GmbH.)

Reversible H 2 storage under mild conditions is one of the most important targets in the field of materials chemistry. Dihydrogen complexes are attractive materials for this target because they possess moderate adsorption enthalpy as well as adsorption without cleavage of the H-H bond. In spite of these advantages, H 2 adsorption studies of dihydrogen complexes in the solid state are scarce. We herein present H 2 adsorption properties of the 16-electron precursor complex ([Mo(PCy 3 ) 2 (CO) 3 ]) in the solid state synthesized by two procedures. One is the direct synthesis under an Ar atmosphere (1), and the other is removal of the N 2 -adduct under vacuum (2). 2 showed ideal Langmuir type reversible ad/desorption of H 2 above room temperature, whereas 1 showed irreversible adsorption. The adsorption enthalpy of 2 was larger than that in THF solution. Using DFT calculation, this difference was explained by the absence of the agostic interaction in the solid state.