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We present the visualization of the experimental valence electron-density distribution (EDD) in the isolated 1,2-digermacyclobutadiene ring system, revealing the unique 4π electron-delocalization on the four-membered Ge 2 C 2 ring. A remarkably high Möbius 4π-electron aromatic character in the Ge 2 C 2 ring can be suggested from theoretical calculations, in sharp contrast to the significant antiaromaticity of the all-carbon cyclobutadiene ring., (© 2024 The Author(s). Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The particular reactivity of the recently discovered class of the main group element polyhedral clusters, pyramidanes, remains largely unexplored. In this communication, we report the reaction of the germapyramidane with tert-butyllithium leading to the rather unusual organogermanium compound [Li + (thf) 2 ]⋅2 - , as the product of the formal insertion of a Ge-apex into the C-Li bond. This reactivity mode exemplifies unusual electrophilic behaviour of a pyramidane, which is a priori considered as a nucleophilic reagent. Being highly reactive, [Li + (thf) 2 ]⋅2 - readily undergoes reactions with electrophiles (MeI, EtBr), initially forming intermediate germahousenes, which isomerize to the thermodynamically more favourable germoles., (© 2024 Wiley-VCH GmbH.)

In this study, compounds with phenylethynyl (PE) groups introduced at all of the possible positions of the methylene-bridged structure of the 1,1'-bi-2-naphthol backbone (3-PE to 8-PE) were synthesized. Compounds with four or six phenylethynyl groups (3,6-PE, 4,6-PE, 5,6-PE, 6,7-PE, and 3,4,6-PE) were also synthesized. The key reaction for the synthesis of these compounds was the Sonogashira reaction using halogen scaffolds. The new transformation methods include (1) selective bromination of the 5-position of the binaphthyl skeleton and (2) bromination of the 6-position and then iodination of the 4-position, followed by the Sonogashira reaction of iodine at the 4-position and lithiation and protonation of bromine at the 6-position. The optical properties of the compounds were evaluated. The extension of the π system greatly differed depending on the position of the phenylethynyl group. 4-PE, 4,6-PE, and 3,4,6-PE, in which the phenylethynyl groups were introduced in the extended direction of the naphthalene linkage axis, showed longer absorption and emission wavelengths and higher fluorescence quantum yields than the other compounds. In circularly polarized luminescence measurements, 7-PE showed a relatively large g lum value, an interesting finding that reverses the sense., (© 2024 Wiley-VCH GmbH.)

Three new ONNO-donor tetradentate unsymmetrical salen ligands were synthesized by using o-phenyl diamine with substituted salicylaldehydes followed by a two-step reaction methodology. These three ligands by reaction with Cu(OAc) 2 .4H 2 O produced three new monomeric Cu(II) complexes, [Cu II (L 1-3 )] (1-3). Elemental analysis, IR, UV-vis, NMR, and HR-ESI-MS techniques were used to analyze and characterize all the synthesized ligands and their corresponding metal complexes. Molecular structures of 1-3 were confirmed by the single-crystal-XRD analysis. Furthermore, the DNA binding ability of these complexes was checked through UV-vis, fluorescence spectroscopy, and also by circular dichroism studies. All the complexes were found to show an intercalation mode of binding with the K b value in the range of 10 4 -10 5  M -1 . Finally, 1-3 was tested against two malignant (HeLa and A549) and non-cancerous (NIH-3T3) cell lines to check their in vitro antiproliferative activities. Among all, 1 is the most cytotoxic of the series having IC 50 values of 5.7 ± 0.9 and 6.0 ± 0.3 μM against HeLa and A549 cell lines, respectively. This result is also consistent with the DNA binding order. Furthermore, the apoptotic mode of cell death of all the complexes was also evaluated by DAPI, AO/EB, and Annexin V-FITC/PI double staining assays., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Dual chalcogen-bonding interactions is proposed as a novel means for the conformational control of urea derivatives. The formation of a chalcogen-bonding interaction at both sides of the urea carbonyl group was unambiguously confirmed by X-ray diffraction as well as computational studies including non-covalent interaction (NCI) plot index analysis, quantum theory of atoms in molecules (QTAIM) analysis, and natural bond orbital (NBO) analysis via DFT calculations. By virtue of this dual interaction, urea derivatives that bear chalcogen atoms (X=S and Se) adopt a planar structure via the carbonyl oxygen (O) with an X⋅⋅⋅O⋅⋅⋅X arrangement on the same side of the molecule. The rigidity of the conformational lock was evaluated using the molecular arrangement in the crystal and the rotational barrier of benzochalcogenophene ring, which indicated a stronger conformational lock in benzoselenophene than in benzothiophene urea derivatives. Furthermore, the acidity of the urea derivatives increases according to the Lewis-acidic properties of the chalcogen-bonding interactions, whereby benzoselenophene urea is more acidic than benzothiophene urea. Tweezer-shaped urea derivatives were prepared, and their stereostructure proved the viability of the conformational control for defining the location of the substituents on the urea framework., (© 2023 Wiley-VCH GmbH.)

Invited for the cover of this issue are Shinobu Aoyagi (Nagoya City University), Takahiro Sasamori (University of Tsukuba), and Hideki Yorimitsu (Kyoto University). The image depicts multiply exo-methylated corannulenes (flowers) synthesized from corannulene (central large flower) by the reduction with sodium (soil) to form anionic corannulenes and the subsequent methylation with reduction-resistant dimethyl sulfate (butterflies). Read the full text of the article at 10.1002/chem.202301557., (© 2023 Wiley-VCH GmbH.)

Objective: This study was aimed to report the clinical characteristics of intramedullary schwannomas and discuss imaging findings and treatment strategies., Methods: The inclusion criterion was consecutive patients with intramedullary schwannomas who were surgically treated at 8 centers between 2009 and 2020. Clinical characteristics included age, sex, clinical presentation, disease duration, and follow-up period. The modified McCormick scale was used to compare the preoperative and postoperative conditions. Pre- and postoperative magnetic resonance images (MRI) of each case were analyzed., Results: The mean age of the total 11 patients at the operation was 50.2 years. The mean duration of the symptoms was 23 months, with limb paresthesia being the most common clinical presentation. The cervical spine was the most common localization level of the tumor in 6 cases. The mean follow-up duration was 49.4 months. Gross total resection (GTR) and subtotal resection (STR) was achieved in 9 and 2 cases, respectively. According to the modified McCormick scale at 6 months postoperatively, 7 cases (63.6%) had improved and 4 cases (36.3%) had unchanged grades. Typical MRI findings of the intramedullary schwannoma included ring-like enhancement, syringomyelia, cystic formation, intramedullary edema, and hemosiderin deposition. Gadolinium enhancement was homogenous in 8 cases (72.7%). The tumor margins were well demarcated in all cases., Conclusion: Intramedullary schwannoma should be considered when sharp margins and well-enhanced tumors are present at the cervical spine level and the initial symptoms are relatively mild, such as dysesthesia. When GTR cannot be achieved, STR for tumor decompression is recommended.

While analogues of allenes with heavier main-group elements (group 14-16) have been extensively studied, 2-heteraallenes are rare chemical species whose properties are mostly unknown. It is also notable that the synthesis and isolation of allene-type molecules are not widespread, despite the extensive study of two-coordinated low-valent chemical species.

In Japan, the recent series of sporadic outbreaks of human trichinellosis caused by Trichinella (Nematoda: Trichocephalida) has occurred owing to the consumption of raw or insufficiently cooked meat from wild bears. However, the infection status and molecular characteristics of Trichinella larvae in Japanese wild bears remain poorly understood. This study investigated the prevalence of Trichinella spp. in brown bears ( Ursus arctos ) from Hokkaido, and Japanese black bears ( Ursus thibetanus japonicus ) from three prefectures (Aomori, Akita, and Iwate) in northern Japan, between April 2019 and August 2022. Trichinella larvae were detected in 2.5% (6/236) of the brown bears and 0.9% (1/117) of the Japanese black bears. Sequence analysis using two genetic loci, the internal transcribed spacer region of nuclear ribosomal DNA and the mitochondrial cytochrome c oxidase subunit I gene, revealed that the larvae collected from the seven infected bears were identical to one of the two haplotypes of Trichinella T9. The prevalence of Trichinella T9 is low but is maintained in bears in the Hokkaido and Iwate prefectures suggesting that undercooked meat from these animals could cause human infection. Thus, continued health education campaigns are needed to raise awareness of the potential risk of trichinellosis among hunters, meat suppliers, consumers, and local governmental health agencies., Competing Interests: The authors declare that they have no conflicts of interest concerning this study., (© 2023 The Authors.)

Tricyclic 1,4-dihydro-1,4-phosphasilines 3a,b were synthesized from Si(NR 2 ) 2 -bridged imidazole-2-thione compounds 2a,b. Based on calculated FMOs of 3b, forecasting a possible P-selective P-N bond cleavage reduction, a redox cycle could be established using solutions of P-centred anionic derivative K[4b]. The cycle started with the oxidation of the latter to give the P-P coupled product 5b which could be chemically reduced by KC 8 to yield K[4b], again. All new products have been unambiguously confirmed in solution and solid state.

Five fluorescent ONO donor-based organotin(IV) complexes, [Sn IV (L 1-5 )Ph 2 ] ( 1-5 ), were synthesized by the one-pot reaction method and fully characterized spectroscopically including the single-crystal X-ray diffraction studies of 2-4 . Detailed photophysical characterization of all compounds was performed. All the compounds exhibited high luminescent properties with a quantum yield of 17-53%. Additionally, the results of cellular permeability analysis suggest that they are lipophilic and easily absorbed by cells. Confocal microscopy was used to examine the live cell imaging capability of 1-5 , and the results show that the compounds are mostly internalized in mitochondria and exhibit negligible cytotoxicity at imaging concentration. Also, 1-5 exhibited high photostability as compared to the commercial dye and can be used in long-term real-time tracking of cell organelles. Also, it is found that the probes ( 1-5 ) are highly tolerable during the changes in mitochondrial morphology. Thus, this kind of low-toxic organotin-based fluorescent probe can assist in imaging of mitochondria within living cells and tracking changes in their morphology.

We present the experimental visualization of the valence-electron-density distribution in benzene and its kinetically stabilized heavier-element analogues, i.e. , 1,2-disilabenzene and 1,2-digermabenzene. The valence-electron-density-distribution (EDD) analysis on the 1,2-disila- and 1,2-digermabenzenes revealed that these contain incompletely delocalized π electrons on their cyclic conjugation systems, making them less aromatic compared to benzene. Based on the results of this EDD analysis in combination with anisotropy of the current-induced density (ACID) calculations, considerable contributions from the characteristic resonance structures of 1,2-disila- and 1,2-digermabenzenes with cleaved EE bonds can be expected.

Persistent radicals have attracted increasing attention owing to their fascinating properties, including multi-step redox and long-wavelength absorption characteristics. In this study, boron complexes with π-extended nitroxide ligands were synthesised via Buchwald-Hartwig amination reactions of the corresponding boron-nitroxide complex and diarylamines. These nitroxide complexes exhibited two-step and reversible one-electron oxidation processes, suggesting stable redox triads involving anionic aminoxide, neutral nitroxide-radical, and cationic oxoammonium ligands. Cationic boron complexes of the nitroxide radical ligands were obtained via chemical oxidation of the aminoxide complexes and structurally characterised. The cationic nitroxide-radical complexes exhibited strong absorptions at approximately 1100 nm, demonstrating their potential as near-infrared (NIR)-II-active functional dyes.

Herein we report the synthesis of five new mononuclear mixed ligand oxidovanadium(IV) complexes [V IV O(L 1-3 )(L NN )] (1-5) with tridentate O,N,O-donor aroylhydrazones as main ligand (H 2 L 1-3 ) and N,N-chelating 2,2'-bipyridine (bipy) and 1,10-phenanthroline (phen) as co-ligand (L NN ). The complexes were characterized by elemental and thermogravimetric analysis (TGA), IR, UV-vis, and electron paramagnetic resonance (EPR) spectroscopy, electrospray ionization-mass spectrometry (ESI-MS) and cyclic voltammetry (CV). The structure of 1-5 was confirmed by single crystal X-ray analysis and also optimized by density functional theory (DFT) methods. At physiological pH an equilibrium [V IV O(L 1-3 )(L NN )] + H 2 O ⇄ [V IV O(L 1-3 )(H 2 O)] + L NN , shifted towards left, is established, with water molecule that could be replaced by the biomolecules of the organism. The studies on the interaction with two proteins, lysozyme (Lyz) chosen as a representative model of a small protein, and human serum albumin (HSA) show that two types of binding are possible: a non-covalent binding through the accessible residues on protein surface with [V IV O(L 1-3 )(L NN )] keeping its octahedral structure, and a covalent binding upon the replacement of water in [V IV O(L 1-3 )(H 2 O)] with His-N donors to form V IV O(L 1-3 )(HSA). In vitro cytotoxicity of ligands and complexes were screened against human cervical cancer (HeLa) (IC 50  = 7.39-15.13 μM), colon cancer (HT-29) (IC 50  = 11.04-28.20 μM) and mouse embryonic fibroblast (NIH-3T3) cell lines (IC 50  = 62.22-87.75 μM) by MTT assay. Particularly, 5 showed higher cytotoxicity than cisplatin and cyclophosphamide, with an IC 50 of 7.39 ± 1.21 μM and 11.04 ± 0.29 μM against HeLa and HT-29., (Copyright © 2022. Published by Elsevier Inc.)

A one-pot transformation of biaryl dicarboxylic acids to ( NH )-phenanthridinone derivatives based on a Curtius rearrangement and subsequent basic hydrolysis was developed. This method is also applicable for the preparation of optically active amide-functionalized [7]helicene-like molecules. Furthermore, aza[5]helicene derivatives with a phosphate moiety were isolated as a product of the Curtius rearrangement step in the case of substrates that bear chalcogen atoms. The stereostructures of these products, revealed by X-ray diffraction analysis, suggested that chalcogen-bonding and pnictogen-bonding interactions might contribute to their stabilization. The configurational stability of the helicene-like molecules and their chiroptical properties were further investigated.

The enantioselective reaction of imines bearing a cyano group as an activating group with malonic acid half thioesters gave chiral cyanamide derivatives with high enantioselectivity. The density functional theory (DFT) calculation clarified the stereochemical outcome and importance of the N -cyano group for imines.

The reduction of fullerene (C 60 ) with sodium dispersion in the presence of an excess amount of dipropyl sulfate was found to yield highly propylated fullerene, C 60 ( n C 3 H 7 ) n (max. n = 24), and C 60 ( n C 3 H 7 ) 20 was predominantly generated as determined by mass spectroscopy.

The preparation, optical resolution, and structural investigations of a series of axially chiral biaryl dicarboxylic acids bearing oxygen, sulfur, and selenium atoms were carried out. The crystal structures of sulfur- and selenium-containing derivatives revealed that the carboxy groups of these compounds are located in a co-planar geometry with the fused aromatic rings including the chalcogen atoms. These conformational controls were found to be achieved by chalcogen-bonding interactions between chalcogen atoms in the aromatic rings and oxygen atoms in the carboxy groups. Even in the case of a binaphthofuran derivative, in which the formation of chalcogen-bonding interactions was expected to be negligible, the carboxy groups were also found to be located in a co-planar geometry toward its fused cyclic rings. Natural bond orbital (NBO) analyses of these dicarboxylic acids indicated the formation not only for the chalcogen-bonding interactions for S and Se derivatives, but also the tetrel-bonding interactions between the oxygen atoms in the carboxy groups and the carbon atoms in the fused cyclic rings for all biaryl dicarboxylic acids. These tetrel-bonding interactions were thought to contribute to conformational control in the binaphthofuran derivative. Physical and chiroptical properties such as the racemization barriers and circular dichroism (CD) spectra of these biaryl dicarboxylic acids were also revealed.

Bridged indigos were synthesized by bridging the two nitrogen atoms in the indigo structure with a carbon chain, and their properties were carefully examined. These bridged indigos have intrinsic planar chirality, and the enantiomers were separated using chiral high-performance liquid chromatography. When the chiral bridged indigos were subjected to thermo- and photoisomerization, the corresponding ( Z )-indigo was not observed at all, and racemization was observed. This phenomenon is caused by the low activation energy of inversion due to the 1.5 bond order of the double bond of the indigo skeleton and the large energy difference between the ground states of ( E )-indigo and ( Z )-indigo.

Background: Weight gain (WG) is a frequently reported side effect of subthalamic deep brain stimulation; however, the underlying mechanisms remain unclear. The active contact locations influence the clinical outcomes of subthalamic deep brain stimulation, but it is unclear whether WG is directly associated with the active contact locations. We aimed to determine whether WG is associated with the subthalamic deep brain stimulation active contact locations., Methods: We enrolled 14 patients with Parkinson's disease who underwent bilateral subthalamic deep brain stimulation between 2013 and 2019. Bodyweight and body mass index were measured before and one year following the surgery. The Lead-DBS Matlab toolbox was used to determine the active contact locations based on magnetic resonance imaging and computed tomography. We also created sweet spot maps for WG using voxel-wise statistics, based on volume of tissue activation and the WG of each patient. Fluorodeoxyglucose-positron emission tomography data were also acquired before and one year following surgery, and statistical parametric mapping was used to evaluate changes in brain metabolism. We examined which brain regions' metabolism fluctuation significantly correlated with increased body mass index scores and positron emission tomography data., Results: One year after surgery, the body mass index increase was 2.03 kg/m 2 . The sweet spots for WG were bilateral, mainly located dorsally outside of the subthalamic nucleus (STN). Furthermore, WG was correlated with increased metabolism in the left limbic and associative regions, including the middle temporal gyrus, inferior frontal gyrus, and orbital gyrus., Conclusions: Although the mechanisms underlying WG following subthalamic deep brain stimulation are possibly multifactorial, our findings suggest that dorsal stimulation outside of STN may lead to WG. The metabolic changes in limbic and associative cortical regions after STN-DBS may also be one of the mechanisms underlying WG. Further studies are warranted to confirm whether dorsal stimulation outside of STN changes the activities of these cortical regions., (© 2021. The Author(s).)

Quadruply BN-fused tetrathia[8]circulenes were synthesized through four-fold electrophilic borylation. The single-crystal X-ray diffraction analysis revealed that the BN-fused tetrathia[8]circulene with peripheral phenyl groups exhibits crystal polymorphism, in which the circulene core adopts both planar and saddle conformations in the solid state. The experimental and theoretical studies revealed that the weaker aromaticity of azaborine compared with benzene renders the flexibility of the BN-fused tetrathia[8]circulenes., (© 2021 Wiley-VCH GmbH.)

Self-assembly of π-conjugated molecules in solution generally occurs owing to either an enthalpic or an entropic gain; however, designing π-conjugated systems that simultaneously exhibit enthalpically and entropically favorable self-assembly behavior is challenging. Herein, the self-assembly behavior of tetraazatetrathia[8]circulenes is disclosed, which is driven by both enthalpy and entropy. Single-crystal X-ray diffraction analysis demonstrated that molecules of these tetraazatetrathia[8]circulenes form face-to-face stacked dimers with a 1D columnar structure owing to the circularly arranged dipole moments. Importantly, concentration- and temperature-dependent 1 H NMR spectra revealed that the formation of self-assemblies of tetraazatetrathia[8]circulenes in chloroform and methanol is favored by both enthalpic and entropic factors. The unique association behavior is due to the presence of sp 2 -hybridized nitrogen atoms, which weakly coordinate to the hydrogen atoms of these solvents and reduce the π-electron density of the circulene cores., (© 2020 Wiley-VCH GmbH.)

Reactions of isolable disilynes and digermynes with alkynes can result in the formation of the corresponding disila- (DSBs) and digermabenzenes (DGBs), wherein two carbon atoms of the benzene ring are replaced by silicon or germanium atoms. Detailed structural and spectroscopic analyses of these DSBs and DGBs have revealed that they exhibit considerable aromaticity, comparable to that of benzene. However, in contrast to the all-carbon system benzene, these DSBs and DGBs are highly reactive toward small molecules such as oxygen, hydrogen, 1,3-dienes, and water. During the investigation of their reactivity, we discovered that a 1,2-DGB works as a catalyst for the cyclotrimerization of arylalkynes, which provides access to the corresponding 1,2,4-triarylbenzenes. In this perspective article, our recent progress in the area of DSB and DGB chemistry is summarized., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Here we report an anionic meso -tetrakis(4-carboxymethylthio-2,3,5,6-tetrafluorophenyl) zinc porphyrin (ZnTF 4 PPTC 4- ) to form a supramolecular complex with a cationic lithium endohedral [60]fullerene (Li + @C 60 ). The supramolecular ZnTF 4 PPTC 4- /Li + @C 60 complex formed by strong electrostatic attraction with a large binding constant generates a long-lived charge-separated (CS) state with low energy loss by photoinduced electron transfer from ZnTF 4 PPTC 4- to Li + @C 60 . The anionic fluorinated zinc porphyrin with high oxidation potential reduces the energy loss associated with the charge separation and enhances the energy level of the CS state. The energy level of the CS state determined by electrochemical measurements is at 0.94 eV, which is much higher than that of a similar supramolecular complex using an anionic meso -tetrakis(sulfonatophenyl) zinc porphyrin (ZnTPPS 4- ) at 0.55 eV. Time-resolved transient absorption spectroscopy demonstrates that ZnTF 4 PPTC 4- /Li + @C 60 generates a long-lived CS state with a lifetime of 0.29 ms in a binary solvent of acetonitrile and chlorobenzene. The lifetime of the CS state is comparable to that of ZnTPPS 4- /Li + @C 60 in benzonitrile.

Divalent silicon species, the so-called silylenes, represent attractive organosilicon building blocks. Isolable stable silylenes remain scarce, and in most hitherto reported examples, the silicon center is stabilized by electron-donating substituents (e.g., heteroatoms such as nitrogen), which results in electronic perturbation. In order to avoid such electronic perturbation, we have been interested in the chemistry of reactive silylenes with carbon-based substituents such as ferrocenyl groups. Due to the presence of a divalent silicon center and the redox-active transition metal iron, ferrocenylsilylenes can be expected to exhibit interesting redox behavior. Herein, we report the design and synthesis of a bis(ferrocenyl)silirane as a precursor for a bis(ferrocenyl)silylene, which could potentially be used as a building block for redox-active organosilicon compounds. It was found that the isolated bis(ferrocenyl)siliranes could be a bottleable precursor for the bis(ferrocenyl)silylene under mild conditions.

We designed and synthesized a novel Si-rhodamine derivative, NORD-1, as a red-light-controllable nitric oxide (NO) releaser, on the basis of photoredox parameter analysis. Red-light-responsive NO release from NORD-1 was confirmed by ESR spin trapping and quantified with an NO electrode and by means of Griess assay. The NO release cross section (ε 656 nm ·Φ NO ) of NORD-1 was calculated to be 3.65 × 10 2 , which is larger than that of a previously reported yellowish-green-light-controllable NO releaser, NO-Rosa5. The photoresponsiveness of NO release from NORD-1 was precise and efficient enough to induce vasodilation ex vivo under Magnus test conditions. Finally, we showed that intracavernous pressure (ICP) could be controlled in rats in vivo with the combination of NORD-1 and a red-light source without increasing systemic blood pressure, which is a serious side effect of usual NO releasers, such as nitroglycerin and isopentyl nitrite. NORD-1 is expected to be a useful chemical tool for NO research, as well as a candidate agent to control the circulatory system.

Several examples of stable low-coordinated species of heavier group 14 elements (Si, Ge, Sb, Pb) such as divalent species and multiple-bond compounds have been reported. With the goal in mind to create unprecedented low-coordinated species of heavier group 14 elements that exhibit considerably increased redox stability, ferrocenyl (Fc)-substituted low-coordinated species of heavier group 14 elements were designed. In this short account article, recent progress on the synthesis of Fc-based low-coordinated species of heavier group 14 elements is summarized.

An S N 2 mechanism was proposed for highly stereoselective glycosylation of benzoic acid with unprotected α-d-glucose under Mitsunobu conditions in dioxane, while an S N 1 mechanism was indicated for nonstereoselective glycosylation in DMF. The S N 2-type stereoselective Mitsunobu glycosylation is generally applicable to various unprotected pyranoses as glycosyl donors in combination with a wide range of acidic glycosyl acceptors such as carboxylic acids, phenols, and imides, retaining its high stereoselectivity (33 examples). Glycosylation of a carboxylic acid with unprotected α-d-mannose proceeded also in an S N 2 manner to directly afford a usually less accessible 1,2- cis -mannoside. One- or two-step total syntheses of five simple natural glycosides were performed using the glycosylation strategy presented here using unprotected α-d-glucose.

The toxicity of lead perovskite hampers the commercialization of perovskite-based photovoltaics. While tin perovskite is a promising alternative, the facile oxidation of tin(II) to tin(IV) causes a high density of defects, resulting in lower solar cell efficiencies. Here, we show that tin(0) nanoparticles in the precursor solution can scavenge tin(IV) impurities, and demonstrate that this treatment leads to effectively tin(IV)-free perovskite films with strong photoluminescence and prolonged decay lifetimes. These nanoparticles are generated by the selective reaction of a dihydropyrazine derivative with the tin(II) fluoride additive already present in the precursor solution. Using this nanoparticle treatment, the power conversion efficiency of tin-based solar cells reaches 11.5%, with an open-circuit voltage of 0.76 V. Our nanoparticle treatment is a simple and broadly effective method that improves the purity and electrical performance of tin perovskite films.

1,2-Insertion reactions of alkynes into the Ge-C bonds in dibromodigermenes afford stable crystalline bromovinylgermylenes. In contrast to previously reported Lewis-base-supported vinylgermylenes, the bromovinylgermylene obtained from reaction of the bromogermylene with 3-hexyne via such an 1,2-insertion is a donor-free monomer. A feasible reaction mechanism, proposed on the basis of the observed experimental results in combination with theoretical calculations, suggests that the [1+2]-cycloadduct and the insertion product are the kinetic and thermodynamic product, respectively.

A general method for alkali-metal-promoted reductive difunctionalization of alkenes has been developed by means of reduction-resistant alkoxy-substituted electrophiles. A series of 1,2-diboration and 1,2-dicarbofunctionalization products can be synthesized by employing trimethoxyborane and strained cyclic ethers such as oxirane and oxetane. In addition, unsymmetrical carbo- or thioborations have been accomplished via sequential treatment with trimethoxyborane and carbon or sulfur electrophiles.

Rationale: Rosette-forming glioneuronal tumor (RGNT) is a rare tumor which has been first reported as the fourth ventricle tumor by Komori et al and is classified as a distinct clinicopathological entity by the WHO Classification of Tumors of the Central Nervous System as in 2007. Although RGNTs were reported to occur in both supratentorial and inflatentorial sites, only 4 case reports of spinal RGNT have been demonstrated., Patient Concerns: A 37-year-old female presenting with slowly progressing right-sided clumsiness. Cervical magnetic resonance imaging revealed a spinal intramedullary tumor between the C2 and C5 levels., Diagnoses: Pathological analysis showed unique biphasic cellular architecture consisting of perivascular pseudorosettes dominantly with few neurocytic rosettes and diffuse astrocytoma component. The tumor cells composed of perivascular pseudorosettes showed positivity for both synaptophysin and glial markers such as GFAP and Olig2. Therefore, the diagnosis of RGNT was made., Interventions: Gross total resection of the tumor was achieved. No adjuvant chemotherapy nor radiotherapy was conducted after operation., Outcomes: At 2 years after the operation, no recurrence was observed., Lessons: Although RGNT arising from the spinal cord is extremely rare, we need to consider the tumor as a differential diagnosis for intramedullary spinal cord tumors.

Background: Because spinal dural arteriovenous fistulae (SDAVF) are rare and their clinical presentation is nonspecific, they are often overlooked during diagnostic evaluations. Typical magnetic resonance imaging (MRI) findings are intramedullary T2-weighted signal hyperintensity and perimedullary flow voids. There are few reports on the characteristic signs of the cauda equina. We assessed the significance of a new imaging parameter, the cauda equina occupation ratio (CEOR), for the evaluation of SDAVF., Methods: We retrospectively analyzed the clinical charts and radiological findings of 20 SDAVF patients treated at our institutions. We evaluated sagittal T2-weighted MRI scans and assessed the CEOR, the occupation ratio of the cauda equina compared to the sagittal diameter of the corresponding lumbar spinal canal. The controls were 21 age- and sex-matched subjects., Results: Of the 20 SDAVF, 10 were at the thoracic and 10 at the lumbar spine. There was no significant difference between the preoperative CEOR and the spinal level of the fistulae or the neurological signs. On preoperative MRI scans, the mean CEOR was 56.0 ± 7.8; postoperatively, it was 37.1 ± 7.4 (P = 0.000). The preoperative CEOR was significantly larger in SDAVF patients than in the controls (P = 0.000); postoperatively, it was smaller than in the controls (P = 0.14)., Conclusions: The preoperative CEOR was larger in patients with SDAVF than in the controls. It normalized after successful occlusion of the fistula. Our findings indicate that the CEOR is a useful parameter for the pre- and postoperative evaluation of SDAVF., (Copyright © 2019 Elsevier Inc. All rights reserved.)

A high-purity methylammonium lead iodide complex with intercalated dimethylformamide (DMF) molecules, CH 3 NH 3 PbI 3 ⋅DMF, is introduced as an effective precursor material for fabricating high-quality solution-processed perovskite layers. Spin-coated films of the solvent-intercalated complex dissolved in pure dimethyl sulfoxide (DMSO) yielded thick, dense perovskite layers after thermal annealing. The low volatility of the pure DMSO solvent extended the allowable time for low-speed spin programs and considerably relaxed the precision needed for the antisolvent addition step. An optimized, reliable fabrication method was devised to take advantage of this extended process window and resulted in highly consistent performance of perovskite solar cell devices, with up to 19.8 % power-conversion efficiency (PCE). The optimized method was also used to fabricate a 22.0 cm 2 , eight-cell module with 14.2 % PCE (active area) and 8.64 V output (1.08 V/cell)., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A stable 1,4-disilabenzene was generated from the reaction of a stable disilyne with 3-hexyne. Its photochemical isomerization afforded the corresponding disilabenzvalene, which was structurally characterized by a single-crystal X-ray diffraction analysis.

Reduction of alkynes with alkali metals in the presence of B 2 pin 2 results in diboration of alkynes. Distinct from conventional dissolving metal hydrogenations, two carbon-boron bonds and also two carbon-alkali metal bonds can be constructed in one operation to form 1,2-diboryl-1,2-dimetalloalkanes. The 1,2-diboryl-1,2-dimetalloalkanes generated are readily convertible to a wide range of vicinal bis(boronate)s. In particular, oxidation of the 1,2-dianionic species provides ( E)-1,2-diborylalkenes, unique anti-selective diboration of alkynes being thus executed.

Purpose: Spinal angiography is the gold standard for evaluation or diagnosis of spinal arteriovenous malformations (AVMs). However, some feeding arteries might be overlooked when multiple feeders exist. This study aimed to retrospectively review cases of spinal intra-dural AVMs, which were identified by three-dimensional digital subtraction angiography (3D-DSA), and attempted to estimate the number of feeding arteries., Methods: We retrospectively reviewed patients with spinal intra-dural AVMs who underwent 3D-DSA at Hokkaido University Hospital from January 2005 to December 2016. We selected 9 patients in whom we could obtain data of multi-planar reconstruction of 3D-DSA. We measured the computed tomography (CT) values of feeding arteries and draining veins. The CT values represented the averages of maximum CT values of 5 continuous axial slices. The ratio of the CT value of feeders to that of drainers (F/D ratio) was calculated. The correlation between the F/D ratio and the number of feeders was examined with Pearson's correlation coefficient., Results: The average number of feeders was 2.3 (1-4), and the number of feeders was significantly positively correlated with the F/D ratio (r = 0.855, P = .003)., Conclusions: We conclude that the number of feeding arteries of spinal intra-dural AVMs can be estimated by using the F/D ratio obtained from 3D-DSA. These slides can be retrieved under Electronic Supplementary Material.

The first examples of stable, crystalline, and air-sensitive 1,4-digermabenzenes were isolated. These species photochemically isomerize into the corresponding air-stable digerma-Dewar-benzenes. More importantly, alkyl-substituted Dewar-type-1,4-digermabenzenes can be considered as reversible "air-stable activators" for small molecules such as dihydrogen, carbon dioxide, and acetylene at room temperature. The regeneration of these activators can be accomplished via a thermal retro-isomerization that affords the corresponding 1,4-digermabenzenes.

Spatiotemporally controllable nitric oxide (NO) releasers are required for biological studies and as candidate therapeutic agents. Here, we investigate the structure-efficiency relationship of a series of photoinduced electron transfer-triggered NO releasers based on our reported yellowish-green light-controllable NO releaser, NO-Rosa. The distance between the NO-releasing N-nitrosoaminophenol moiety and the rosamine antenna moiety was critical for efficient NO release. Notably, substitution at the phenolic hydroxyl group blocked NO release. We synthesized NO-Rosa-Gal bearing D-galactose (Gal) at this location, and showed that hydrolysis by β-galactosidase restored the photoresponse. This represents proof-of-concept of a strategy for highly specific control of NO release by using a double-lock system involving both enzymatic reactivation and photo-control.

Dimetallynes (RE≡ER; E=Si, Ge, Sn, Pb), i.e., systems that contain triple bonds between heavier group-14 elements represent the heavier homologues of alkynes. The high reactivity of disilynes, digermynes, distannynes, and diplumbynes can be interpreted in terms of their unique bonding situation, which includes a trans-bent structure, a small HOMO-LUMO gap, a partial diradical character, their electronic nature, and interactions between bulky substituents. Relatively recent developments in the area of sterically demanding substituents have permitted isolating some stable compounds with a triple bond between heavier group-14 elements. The structural features of these triple-bonded compounds and their reactivity toward small molecules have been investigated using experimental and theoretical approaches. This review focuses on recent developments regarding the reactivity of stable compounds with a triple bond between heavier group-14 elements toward small molecules, where the results were examined using quantum chemical methods. A comprehensive review on carbon chemistry is beyond the scope of this focus review., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A stable 3,5-diphenyl-1,2-disilabenzene was selectively synthesized by the reaction between the isolable disilyne TbbSi[triple bond, length as m-dash]SiTbb (Tbb = 2,6-[CH(SiMe3)2]2-4-t-Bu-phenyl) with phenylacetylenes. Its molecular structure and physical properties were examined and compared to those of the 1,2-disilabenzene that was obtained from the reaction between TbbSi[triple bond, length as m-dash]SiTbb and acetylene. Moreover, a plausible formation mechanism for this reaction is discussed.

A stable crystalline 2,5-digermaselenophene was synthesized. In contrast to hitherto reported selenophenes, this digermaselenophene exhibits a trans-pyramidalized structure, which is due to its electronic properties. The practical utility of this 2,5-digermaselenophene is reflected in its ability to activate dihydrogen and acetylene at room temperature in the absence of a transition-metal complex, and this behavior can be rationalized on the basis of its physicochemical properties, which are characterized by considerable electron-donating and -accepting abilities.

Tetrylones (ylidones) represent a class of zero-valent group 14 compounds with the general formula EL 2 (E=C, Si, Ge, Sn, or Pb; L=neutral σ-donating ligand), wherein the tetrel atom, E(0), possess its four valence electrons in the form of two electron lone pairs, and is moreover coordinated by two ligands (L) via donor-acceptor interactions (L→E←L). This review focuses on the synthesis, structure, reactivity, and computational examination of the isolable heavier tetrylones (Si, Ge, Sn) that have been discovered recently. A comprehensive review on carbone chemistry is beyond the scope of this review. It should also be noted that tetrylones contain two different types of lone pairs, that is, one that exhibits p-type and one that exhibits s-type characteristics. Different behavior should thus be expected when these lone pairs react with Lewis acids., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Bis(methylene)-λ 4 -sulfane 1, a >C=S=C< heterocumulene, was obtained as a red crystalline solid from the reaction between elemental sulfur and a carbenoid that contains sterically demanding silylalkyl groups. Under atmospheric conditions, and even at elevated temperatures, 1 exhibits extraordinary stability. The molecular structure and electron-density distribution of 1 were analyzed by single-crystal X-ray diffraction analysis, which revealed a bent C=S=C geometry with C=S=C π-bonds. These results, combined with those of variable-temperature NMR measurements and theoretical calculations suggest a slow rotation of the S=C moieties in 1, the stability and structure of which were further examined by theoretical calculations., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)