Showing papers by "Hiroshi Nishihara published in 2020"
TL;DR: This work explores a new area of organosilicon chemistry, and presents a potential utility of disilanyl macrocycle C4 possessing four p-phenylenes circularly connected by four flexible disilane bonds as soft crystals.
Abstract: We describe here the preparation of soft crystals using disilanyl macrocycle C4 possessing four p-phenylenes circularly connected by four flexible disilane bonds Single crystals of C4 exhibited a reversible thermal single-crystal-to-single-crystal (SCSC) phase transition behavior between two crystal phases accompanied by remarkable mechanical motion (thermosalient effect), as revealed by thermal analyses and X-ray diffraction measurements Detailed structural analyses implied that flexibility of the parallelogram disilanyl architecture and molecular packing mode via weak intermolecular interactions facilitated a concerted structural transformation (parallel crank motion) of macrocycles in the crystal, thus resulting in the SCSC phase transition accompanied by anisotropic shrinking/elongation of the cells to induce the thermosalient effect This work explores a new area of organosilicon chemistry and presents the potential utility of disilanyl macrocycles as soft crystals
32 citations
TL;DR: Coordination polymers represent a suitable model to study redox mechanisms in materials where both metal cation and ligand undergo electrochemical reactions and are capable to proceed through rever... as mentioned in this paper.
Abstract: Coordination polymers represent a suitable model to study redox mechanisms in materials where both metal cation and ligand undergo electrochemical reactions and are capable to proceed through rever...
24 citations
TL;DR: Combined treatment with alectinib and EGFR-TKIs, such as erlotin ib and osimertinib, successfully controlled progression of LMC and indicate the potential of novel therapies targeting both ALK and EG FR for the treatment of ALK-TKI-resistant LMC in AlK-rearranged NSCLC.
20 citations
TL;DR: Compounds 1–6 were characterized experimentally by multinuclear NMR spectroscopy and X‐ray crystallography and computationally using a set of real‐space bond indicators (RSBIs) derived from electron density methods including Atoms In Molecules (AIM), the Electron Localizability Indicator (ELI‐D) as well as the Non‐Covalent Interaction (NCI) Index.
Abstract: The reaction of 2,6-F2 C6 H3 SiMe3 with Ph2 PLi provided 2,6-(Ph2 P)2 C6 H3 SiMe3 (1), which can be regarded as precursor for the novel anionic tridentate ligand [2,6-(Ph2 P)2 C6 H3 ]- (PCP)- . The reaction of 1 with [AuCl(tht)] (tht=tetrahydrothiophene) afforded 2,6-(Ph2 PAuCl)2 C6 H3 SiMe3 (2). The subsequent reaction of 2 with CsF proceeded with elimination of Me3 SiF and yielded the neutral tetranuclear complex linear-[Au4 Cl2 (PCP)2 ] (3) comprising a string-like arrangement of four Au atoms. Upon chloride abstraction from 3 with NaBArF4 (ArF =3,5-(CF3 )2 C6 H3 ) in the presence of tht, the formation of the dicationic tetranuclear complex linear-[Au4 (PCP)2 (tht)2 ](BArF4 )2 (4) was observed, in which the string-like structural motif is retained. Irradiation of 4 with UV light triggered a facile rearrangement in solution giving rise to the dicationic tetranuclear complex cyclo-[Au4 (PCP)2 (tht)2 ](BArF4 ) (5), which comprises a rhomboidal motif of four Au atoms. In 3-5, the Au atoms are associated by a number of significant aurophilic interactions. The atom-economic and selective reaction of 3 with HgCl2 yielded the neutral trinuclear bimetallic complex [HgAu2 Cl3 (PCP)] (6) comprising significant metallophilic interactions between the Au and Hg atoms. Therefore, 6 may be also regarded as a metallopincer complex [ClHg(AuCAu)] between HgII and the anionic tridentate ligand [2,6-(Ph2 PAuCl)2 C6 H3 ]- (AuCAu)- containing a central carbanionic binding site and two "gold-arms" contributing pincer-type chelation trough metallophilic interactions. Compounds 1-6 were characterized experimentally by multinuclear NMR spectroscopy and X-ray crystallography and computationally using a set of real-space bond indicators (RSBIs) derived from electron density (ED) methods including Atoms In Molecules (AIM), the Electron Localizability Indicator (ELI-D) as well as the Non-Covalent Interaction (NCI) Index.
19 citations
TL;DR: The results suggest the general nature of magnetic field effects on the luminescence of radicals as well as the importance of the type of interaction between radicals.
19 citations
TL;DR: Genomic examination of cytology samples was conventionally performed on cell block or smear specimens than on residual liquid‐based cytology specimens, which are high‐quality DNA sources even after long‐term storage.
Abstract: BACKGROUND Cancer genome profiling of cytology specimens using next-generation sequencing (NGS) requires adequate and good-quality DNA. Genomic examination of cytology samples was conventionally performed on cell block (CB) or smear specimens than on residual liquid-based cytology (LBC) specimens, which are high-quality DNA sources even after long-term storage. METHODS We estimated tumor fractions of 37 residual LBC specimens, including 30 fine needle aspiration (FNA) samples from the thyroid (12 papillary thyroid carcinomas and two malignant lymphomas), lymph node (13 metastatic carcinomas and one malignant lymphoma), and breast cancer (one phyllodes tumor and one invasive ductal carcinoma), two pancreatic carcinoma samples, and five liquid (ascites, pleural effusion, and cerebrospinal fluid) samples. The DNA was extracted from all samples and subjected to NGS using a customized cancer gene panel comprising 28 cancer-related genes. RESULTS NGS analysis revealed somatic mutations corresponding to pathological diagnosis with adequate variant allele frequency (VAF) in 24 LBC specimens, which had significantly higher tumor fraction (72.5% ± 4.9%). Ten cases, including the five fluid samples, had very small tumor fractions (7.5% ± 2.3%) to obtain sufficient VAF. Other two samples had high tumor fractions but showed very low VAF, indicating the presence of fusion genes. The remaining one sample yielded no DNA recovery. CONCLUSION The residual LBC specimens collected by FNA from the thyroid gland and lymph node were verified to carry high tumor fraction and could serve as an alternate source for molecular testing to screen and diagnose cancers without the use of CB or smears.
19 citations
TL;DR: This provisional clinical opinion proposes the requirements for performing dMMR testing properly to select patients who are likely to benefit from immune checkpoint inhibitors and administering them safely.
Abstract: Novel therapeutic agents have improved survival outcomes in patients with advanced solid tumors In parallel, the development of predictive biomarkers to identify patients who are likely to benefit from a certain treatment has also contributed to the improvement of survival Recently, clinical trials have reported the efficacy of immune checkpoint inhibitors in the treatment of mismatch repair-deficient (dMMR) advanced solid tumors In Japan, a PD-1 inhibitor for dMMR advanced solid tumors, regardless of the primary tumor site, has been approved However, there are some issues related to administering immune checkpoint inhibitors in the clinical practice setting, making it necessary to develop the guidelines Clinical questions (CQs) regarding medical care were formulated for patients with dMMR advanced solid tumors, and evidence to the CQs was collected by manual search to prepare recommendations Then, the committee members voted to determine the level of each recommendation considering the strength of evidence, expected risks and benefits to patients, and other factors The current guideline, which we consider a provisional clinical opinion at this point, describes the 11 requirements to be considered in terms of patients for whom dMMR testing is recommended, the timing and methods of dMMR testing, and clinical care systems required to perform dMMR testing properly and to administer immune checkpoint inhibitors safely This provisional clinical opinion proposes the requirements for performing dMMR testing properly to select patients who are likely to benefit from immune checkpoint inhibitors and administering them safely
18 citations
TL;DR: This study shows that targeted agents can be detected in approximately 40% of malignant ovarian tumors via multigene panel testing, and copy number alteration count can be a useful marker to help assess risks in malign ovarian tumor patients.
Abstract: Precision medicine based on cancer genomics is being applied in clinical practice. However, patients do not always derive benefits from genomic testing. Here, we performed targeted amplicon exome sequencing-based panel tests, including 160 cancer-related genes (PleSSision-160), on 88 malignant ovarian tumors (high-grade serous carcinoma, 27; endometrioid carcinoma, 15; clear cell carcinoma, 30; mucinous carcinoma, 6; undifferentiated carcinoma, 4; and others, 6 (immature teratoma, 1; carcinosarcoma, 3; squamous cell carcinoma, 1; and mixed, 1)), to assess treatment strategies and useful biomarkers for malignant ovarian tumors. Overall, actionable gene variants were found in 90.9%, and druggable gene variants were found in 40.9% of the cases. Actionable BRCA1 and BRCA2 variants were found in 4.5% of each of the cases. ERBB2 amplification was found in 33.3% of mucinous carcinoma cases. Druggable hypermutation/ultramutation (tumor mutation burden ≥ 10 SNVs/Mbp) was found in 7.4% of high-grade serous carcinoma, 46.7% of endometrioid carcinoma, 10% of clear cell carcinoma, 0% of mucinous carcinoma, 25% of undifferentiated carcinoma, and 33.3% of the other cancer cases. Copy number alterations were significantly higher in high-grade serous carcinoma (P < .005) than in other histologic subtypes; some clear cell carcinoma showed high copy number alterations that were correlated with advanced stage (P < .05) and worse survival (P < .01). A high count of copy number alteration was associated with worse survival in all malignant ovarian tumors (P < .05). Our study shows that targeted agents can be detected in approximately 40% of malignant ovarian tumors via multigene panel testing, and copy number alteration count can be a useful marker to help assess risks in malignant ovarian tumor patients.
17 citations
TL;DR: In this article, the authors proposed a guideline for the diagnosis and use of immunotherapy in patients with deficient DNA mismatch repair (DMM) tumors, where the authors formulated clinical questions regarding medical care for patients with NTRK-positive advanced solid tumors.
Abstract: The development of novel antitumor agents and accompanying biomarkers has improved survival across several tumor types. Previously, we published provisional clinical opinion for the diagnosis and use of immunotherapy in patients with deficient DNA mismatch repair tumors. Recently, efficacy of tropomyosin receptor kinase inhibitors against neurotrophic receptor tyrosine kinase (NTRK) fusion gene-positive advanced solid tumors have been established as the second tumor-agnostic treatment, making it necessary to develop the guideline prioritized for these patients. Clinical questions regarding medical care were formulated for patients with NTRK-positive advanced solid tumors. Relevant publications were searched by PubMed and Cochrane Database. Critical publications and conference reports were added manually. Systematic reviews were performed for each clinical question for the purpose of developing clinical recommendations. The committee members identified by Japan Society of Clinical Oncology (JSCO) and Japanese Society of Medical Oncology (JSMO) voted to determine the level of each recommendation considering the strength of evidence, expected risks and benefits to patients, and other related factors. Thereafter, a peer review by experts nominated from JSCO, JSMO, and Japanese Society of Pediatric Hematology/Oncology, and the public comments among all Societies’ members was done. The current guideline describes 3 clinical questions and 15 recommendations for whom, when, and how NTRK fusion should be tested, and what is recommended for patients with NTRK fusion-positive advanced solid tumors. In the NTRK guideline, the committee proposed 15 recommendations for performing NTRK testing properly to select patients who are likely to benefit from tropomyosin receptor kinase inhibitors.
16 citations
TL;DR: This PDX model (EMPD-PDX-H1) could be a powerful tool for the research and development of EMPD treatments.
Abstract: Although the prognosis of advanced extramammary Paget's disease (EMPD) is poor, there have been no preclinical research models for the development of novel therapeutics. This study aims to establish a preclinical research model for EMPD. We transplanted EMPD tissue into immunodeficient NOD/Scid mice. Histopathological and genetic analyses using a comprehensive cancer panel were performed. For in vivo preclinical treatments, trastuzumab, lapatinib, docetaxel, or eribulin were administered to patient-derived xenograft (PDX) models. Tissue transplanted from the EMPD patient was enlarged in NOD/Scid mice and was transplanted into further generations. Both the transplantation of PDX into nu/nu mice and the reanimation of the cryopreserved xenografted tumors in NOD/Scid mice were successful. We also established an EMPD-PDX-derived primary cell culture. Histopathologically, the xenografted tumors were positive for CK7, which was consistent with the patient's tumors. Genetically, the pathogenic mutation ERBB2 S310F was detected in the patient's tumors (primary intraepidermal lesion, metastatic lymph node) and was observed in the xenografted tumors even after continued passages. The xenografted tumors responded well to trastuzumab and lapatinib therapy. Also, cytotoxic agents (docetaxel and eribulin) were effective against the xenografted tumors. This PDX model (EMPD-PDX-H1) could be a powerful tool for the research and development of EMPD treatments.
14 citations
TL;DR: The results of the present study prove the feasibility of implementing in‐house clinical sequencing as a promising laboratory examination technique for precision cancer medicine.
Abstract: Precision medicine is a promising strategy for cancer treatment. In this study, we developed an in-house clinical sequencing system to perform a comprehensive cancer genomic profiling test as a clinical examination and analyzed the utility of this system. Genomic DNA was extracted from tumor tissues and peripheral blood cells collected from 161 patients with different stages and types of cancer. A comprehensive targeted amplicon exome sequencing for 160 cancer-related genes was performed using next-generation sequencing (NGS). The sequencing data were analyzed using an original bioinformatics pipeline, and multiple cancer-specific gene alterations were identified. The success rate of our test was 99% (160/161), while re-biopsy was required for 24% (39/161) of the cases. Potentially actionable and actionable gene alterations were detected in 91% (145/160) and 46% (73/160) of the patients, respectively. The actionable gene alterations were frequently detected in PIK3CA (9%), ERBB2 (8%), and EGFR (4%). High tumor mutation burden (TMB) (≥10 mut/Mb) was observed in 12% (19/160) of the patients. The secondary findings in germline variants considered to be associated with hereditary tumors were detected in 9% (15/160) of the patients. Seventeen patients (11%, 17/160) were treated with genotype-matched therapeutic agents, and the response rate was 47% (8/17). The median turnaround time for physicians was 20 days, and the median survival time after the initial visit was 8.7 months. The results of the present study prove the feasibility of implementing in-house clinical sequencing as a promising laboratory examination technique for precision cancer medicine.
09 Apr 2020
TL;DR: The prognosis for women with high-grade endometrial cancers is poor, with little improvement in the last two decades, and biomarkers predicting chemotherapeutic benefits have not been defined.
Abstract: The prognosis for women with high-grade endometrial cancers is poor, with little improvement in the last two decades. The mainstay of treatment is surgery (hysterectomy) with or without lymphadenectomy. Although adjuvant radiotherapy is considered standard for high-risk endometrial cancers, the added value of chemotherapy has been the subject of recent trials. However, biomarkers predicting chemotherapeutic benefits have not been defined. BRCA1 and BRCA2 encode proteins that repair breaks in doublestranded DNA via the homologous recombination repair (HRR) pathway, and mutations in these genes cause HRR deficiency. Recently, other mutations were reported in ovarian cancers, such as those in Fanconi anemia genes (eg, PALB2 [FANCN], BRIP1 [FANCJ], and RAD51C) and other genes involved in HRR (eg, ATM, BARD1, NBN, CDK12, TP53, and CHEK2).
TL;DR: Dysregulated EP4 overexpression in VSMCs promotes inflammatory monocyte/macrophage infiltration and attenuates elastin/collagen fiber formation, leading to AAAs exacerbation, and inhibition of IL-6 prevented Ang II–induced AAA formation in EP4-Tg.
Abstract: Objective: Excessive prostaglandin E2 production is a hallmark of abdominal aortic aneurysm (AAA). Enhanced expression of prostaglandin E2 receptor EP4 (prostaglandin E receptor 4) in vascular smoo...
TL;DR: Density functional theory calculations indicate that the energy levels of the antibonding orbitals around the metals and interlayer spaces are important factors in tailoring the electrochemical properties of CoxNi1-xDI.
Abstract: Bis(diimino)metal coordination frameworks (MDI, M = transition metal), which are a class of metal organic frameworks with two-dimensional anisotropy, high electric conductivity, and redox activity,
TL;DR: This research presents a novel probabilistic procedure called “spot-spot analysis” that allows for real-time analysis of the response of the immune system to foreign substance abuse.
TL;DR: The electrochemical reaction during pre-doping formed a high-quality solid electrolyte interface (SEI) on the surface of silicon particles, which improved the charge and discharge cycle life with a small irreversible capacity.
Abstract: Electrochemical pre-doping of a silicon electrode was investigated to create a new class of rechargeable battery with higher energy density. The electrochemical reaction during pre-doping formed a high-quality solid electrolyte interface (SEI) on the surface of silicon particles, which improved the charge and discharge cycle life with a small irreversible capacity. The surface composition of the pre-doped silicon particles was characterized using transmission electron microscopy (TEM), solid state magic-angle-spinning (MAS) nuclear magnetic resonance (NMR) and X-ray diffraction analysis (XRD). Pressurization promoted SEI growth and lithium binding with silicon to form Li15Si4 accompanied by the reductive reaction product of Li2CO3 originated from electrolyte. The Li15Si4 was highly stable when the silicon anode was used in a full cell, thus resulting in a silicon anode with a long cycle life.
TL;DR: A facile route using an oil-water interfacial coordination reaction between organic ligands and divalent metal ions is reported to synthesize crystalline quasi-2D organometallic bis(dithiolato)nickel (NiDT) nanosheets with a centimeter scale and a tunable thickness, which are integrated into OLEDs with comparable efficiency and prolonged device lifetime by nearly 2 times.
Abstract: Two-dimensional (2D) vdW materials have been integrated into optoelectronic devices to achieve exceptional functionality. However, the integration of large-area 2D thin films into organic light-emitting devices (OLEDs) remains challenging because of the finite number of inorganic 2D materials and the high-temperature requirements of their deposition process. The construction of 2D organometallic materials holds immense potential because of their solution synthesis and unlimited structural and functional diversity. Here, we report a facile route using an oil–water interfacial coordination reaction between organic ligands and divalent metal ions to synthesize crystalline quasi-2D organometallic bis(dithiolato)nickel (NiDT) nanosheets with a centimeter scale and a tunable thickness. The NiDT nanosheets can be directly integrated into OLEDs for use as a hole buffer layer and a fluorescent mounting medium without the aid of a transfer process. Moreover, OLEDs with NiDT nanosheets show not only comparable efficiency to conventional OLEDs but also prolonged device lifetime by nearly 2 times. These results open up a new dimension to use quasi-2D organometallic nanosheets as functional layers in large-area organic devices.
TL;DR: Two-dimensional coordination nanosheets (CONASHs) are grown at the spherical liquid–liquid interface of a dichloromethane droplet in water to form zero-dimensional nano- and micro-capsules using a simple dropping method, a syringe-pump method, and an emulsion method to indicate that physicochemically functional CONASH capsules are suitable for incorporating other functional materials to develop hybrid systems.
Abstract: Two-dimensional coordination nanosheets (CONASHs) are grown at the spherical liquid-liquid interface of a dichloromethane droplet in water to form zero-dimensional nano- and micro-capsules using a simple dropping method, a syringe-pump method, and an emulsion method. Reaction of 1,3,5-tris[4-(4'-2,2':6',2″-terpyridyl)phenyl]benzene (1) with Fe(BF4)2 affords electrochromic Fe(tpy)2 CONASH capsules and that of ligand 1 with ZnSO4 does photoluminescent Zn2(μ-O2SO2)2(tpy)2 CONASH capsules. Fe(tpy)2 CONASH capsules containing magnetite particles were produced by the syringe-pump method by adding magnetite to the aqueous phase, with the assembly and dispersion of the magnetite-containing CONASH capsules being easily controlled with a magnet. This indicates that physicochemically functional CONASH capsules are suitable for incorporating other functional materials to develop hybrid systems.
TL;DR: A better understanding of the underlying genetic mechanisms will help to clarify the carcinogenesis of BG-ACC and enable treatment with novel targeting agents, as well as the initial exploration of gene-based precision oncological therapies, which aim to improve treatment outcomes for patients with this disease.
Abstract: Bartholin gland carcinomas (BGCs) are rare tumor types, for which no molecular analyses including genomic sequencing have been reported to date. Adenoid cystic carcinomas (ACCs) of the Bartholin’s glands are an atypical histological type of BGC, and currently nothing is known regarding their genetic profiles or similarity to ACC carcinogenesis in other organs including the salivary glands, thereby limiting possible therapeutic options using precision medicine. We used targeted gene sequencing to analyze the occurrence of 160 cancer-related genes in two patients with BG-ACC. KRAS and KDM6A mutations were detected in tumor samples collected from each patient. No KRAS mutations have been previously reported in salivary gland ACCs, indicating that the carcinogenesis of BG-ACC differs from that of the salivary gland ACCs. KDM6A mutations are often reported in salivary gland ACCs and facilitate novel gene-targeted therapy, including the use of BET and HDAC inhibitors. A better understanding of the underlying genetic mechanisms will help to clarify the carcinogenesis of BG-ACC. In turn, this will enable treatment with novel targeting agents, as well as the initial exploration of gene-based precision oncological therapies, which aim to improve treatment outcomes for patients with this disease.
TL;DR: A novel photoelectrode is developed by integrating a newly designed gene-recombined PSI (G-PSI) with platinum nanoparticles (PtNPs) on substrates using a simple stacking method, which can control the orientation of PSI on the electrode.
Abstract: Photosynthesis is one of the most vital process in nature, which consists of two main photoreaction centers called photosystem I and II. The high quantum yield of photosystem I (PSI) makes it attra...
TL;DR: In this article, selective formation of non-centrosymmetric (Cc; α-crystal) and centrosymetric (P21/c; β-crystals) 1,1,2,2-tetramethyl-1-(4-(N,N-dimethylamino)phenyl)-2-(2′-cyanophenyl)disilane (1) wa...
Abstract: In this paper, selective formation of noncentrosymmetric (Cc; α-crystal) and centrosymmetric (P21/c; β-crystal) 1,1,2,2-tetramethyl-1-(4-(N,N-dimethylamino)phenyl)-2-(2′-cyanophenyl)disilane (1) wa...
TL;DR: This is the first report of ductal carcinoma of the prostate with an adenomatosis polyposis coli ( APC) gene mutation in Japan and the development of a therapeutic Wnt inhibitor is discussed.
Abstract: Ductal carcinoma of the prostate is a histological subtype with a higher mortality than acinar adenocarcinoma. The number of cases is small and there are no treatment guidelines. We believe that this is the first report of ductal carcinoma of the prostate with an adenomatosis polyposis coli (APC) gene mutation in Japan. An 85-year-old man presented with gross hematuria, and a papillary tumor in the prostatic urethra that was diagnosed as ductal carcinoma of the prostate following transurethral resection. Genetic analysis found an APC mutation with loss of heterozygosity. Immunostaining revealed focal nuclear translocation of β-catenin. APC mutations associated with loss of β-catenin degradation in the Wnt signaling pathway and result in over accumulation of β-catenin are thought to increase mortality. In this patient, β-catenin migrated into tumor cell nuclei. To the best of our knowledge, this is the first report of ductal carcinoma of the prostate with an APC mutation in Japan. The development of a therapeutic Wnt inhibitor is discussed.
TL;DR: Genomic analysis of prostate cancer tissue can be useful to determine optimal treatment of such cancers, and a case of aggressive, castration-resistant prostate cancer with FANCA homodeletion is described.
Abstract: Precision medicine based on genomic analysis of germline or tumor tissue is attracting attention. However, there is no consensus on how to apply the results of genomic analysis to treatment. A 59-year-old man diagnosed with metastatic prostate cancer was diagnosed with castration-resistant prostate cancer. Although he was sequentially treated with enzalutamide and abiraterone, bone metastasis progression was identified by skeletal scintigraphy. Therefore, we sequentially performed docetaxel therapy followed by cabazitaxel. After the third cycle of cabazitaxel, his prostate-specific antigen level was stable at < 10 ng/mL, and no radiological progression was detected. The patient’s formalin-fixed paraffin-embedded tumor biopsy specimen underwent multiple-gene testing by next-generation sequencing, which identified a FANCA homodeletion. No significant germline mutation was observed. We describe a case of aggressive, castration-resistant prostate cancer with FANCA homodeletion. Genomic analysis of prostate cancer tissue can be useful to determine optimal treatment of such cancers.
TL;DR: The data suggested that TES may play a critical role for promoting reverse-translational studies, including investigations of the biology of TP53 mutations in different stages of SCLC.
TL;DR: A liquid/liquid interfacial method is used to synthesize a conjugated porous polymer nanofilm with a large domain size featuring a large aspect ratio and robustness against heat and pH.
TL;DR: Novel diarylethenes having an azulene ring with a strong donor or acceptor were synthesized and the photoreactivities of these compounds were explained by calculating forces and bond orders on the excited states using density functional theory (DFT) and time-dependent (TD)-DFT.
Abstract: The cyclization reaction of diarylethenes having an azulene ring occurs only via higher excited states. Novel diarylethenes having an azulene ring with a strong donor or acceptor were synthesized and examined in these reactions. A derivative having an electron-donating 1,3-benzodithiol-2-ylidenemethyl group at the 1-position of the azulene ring showed photochromism, whereas neither a derivative having a π-conjugated electron-donating group at the 3-position of the azulene ring nor derivatives having a π-conjugated electron-withdrawing group at the 1- or 3-position of the azulene ring showed any photochromism. The photoreactivities of these compounds were explained by calculating forces and bond orders on the excited states using density functional theory (DFT) and time-dependent (TD)-DFT.
TL;DR: In this paper, a coordination polymer composed of ferrous ion and a ligand with 2,6-bis(1-methylbenzimidazol-2-yl)pyridine (mbzimpy) ligating groups was synthesized to incorporate spin crossover (SCO) activity.
Abstract: Low-dimensional coordination polymers are attractive materials because the infinite combination of metal ions and ligands allows us to produce various chemical structures and functions. Spin crossover (SCO) is one of the curious magnetic functions because the electronic state of metal complex can be controlled by external stimuli. It is expected that the introduction of SCO-active metal complex to a coordination polymer will contribute to produce a multifunctional material. In this research, a coordination polymer composed of ferrous ion and a ligand with 2,6-bis(1-methylbenzimidazol-2-yl)pyridine (mbzimpy) ligating groups $$([\mathbf{FeL}_\mathrm{mbi}]_n)$$ was synthesized to incorporate SCO activity. The polymer was synthesized using a liquid–liquid interfacial reaction and a one-phase reaction, and was obtained as a film and a powder, respectively. Electrochemical and spectroscopic measurements revealed the formation of $$[\mathrm{Fe}(\mathrm{mbzimpy})_2]$$ complex. The magnetic susceptibility measurement displayed the partial SCO of $$[\mathbf{FeL}_\mathrm{mbi}]_n$$ polymer from 350 K to 250 K.
TL;DR: The results suggest that CDK12 coamplification with Erb‐B2 receptor tyrosine kinase 2 might be associated with tumor aggressiveness and contribution to cancer pathogenesis.
Abstract: Cyclin-dependent kinase 12 (CDK12), one of the key factors associated with DNA damage response pathways, is located on chromosome 17 proximal to Erb-B2 receptor tyrosine kinase 2 (ERBB2). In this report, CDK12 and ERBB2 coamplification was detected by targeted next-generation sequencing in two urothelial carcinomas. The staining intensity of the CDK12 and human epidermal growth factor receptor-2 proteins was associated with the prognosis of each urothelial carcinoma case. Our results suggest that CDK12 coamplification with ERBB2 might be associated with tumor aggressiveness and contribution to cancer pathogenesis. Therapies targeting CDK12 should be developed for these patients.
TL;DR: In this paper, a Pt(mnt)2 (mnt=maleonitriledithiolato) anion radical salt (ethyl-4-iodothiazolium)2[Pt(mnd)2]3 (Pt-I) was investigated and the structure and magnetic properties of Pt-I and Pt-Br were compared.
Journal Article•
TL;DR: The use of water-soluble contrast agent in the stomach was safe, reliable, and cost effective for PEG tube placement, and is recommended to decrease surgical gastrostomy.
Abstract: AIM: A colocutaneous fistula is a rare late complication of percutaneous endoscopic gastrostomy (PEG) feeding placement that occurs as a result of the interposition of the colon between the anterior abdominal and gastric walls. In the current study, we sought to retrospectively study the method of introducing the water-soluble contrast agent into the stomach by using a nasogastric tube before PEG feeding placement, with the intention to develop a method to prevent PEG-related colocutaneous fistula. MATERIALS AND METHODS: Between October 2003 and April 2020, 341 patients underwent PEG placement at Seiwa Memorial Hospital. Patients were divided into two groups: 232 patients in Group A were given water-soluble contrast agent and 109 patients in Group B were not. All patients underwent PEG using introducer method placement after gastropexy under fluoroscopy. RESULTS: In Group A, 139 (59.9%) patients received PEG with a water-soluble contrast agent placed into the transverse colon, 75 (32.3%) received PEG with gas in the colon, and 7 (3.0%) patients received surgical gastrostomy. In Group B, 38 (34.8%) patients received PEG with gas in the colon, 60 (55.1%) patients received PEG with finger palpation and transillumination, and 10 (9.2%) patients received surgical gastrostomy. Colocutaneous fistula was not observed in either group, but there was a significant difference in the frequency of surgical gastrostomy between Group A and B ( p = 0.0148). CONCLUSION: The use of water-soluble contrast agent in the stomach was safe, reliable, and cost effective for PEG tube placement, and is recommended to decrease surgical gastrostomy.