Palladium-Catalyzed Skeletal Rearrangement of Substituted 2-Silylaryl Triflates via 1,5-C-Pd/C-Si Bond Exchange.

A palladium-catalyzed skeletal rearrangement of 2-(2-allylarylsilyl)aryl triflates has been developed to give highly fused tetrahydrophenanthrosilole derivatives via unprecedented 1,5-C-Pd/C-Si bond exchange. The reaction pathways can be switched toward 4-membered ring-forming C(sp2 )-H alkylation by tuning the reaction conditions to give completely different products, fused dihydrodibenzosilepin derivatives, from the same starting materials. The inspection of the reaction conditions revealed the importance of carboxylates in promoting the C-Pd/C-Si bond exchange.

Iron phosphide nanocrystals as an air-stable heterogeneous catalyst for liquid-phase nitrile hydrogenation.

Iron-based heterogeneous catalysts are ideal metal catalysts owing to their abundance and low-toxicity. However, conventional iron nanoparticle catalysts exhibit extremely low activity in liquid-phase reactions and lack air stability. Previous attempts to encapsulate iron nanoparticles in shell materials toward air stability improvement were offset by the low activity of the iron nanoparticles. To overcome the trade-off between activity and stability in conventional iron nanoparticle catalysts, we developed air-stable iron phosphide nanocrystal catalysts. The iron phosphide nanocrystal exhibits high activity for liquid-phase nitrile hydrogenation, whereas the conventional iron nanoparticles demonstrate no activity. Furthermore, the air stability of the iron phosphide nanocrystal allows facile immobilization on appropriate supports, wherein TiO2 enhances the activity. The resulting TiO2-supported iron phosphide nanocrystal successfully converts various nitriles to primary amines and demonstrates high reusability. The development of air-stable and active iron phosphide nanocrystal catalysts significantly expands the application scope of iron catalysts.

Vasoreactivity of the optic nerve head, nailfold, and facial skin in response to cold provocation in normal-tension glaucoma patients.

BACKGROUND: The dysfunction of optic nerve head (ONH) hemodynamics has been suggested to be involved in the pathogenesis of normal-tension glaucoma (NTG). The aim of this study was to compare vasoreactivity in the ONH, nailfold, and facial skin in response to cold-water provocation in NTG patients and healthy controls. METHODS: We performed cold-water provocation in 14 eyes of 14 NTG patients and 15 eyes of 15 age-matched control subjects. Laser speckle flowgraphy-derived tissue-area mean blur rate (MT), skin blood flowmetry-derived pulse wave amplitude (PA), nailfold capillaroscopy-derived nailfold capillary diameter, and other clinical parameters were recorded at baseline and 4 and 6 min after the cold stimulus. We compared changes (as percentages) in these variables in the NTG and control subjects with a linear mixed-effects model and evaluated correlations between these changes with Spearman's rank correlation coefficient. RESULTS: The interaction term between the NTG group (reference, control group) and the 4-min protocol step (reference, baseline) significantly affected the changes in MT, nailfold capillary diameter and PA (ß = -9.51%, P = 0.017, ß = -20.32%, P = 0.002; ß = + 18.06%, P = 0.017, respectively). The change in MT was positively correlated with the change in nailfold capillary diameter, and negatively correlated with the change in PA (r = 0.39, P = 0.036; r = -0.40, P = 0.031, respectively). CONCLUSION: NTG patients showed abnormal vasoconstriction in the ONH and nailfold and vasodilation in the facial skin in response to cold-water provocation.

Artificial intelligence in food science and nutrition: a narrative review.

In the late 2010s, artificial intelligence (AI) technologies became complementary to the research areas of food science and nutrition. This review aims to summarize these technological advances by systematically describing the following: the use of AI in other fields (eg, engineering, pharmacy, and medicine); the history of AI in relation to food science and nutrition; the AI technologies currently used in the agricultural and food industries; and some of the important applications of AI in areas such as immunity-boosting foods, dietary assessment, gut microbiome profile analysis, and toxicity prediction of food ingredients. These applications are likely to be in great demand in the near future. This review can provide a starting point for brainstorming and for generating new AI applications in food science and nutrition that have yet to be imagined.

Palladium-Catalyzed Synthesis of Dibenzosilepin Derivatives via 1,n-Palladium Migration Coupled with anti-Carbopalladation of Alkyne.

Catalytic reactions involving 1,n-metal migration represent a powerful method for the synthesis of complex molecules from simple precursors through the activation of C-H bonds. By utilizing this attractive feature, herein we devised a palladium-catalyzed synthesis of new members of 5H-dibenzo[b,f]silepins, a class of underexplored but potentially useful silicon-bridged π-conjugated compounds. The reaction sequence is composed of 1,n-palladium migrations and unusual anti-carbopalladation of alkynes, which was realized by the proper choice of ligand for palladium. A series of deuterium-labeling experiments were conducted toward an understanding of the reaction mechanism to propose plausible catalytic cycles. The newly obtained 5H-dibenzo[b,f]silepins exhibited tunable optical and electronic properties, demonstrating the power and importance of developing a new synthetic method based on 1,n-metal migration processes.

[EXPLORATORY EXAMINATION FOR THE FACTORS RELATED TO VOIDING DYSFUNCTION IN PATIENTS AFTER SURGERY FOR PROXIMAL FEMORAL FRACTURES].

(Purpose) While urinary retention and urinary tract infections accompanying residual urine are often experienced following proximal femoral fractures (femoral neck fractures and trochanteric fractures) in clinical practice, the pathology of the onset of voiding dysfunction for this disease is unclear since the nervous system associated with urination is not damaged due to the fracture not reaching the pelvis. Therefore, we exploratorily examined the factors related to voiding dysfunction in proximal femoral fractures. (Subjects and method) Among the patients who underwent surgery for proximal femoral fractures, we examined the relation between the proportion of cases in which withdrawing urine was required for residual urine after removing the urethral catheter and the differences in the fracture sites, pain, the ability to maintain a sitting position, the strength to bend the hip joints, and the volume of the iliopsoas muscle. (Results) The proportion of cases in which withdrawing urine was required was higher in the group suffering trochanteric fractures than the group suffering femoral neck fractures (41% vs. 11%), while the strength to bend the hip joints was lower. Regarding trochanteric fractures, compared to the group in which no urine was withdrawn, the group in which urine was withdrawn included more of the unstable type in which the fracture reached the lesser trochanter, which is the femoral insertion of the iliopsoas muscle (56% vs. 82%), in addition to having a significant decrease in the strength to bend the hip joints. Regarding trochanteric fractures, compared to the group without injury in lesser trochanter, the group with injury in lesser trochanter had a higher proportion of cases in which withdrawing urine was required (23% vs. 51%), in addition to the iliopsoas muscle thereof having been atrophied (-15.7% vs. -35.2%). (Conclusion) As factors related to voiding dysfunction following surgery for proximal femoral fractures, the relation between fracture sites, the strength to bend the hip joints associated with maintaining posture, the presence of injuries in the lesser trochanter, and the volume of the iliopsoas muscle were suggested. Therefore, it is possible that the proportion of cases in which the withdrawal of urine was required increased with the increase in residual urine due to the decrease in the ability to maintain a urinating posture until the bladder is completely empty.

Palladium-Catalyzed Synthesis of Benzophenanthrosilines by C-H/C-H Coupling through 1,4-Palladium Migration/Alkene Stereoisomerization.

A new and efficient synthesis of 8H-benzo[e]phenanthro[1,10-bc]silines from 2-((2-(arylethynyl)aryl)silyl)aryl triflates under palladium catalysis has been developed. The reaction mechanism was experimentally investigated and a catalytic cycle involving C-H/C-H coupling through a new mode of 1,4-palladium migration with concomitant alkene stereoisomerization is proposed.

Synthesis of carbonyl-bridged dibenzofulvalenes and related compounds by rhodium-catalyzed stitching reaction.

Various carbonyl-bridged dibenzofulvalenes were synthesized by a sequence of rhodium-catalyzed stitching reaction and post-functionalization, and their optical and electronic properties could be tuned by changing the terminal substituents. The present stitching reaction also allowed for facile synthesis of dibenzofulvalenes having C, Si, Ge, S, and P as the bridging elements.

Palladium-Catalyzed Intramolecular C-H Arylation versus 1,5-Palladium Migration: A Theoretical Investigation.

Theoretical investigations were carried out to elucidate the origin of chemoselectivity in the palladium-catalyzed reactions of 2-(dimethylphenylsilyl)phenyl triflates with or without an amino group at the 3-position. The selective formation of a 5,10-dihydrophenazasiline rather than a dibenzosilole from the substrate with an amino group at the 3-position could be successfully explained by proposing a new 1,5-palladium migration pathway that involves a neutral diorganopalladium(II) intermediate along with the subsequent formation of a low-energy amine-coordinated palladacycle intermediate prior to the C-N bond-forming process.

Silicosis, then microscopic polyangiitis-antineutrophil cytoplasmic antibodies-associated vasculitis may be work-related disease in patients with silicosis.

A 74-year-old man with silicosis was admitted to the hospital because of prolonged fever. After referral to internal medicine for persistent fever and renal dysfunction, workup revealed antineutrophil cytoplasmic antibodies (ANCA) positivity. He was diagnosed with microscopic polyangiitis (MPA). After treatment with immunosuppressive therapy, his condition improved. Herein, we discuss silica exposure and the risk of ANCA-associated vasculitis (AAV), particularly in terms of work-related diseases. Silica exposure is a notorious risk factor for developing AAV, which is potentially lethal when not identified. When we see a silicosis patient with new-onset prolonged fever and generalized fatigue, AAV should be taken into consideration. This case report provides beneficial information to reliably assess patients at high risk of developing AAV in primary care settings.

Synthesis of Quinoidal Fused Oligosiloles by Rhodium-Catalyzed Stitching Reaction and Theoretical Investigation of Their Properties.

New quinoidal fused oligosiloles containing an even number of silole units have been synthesized by a rhodium-catalyzed stitching reaction. Employing [RhCl(tfb)]2 as the catalyst significantly improved the stitching efficiency, and up to six siloles could be fused in quinoidal form. A systematic comparison of the physical properties of Si1-Si6' confirmed the unique trend in their LUMO levels, which become higher with longer π conjugation. To understand the origin of this unusual trend, theoretical calculations were also carried out using various model compounds, and the results indicated that the terminal indenylidene (cyclopentadienylidene) moieties in Si1-Si6 (Si1a-Si6a) are primarily responsible for this phenomenon through their frontier orbital correlations with the HOMO of the central polyene unit, which becomes higher in energy with longer π conjugation.

Optimal cut-off value of alanine aminotransferase level to precisely estimate the presence of fatty liver in patients with poorly controlled type 2 diabetes.

Optimal cut-off value of ALT level to precisely estimate the presence of fatty liver was as low as 28.0 U/L. We should consider the possibility of fatty liver even when ALT level is within normal range in subjects with poorly controlled type 2 diabetes.

Characterization and crystal structure determination of ß-1,2-mannobiose phosphorylase from Listeria innocua.

Glycoside hydrolase family 130 consists of phosphorylases and hydrolases for ß-mannosides. Here, we characterized ß-1,2-mannobiose phosphorylase from Listeria innocua (Lin0857) and determined its crystal structures complexed with ß-1,2-linked mannooligosaccharides. ß-1,2-Mannotriose was bound in a U-shape, interacting with a phosphate analog at both ends. Lin0857 has a unique dimer structure connected by a loop, and a significant open-close loop displacement was observed for substrate entry. A long loop, which is exclusively present in Lin0857, covers the active site to limit the pocket size. A structural basis for substrate recognition and phosphorolysis was provided.

[A case report of primary small cell esophageal carcinoma responding successfully to radiochemotherapy].

Primary small cell esophageal carcinoma is a rare cancer with a poor prognosis, for which to date there is no recommended standard treatment. We present a 60-year-old male with this disease who was successfully managed by the combination of radiation and chemotherapy. The patient was referred to our hospital for liver dysfunction of unknown cause. On admission, he was diagnosed as having a primary small cell esophageal carcinoma and multifocal metastasis in the liver. He received cisplatin and 5-fluorouracil(CDDP 40mg/m2-days 1, 8, 5-FU 400 mg/m2-days 1-5, 8-12)and local radiation of 50 Gy for the esophagus, followed by 4 courses of chemotherapy the same as listed above. At the end of therapy, radiological findings showed that both primary and metastatic lesions completely disappeared. Unfortunately, he died of liver failure due to the recurrence of metastatic small cell carcinoma in the liver 13 months after the end of initial therapy. However, the primary cancer lesion had not recurred by that time. These findings suggest the beneficial effect of the combination of radiotherapy and chemotherapy for advanced-stage small cell esophageal carcinoma.

Successful resection of advanced pancreatic tail cancer after neoadjuvant gemcitabine chemotherapy: report of a case.

Pancreatic cancer with distant metastasis is not an indication for surgery, and the median survival of these patients is less than 3 months. We report the case of a patient who has survived for 21 months without any signs of recurrence after resection of advanced pancreatic cancer following a course of chemotherapy with gemcitabine (GEM). A 75-year-old man was hospitalized for anorexia and emaciation. Examinations showed pancreatic cancer with distant peritoneal metastasis. After the main tumor and metastasis had been shrunk by GEM chemotherapy, we performed distal pancreatectomy combined with splenectomy. Microscopically, the main tumor was confirmed as moderately differentiated tubular adenocarcinoma with interstitium and fibrosis. The radicality of the surgery was R0, according to the TNM classification of the UICC. The patient recovered well and has had no clinical symptoms for 40 months since the initial chemotherapy. This case suggests that multidisciplinary treatment with GEM may prolong the survival of some patients with unresectable pancreatic cancer.

[A case of advanced pancreatic cancer treated with gemcitabine hydrochloride].

We report the case of 75-year-old man with advanced pancreatic cancer who was successfully treated with gemcitabine. The patient was admitted to our hospital suffering from anorexia and body weight loss. CT and ERCP showed pancreatic tail cancer with Schnitzler metastasis. We judged that a curative operation was impossible. Gemcitabine was infused over 30 minutes on an outpatient basis (1,000 mg/m2/week x 3/4 weeks). After 4 courses, the tumor was reduced and the tumor markers decreased. Furthermore, the patient can take sufficient meals without any adverse effects. The patient continues to undergoing the therapy with gemcitabine, and his quality of life has been preserved.

Obstructive ileitis secondary to colon cancer: report of a case.

We report a case of obstructive ileitis (OI) secondary to colon cancer. A 62-year-old man was hospitalized for abdominal pain and a feeling of fullness. Examinations revealed a mechanical ileus caused by an obstructing carcinomatous lesion of the cecum. He underwent laparotomy on the tenth hospital day, and a right hemicolectomy was carried out with resection of the distended and edematous ileum. The histopathologic diagnosis was adenocarcinoma in the cecum involving the ileocecal valve and nonspecific inflammatory change of the ileum, with mucosal necrosis and neutrophilic infiltration involving the subserosal layer. His postoperative course was uneventful. OI does not always show similar histological features to obstructive colitis; however, they are both important types of obstructing lesions, and their possibility must be kept in mind during colorectal cancer surgery.