Chemoselective one-pot cleavage and oxidation of silyl ethers to corresponding carbonyl compounds using IBX and acid catalysts.

Herein, we describe the chemoselective one-pot cleavage and oxidation of silyl ethers using catalytic amount of TsOH·H2O and IBX in DMSO. The oxidation of primary alkyl TBS ethers afforded the corresponding aldehydes in 51-94% yields, in the presence of aryl TBS, MOM, and PMB ethers, as well as N-Boc and acetonide groups. Secondary benzyl TBS ethers bearing aryl TBS ethers were also oxidized to ketones in moderate yields. A possible reaction pathway was also proposed.

Health Care Access and Cognitive Function in Older Adults: A Cross-Lagged Panel Longitudinal Analysis.

Objective: The current longitudinal study examined how (1) cognitive measures, including episodic memory, executive function, and global cognition, predict later healthcare access and how (2) healthcare access predicts later cognition. Methods: Drawing a sample (n = 9920) from the Health and Retirement Study dataset, we created a cross-lagged panel model to examine the longitudinal association between cognitive measures and healthcare access from 2012 to 2018. Results: Results revealed that cognitive measures significantly predict later healthcare access, with effects increasing across waves. However, within sub-domains, memory was more predictive of later healthcare access over time compared to executive function. Discussions: Our study suggested an increased link between cognition and healthcare access during aging. Even outside of the context of AD, there are likely both policy-based and practical implications to ensure those experiencing cognitive decline continue to maintain access to care.

Cross-level covariance approach to the disaggregation of between-person effect and within-person effect.

In longitudinal studies, researchers are often interested in investigating relations between variables over time. A well-known issue in such a situation is that naively regressing an outcome on a predictor results in a coefficient that is a weighted average of the between-person and within-person effect, which is difficult to interpret. This article focuses on the cross-level covariance approach to disaggregating the two effects. Unlike the traditional centering/detrending approach, the cross-level covariance approach estimates the within-person effect by correlating the within-level observed variables with the between-level latent factors; thereby, partialing out the between-person association from the within-level predictor. With this key device kept, we develop novel latent growth curve models, which can estimate the between-person effects of the predictor's change rate. The proposed models are compared with an existing cross-level covariance model and a centering/detrending model through a real data analysis and a small simulation. The real data analysis shows that the interpretation of the effect parameters and other between-level parameters depends on how a model deals with the time-varying predictors. The simulation reveals that our proposed models can unbiasedly estimate the between- and within-person effects but tend to be more unstable than the existing models. (PsycInfo Database Record (c) 2023 APA, all rights reserved).

Total syntheses of Ganoderma-derived meroterpenoids, (-)-oregonensin A, (-)-chizhine E, (-)-applanatumol U, and (-)-ent-fornicin A.

In this study, we report the total syntheses of Ganoderma-derived meroterpenoids, (-)-oregonensin A, (-)-chizhine E, (-)-applanatumol U, and (-)-ent-fornicin A. The 3-alkyl-5-aryl-γ-butenolide skeleton, a common motif of these meroterpenoids, was constructed through the enantioselective reductive lactonization of the γ-keto ester, alkylation, and sulfoxide-ß-syn-elimination. This flexible approach enabled enantioselective access to these meroterpenoids with the longest linear sequence of 6-8 steps, and in 21-36% overall yield, respectively.

Successful treatment of a bowel fistula in the open abdomen by perforator flaps and an aponeurosis plug.

In this report, we present a case of successful treatment of a bowel fistula in the open abdomen by perforator flaps and an aponeurosis plug. A 70-year-old man underwent total gastrectomy and developed anastomotic leakage and dehiscence of the abdominal wound a week later. He was dependent upon extracorporeal membrane oxygenation, continuous hemodiafiltration, and a respirator. Bowel fluids contaminated the open abdomen. Two months after the gastric operation, a plastic surgery team, in consultation with general surgeons, performed perforator flaps on both sides and constructed, as it were, a bridge of skin sealing the orifice of the fistula. The aponeurosis of the external oblique muscle was elevated with the flap to be used as a plug. The perforators of the flaps were identified on preoperative and intraoperative ultrasonography. This modality allowed us to locate the perforators precisely and to evaluate the perforators by assessing their diameters and performing a waveform analysis. The contamination decreased dramatically afterwards. The bare areas were gradually covered by skin grafts. The fistula was closed completely 18 days after the perforator flap. An ultrasoundguided perforator flap with an aponeurosis plug can be an option for patients suffering from an open abdomen with a bowel fistula.

Discovery, primary, and crystal structures and capacitation-related properties of a prostate-derived heparin-binding protein WGA16 from boar sperm.

Mammalian sperm acquire fertility through a functional maturation process called capacitation, where sperm membrane molecules are drastically remodeled. In this study, we found that a wheat germ agglutinin (WGA)-reactive protein on lipid rafts, named WGA16, is removed from the sperm surface on capacitation. WGA16 is a prostate-derived seminal plasma protein that has never been reported and is deposited on the sperm surface in the male reproductive tract. Based on protein and cDNA sequences for purified WGA16, it is a homologue of human zymogen granule protein 16 (ZG16) belonging to the Jacalin-related lectin (JRL) family in crystal and primary structures. A glycan array shows that WGA16 binds heparin through a basic patch containing Lys-53/Lys-73 residues but not the conventional lectin domain of the JRL family. WGA16 is glycosylated, contrary to other ZG16 members, and comparative mass spectrometry clearly shows its unique N-glycosylation profile among seminal plasma proteins. It has exposed GlcNAc and GalNAc residues without additional Gal residues. The GlcNAc/GalNAc residues can work as binding ligands for a sperm surface galactosyltransferase, which actually galactosylates WGA16 in situ in the presence of UDP-Gal. Interestingly, surface removal of WGA16 is experimentally induced by either UDP-Gal or heparin. In the crystal structure, N-glycosylated sites and a potential heparin-binding site face opposite sides. This geography of two functional sites suggest that WGA16 is deposited on the sperm surface through interaction between its N-glycans and the surface galactosyltransferase, whereas its heparin-binding domain may be involved in binding to sulfated glycosaminoglycans in the female tract, enabling removal of WGA16 from the sperm surface.

[Two cases of recurrent GIST successfully treated with imatinib mesylate at 100mg/day].

Case 1: Recurrent tumors from gastric GIST in the liver and the abdominal wall showed partial response with 200mg/day imatinib and maintained partial response at 100mg/day. Case 2: Metastatic liver tumors from the jejunal GIST showed partial response with 200mg/day imatinib. The tumors have been enlarged for interruption of imatinib administration, however, re- treatment with imatinib resulted in partial response again and kept partial response at 100mg/day of imatinib. The two cases seldom encountered adverse events at 100mg/day of imatinib. There are some cases successfully treated with low-dose imatinib mesylate for recurrent GIST.

Pig sperm membrane microdomains contain a highly glycosylated 15-25-kDa wheat germ agglutinin-binding protein.

A highly glycosylated protein, which has unique, novel features in localization, structure, and potential function, is found in pig sperm, and named WGA-gp due to its high binding property with wheat germ agglutinin (WGA). WGA-gp is localized mainly in flagella and enriched in membrane microdomains or lipid rafts. It is not detected by ordinary protein staining methods due to a high content of both N- and O-glycans consisting of neutral monosaccharides. Interestingly, WGA-gp may be involved in intracellular Ca(2+) regulation. Treatment of sperm with anti-WGA-gp antibody enhances the amplitude of Ca(2+) oscillation without changing the basal intracellular Ca(2+) concentrations. All these features of WGA-gp, except for different carbohydrate structures occupying most part of the molecules, are similar to those of flagellasialin in sea urchin sperm, which regulates the intracellular Ca(2+) concentration. Presence of carbohydrate-enriched flagellar proteins involved in intracellular Ca(2+) regulation may be a common feature among animal sperm.

[A case of recurrent breast cancer with lung metastasis resection showing four disease-free years under trastuzumab treatment].

We report a case of recurrent breast cancer with solitary lung metastasis that has shown no recurrence with treatment by trastuzumab alone after partial resection of the right lung upper lobe. A 56-year-old woman, who presented with left breast cancer, underwent quadrantectomy and axillar lymph node dissection in March 2004. Pathological findings were as follows: invasive ductal carcinoma, 3. 7 cm in size, histological grade 3, positive invasion of lymphatic and blood vessels, negative nodal status, negative ER/PgR status, and overexpression of HER2/ neu. She had received adjuvant radiotherapy followed by cyclophosphamide, methotrexate and fluorouracil combination chemotherapy; however, a lung nodule developed 14 months after first operation, which had grown gradually. Partial resection of the lung with thoracoscope assistance revealed metastatic lung cancer from breast cancer. Trastuzumab treatment for 6 months after second operation has maintained no recurrence for 4 years.

[A case of gastric gastrointestinal stromal tumor operated after low-dose chemotherapy with imatinib mesylate].

A 76-year-old man was admitted to our hospital because of tarry motions. Endoscopic findings showed an ulcer on a large submucosal tumor in the stomach. Abodminal CT scan showed a protruding lesion of approximately 13 cm at the lumen of the gastric body. FDG-PET imaging revealed FDG uptake in the gastric body and abdominal cavity. We diagnosed it as GIST with peritoneal dissemination clinically, and treatment with 300 mg of imatinib mesylate was started in December 2006. The main tumor was reduced(reduction rate of 27%)and FDG-PET imaging revealed a decrease in FDG uptake in the main tumor and all disseminated tumors after 5 months of treatment. However, the drug was discontinued for arthritis(grade 3). Partial gastrectomy with sampling peritoneal nodules was performed in June 2007. The present case suggests that low-dose chemotherapy with imatinib mesylate may be useful as a preoperative therapy for a minimal surgery.

[Good response in ARDS treated with sivelestat sodium hydrate during chemotherapy for cholangiocarcinoma].

We experienced a case of good response in acute respiratory distress syndrome (ARDS) treated with sivelestat sodium hydrate during chemotherapy for cholangiocarcinoma. A 66-year-old male treated with combined paclitaxel (PTX) and S-1 suffered from ARDS following neutropenia. Sputum and blood culture examinations demonstrated an unknown origin, so sivelestat sodium hydrate was considered more effective than antibiotics. Sivelestat sodium hydrate ought to be used for ARDS treatment even during administration of anti-cancer agent.