Harnessing Free Sulfate Groups in Glycosylation Reactions.

General strategies for synthesizing sulfated oligosaccharides employ the protection of sulfate groups for glycosylation or post-sulfation after the synthesis of oligosaccharides. However, the chemical behavior of free sulfate groups in glycosylation reactions has not been thoroughly studied. We examined several glycosyl donors with free sulfate groups, but neither glycosyl imidates nor thioglycosides achieved products.

Intraoperatively measured prehepatectomy portal vein pressure as a useful predictor of posthepatectomy liver failure.

Background: Predicting posthepatectomy liver failure (PHLF) may be a critical requirement for liver disease patients undergoing hepatectomy. This study retrospectively analyzed the impact of the intraoperatively measured portal vein pressure (PVP) prior to hepatectomy on the prediction of PHLF in hepatectomized patients.

Methods: A total of 334 hepatectomized patients in whom the PVP was intraoperatively measured before resection at our institution were enrolled in the present study.

Uncovering a Latent Bioactive Interleukin-6 Glycoform.

A bioinspired semisynthesis of human-interleukin-6 bearing N-glycan at Asn143 (143glycosyl-IL-6) was performed by intentional glycosylation effects and protein folding chemistry for regioselective peptide-backbone activation. 143Glycosyl-IL-6 is a genetically coded cytokine, but isolation was difficult owing to a tiny amount. IL6-polypeptide (1-141-position) with an intentionally inserted cysteine at 142-position was expressed in E.

Post-translational activation of the C-terminus of polypeptides for the synthesis of peptide thioesters and peptide thioester surrogates.

Semisynthesis using recombinant polypeptides is a powerful approach for the synthesis of proteins having a variety of modifications. Peptide thioesters, of which the peptide C-terminus is activated by a thioester, are utilized for coupling peptide building blocks. Biological methods employing intein have been a center for the C-terminal thioesterification of recombinant polypeptides.

High hand grip strength is a significant risk factor and a useful predictor of postoperative pancreatic fistula following pancreaticoduodenectomy.

Background: Postoperative pancreatic fistula (POPF) is one of the most critical complications of pancreaticoduodenectomy (PD). Studies on predictive factors for POPF that can be identified preoperatively are limited. Recent reports have highlighted the association between the preoperative nutritional status, including sarcopenia, and postoperative complications.

Isopeptide bond formation mediated by δ-selenolysine for chemical ubiquitination.

Protein ubiquitination is involved in nearly all biological processes in Eukaryotes. To gain precise insights into the function of ubiquitination in these processes, researchers frequently employ ubiquitinated protein probes with well-defined structures. While chemical protein synthesis has afforded a variety of ubiquitinated protein probes, there remains a demand for efficient synthesis methods for complex probes, such as ubiquitinated glycoproteins and ubiquitinated cysteine-containing proteins.

Convergent synthesis of proteins using peptide-aminothiazoline.

Sequential peptide coupling plays a central role in chemical protein synthesis. This paper describes a new peptide derivative, peptide-aminothiazoline (At), whereof the C-terminus is functionalized with 2-aminothiazoline. Peptide-At streamlined the sequential peptide ligation in a one-pot manner and demonstrated the convergent synthesis of a circular protein and homogeneous glycoproteins.

Downregulation of long noncoding RNA expression confers resistance to temozolomide in human glioblastoma cells.

Glioblastoma multiforme (GBM), the most aggressive primary malignant brain tumor, is resistant to conventional radiotherapies and chemotherapies, including temozolomide (TMZ). Overcoming GBM resistance to the chemotherapeutic agent TMZ poses an important therapeutic problem. This study established an association between the long noncoding RNA and TMZ sensitivity regulation in human GBM cells (U87MG).

Semisynthesis of homogeneous misfolded glycoprotein interleukin-8.

To uncover how cells distinguish between misfolded and correctly-folded glycoproteins, homogeneous misfolded glycoproteins are needed as a probe for analysis of their structure and chemical characteristic nature. In this study, we have synthesized misfolded glycosyl interleukin-8 (IL-8) by combining E. coli expression and chemical synthesis to improve the synthetic efficiency.

Rapid Chemical Synthesis of Serine Protease Inhibitor Kazal-type 13 (SPINK13) Glycoform by a Combined Method with Glycan Insertion Strategy and Fast-Flow Fmoc SPPS.

Serine protease inhibitor Kazal type 13 (SPINK13) is a secreted protein that has been recently studied as a therapeutic drug and an interesting biomarker for cancer cells. Although SPINK13 has a consensus sequence (Pro-Asn-Val-Thr) for N-glycosylation, the existence of N-glycosylation and its functions are still unclear. In addition to this, the preparation of glycosylated SPINK 13 has not been examined by both the cell expression method and chemical synthesis.

Experimentally probing anomalous time evolution of a single photon.

In quantum mechanics, a quantum system is irreversibly collapsed by a projective measurement. Hence, delicately probing the time evolution of a quantum system holds the key to understanding curious phenomena. Here, we experimentally explore an anomalous time evolution, where, illustratively, a particle disappears from a box and emerges in a different box, with a certain moment in which it can be found in neither of them.

[Clinical Study of Peritoneovenous Shunt for Patients with Refractory Ascites Accompanied with Hepatocellular Carcinoma].

Background: Hepatic ascites may cause a variety of symptoms and may progress deterioration of quality of life. Peritoneovenous shunt(PV shunt)is technically feasible and useful for the treating of refractory ascites, but sometimes it can be associated with fatal complications. This retrospective study aimed to investigate the effect of PV shunt for patients with refractory ascites, including hepatocellular carcinoma(HCC)patients.

[Two Cases of Elderly Patients with Giant Intrahepatic Cholangiocarcinoma Treated with Multidisciplinary Therapy including Ablation Therapy].

Case 1 consisted of an 86-year-old male diagnosed with intrahepatic cholangiocarcinoma(ICC), approximately 11 cm in diameter, at segment S7/8 of the liver. A total of 4 percutaneous radiofrequency ablations(PRFA)and 3 hepatic arterial infusion chemotherapies(HAIC)of 5-FU were performed. He died after developing lung metastases 27 months after the initial treatment.

[A Rapid Clinical Course of Pulmonary Embolism Associated with Gallbladder Mucinous Carcinoma].

A 51-year-old woman with edema of the lower extremities and exertional dyspnea was admitted to our hospital. Enhanced CT revealed thrombi of the pulmonary artery and a gallbladder tumor. After anticoagulation therapy was started on her, anemia and jaundice progressed; thus, endoscopic retrograde cholangiopancreatography(ERCP)was performed on suspicion of bleeding from a gallbladder tumor.

[Clinical Efficacy of Recombinant Human Thrombomodulin for Surgical Patients with Disseminated Intravascular Coagulation Associated with Oncologic Emergency].

Aim: We evaluated the clinical efficacy of recombinant human thrombomodulin(rTM)for surgical patients with disseminated intravascular coagulation syndrome(DIC)associated with an oncologic emergency(OE).

Subjects And Methods: Thirteen patients who underwent surgery for OE complicated with DIC and were treated with rTM in our institution were evaluated. We retrospectively analyzed the clinical changes of parameters in white blood cell count(WBC), platelet count, CRP, PT-INR and DIC scores after the rTM treatment.

[A Case of Long-Term Survival with S-1/Cisplatin for Liver Hilum Lymph Node Metastasis of Anal Canal Squamous Cell Carcinoma after Chemoradiotherapy].

A 70-year-old woman was admitted to a local hospital because of anal pain during defecation. Anoscopy revealed an anal mass lesion, and the patient was referred to our hospital. Colonoscopy revealed an anal canal tumor with ulceration, and biopsy showed squamous cell carcinoma.

Regulating Antifreeze Activity through Water: Latent Functions of the Sugars of Antifreeze Glycoprotein Revealed by Total Chemical Synthesis.

Antifreeze glycoprotein (AFGP), which inhibits the freezing of water, is highly O-glycosylated with a disaccharide, d-Galβ1-3-d-GalNAcα (GalGalNAc). To elucidate the function of the sugar residues for antifreeze activity at the molecular level, we conducted a total chemical synthesis of partially sugar deleted AFGP derivatives, and unnatural forms of AFGPs incorporating glucose (Glc)-type sugars instead of galactose (Gal)-type sugars. These elaborated AFGP derivatives demonstrated that the stereochemistry of each sugar residue on AFGPs precisely correlates with the antifreeze activity.

Isolation and characterization of high-mannose type glycans containing five or six mannose residues from hen egg yolk.

High-mannose type glycans play important roles in biosynthesis of glycoproteins including glycoprotein quality control system. In the endoplasmic reticulum (ER), α1,2-mannosidases cleave several mannose (Man) residues to give small high-mannose type glycans, such as glycans containing five or six mannose residues (M5-glycan or M6-glycan). These glycans are reported to act as a signal for degradation processes of glycoproteins in the ER.

Design and Synthesis of Glycosylated Cholera Toxin B Subunit as a Tracer of Glycoprotein Trafficking in Organelles of Living Cells.

Glycosylation of proteins is known to be essential for changing biological activity and stability of glycoproteins on the cell surfaces and in body fluids. Delivering of homogeneous glycoproteins into the endoplasmic reticulum (ER) and the Golgi apparatus would enable us to investigate the function of asparagine-linked (N-) glycans in the organelles. In this work, we designed and synthesized an intentionally glycosylated cholera toxin B-subunit (CTB) to be transported to the organelles of mammalian cells.

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