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The anharmonic vibrational frequencies of FHF- were computed by the vibrational self-consistent-field, configuration-interaction, and second-order perturbation methods with a multiresolution composite potential energy surface generated by the electronic coupled-cluster method with various basis sets. Anharmonic vibrational averaging was performed for the bond length and nuclear magnetic resonance indirect spin-spin coupling constants, where the latter computed by the equation-of-motion coupled-cluster method. The calculations placed the vibrational frequencies at 580 (ν1), 1292 (ν2), 1313 (ν3), 1837 (ν1+ν3), and 1864 cm-1 (ν1+ν2), the zero-point H–F bond length (r0) at 1.1539 Å, the zero-point one-bond spin-spin coupling constant [1J0(HF)] at 124 Hz, and the bond dissociation energy (D0) at 43.3 kcal/mol. They agreed excellently with the corresponding experimental values: ν1=583 cm-1, ν2=1286 cm-1, ν3=1331 cm-1, ν1+ν3=1849 cm-1, ν1+ν2=1858 cm-1, r0=1.1522 Å, 1J0(HF)=124±3 Hz, and D0=44.4±1.6 kcal/mol. The vibrationally averaged bond lengths matched closely the experimental values of five excited vibrational states, furnishing a highly dependable basis for correct band assignments. An adiabatic separation of high- (ν3) and low-frequency (ν1) stretching modes was examined and found to explain semiquantitatively the appearance of a ν1 progression on ν3. Our calculations predicted a value of 186 Hz for experimentally inaccessible 2J0(FF). [ABSTRACT FROM AUTHOR]

The anharmonic vibrational frequencies of FHF- were computed by the vibrational self-consistent-field, configuration-interaction, and second-order perturbation methods with a multiresolution composite potential energy surface generated by the electronic coupled-cluster method with various basis sets. Anharmonic vibrational averaging was performed for the bond length and nuclear magnetic resonance indirect spin-spin coupling constants, where the latter computed by the equation-of-motion coupled-cluster method. The calculations placed the vibrational frequencies at 580 (ν1), 1292 (ν2), 1313 (ν3), 1837 (ν1+ν3), and 1864 cm-1 (ν1+ν2), the zero-point H–F bond length (r0) at 1.1539 Å, the zero-point one-bond spin-spin coupling constant [1J0(HF)] at 124 Hz, and the bond dissociation energy (D0) at 43.3 kcal/mol. They agreed excellently with the corresponding experimental values: ν1=583 cm-1, ν2=1286 cm-1, ν3=1331 cm-1, ν1+ν3=1849 cm-1, ν1+ν2=1858 cm-1, r0=1.1522 Å, 1J0(HF)=124±3 Hz, and D0=44.4±1.6 kcal/mol. The vibrationally averaged bond lengths matched closely the experimental values of five excited vibrational states, furnishing a highly dependable basis for correct band assignments. An adiabatic separation of high- (ν3) and low-frequency (ν1) stretching modes was examined and found to explain semiquantitatively the appearance of a ν1 progression on ν3. Our calculations predicted a value of 186 Hz for experimentally inaccessible 2J0(FF). [ABSTRACT FROM AUTHOR]

Objectives: Postoperative pancreatic fistula (POPF) is the most significant and potentially lethal complication of pancreatectomy. This study evaluated the association between MRI pancreatic T1 mapping and POPF and developed a new, useful, and noninvasive predictor of distal pancreatectomy (DP)., Methods: The study included 39 patients who underwent preoperative MRI T1 mapping using the Modified Look-Locker Inversion Recovery Sequence (MOLLI) followed by DP between January 2018 and July 2024. Patients with (POPF (+), n=15) and those without POPF (POPF (-), n=24) were compared for their characteristics, perioperative outcomes, and parameters derived from MRI. The circular region of interest was positioned on the pancreatic head, ventral side of the portal vein, and transection site to measure the T1 mapping value. The data were analyzed using R1 values (R1=1/T1), and the cut-off values were calculated using the receiver operating characteristic (ROC) curve., Results: The R1 value of the pancreatic transection site in the POPF (+) group was significantly higher than that in the POPF (-) group (1.180 vs. 1.066 sec-1; P<0.001). The R1 value of the pancreatic transection site was an independent risk factor for grade B/C POPF (odds ratio, 5.01; P=0.005). To predict POPF, a cutoff R1 value of 1.116 sec-1 at the transection site was obtained by maximizing the Youden index., Conclusions: High R1 values at the pancreatic transection site indicate a higher possibility of developing grade B/C POPF. Preoperative MRI T1 mapping may be valuable for predicting POPF after DP., Competing Interests: Disclosure: The authors have no conflicts of interest to disclose., (Copyright © 2025 Wolters Kluwer Health, Inc. All rights reserved.)

Cholangiocarcinoma has a poor prognosis, and resection is the only curative treatment. Pembrolizumab, a programmed death receptor 1 inhibitor, has proven effective against unresectable or metastatic solid tumors with high microsatellite instability (MSI-H) or a high tumor mutation burden (TMB-H). In the present case, pembrolizumab treatment was initiated after standard chemotherapy for MSI-H and TMB-H unresectable intrahepatic cholangiocarcinoma. Intrahepatic tumor necrosis perforated the abdominal cavity. Emergency surgery was performed, but the patient died 36 days after admission. A pathological autopsy revealed that the intrahepatic tumor had almost completely disappeared.

Leucine-rich repeat-containing G-protein-coupled receptor 5 (LGR5) is a known cancer stem cell marker. However, there are no reported analyses of LGR5 mRNA expression in normal liver and liver cancer tissues. Here, we evaluated LGR5 expression by RNAscope, a newly developed RNA in situ hybridization technique, using a tissue microarray consisting of 25 samples of intrahepatic cholangiocarcinoma (ICC) selected from the medical archives at our hospital. LGR5 expression levels were divided into high and low expression groups by the five-grade scoring system, and clinicopathological features were analyzed. Low LGR5 expression was identified in some normal hepatocytes and bile duct cells. In addition, LGR5 expression was identified in all bile duct cancer samples except one case. Well-differentiated to moderately-differentiated adenocarcinoma tended to show higher LGR5 expression than poorly-differentiated adenocarcinoma (P = 0.0561), and the large duct type showed significantly higher LGR5 expression levels than the small duct type (P = 0.0225). Patients in the high LGR5 expression group tended to have good overall survival (OS) (P = 0.0623). The Cox proportional hazard regression model revealed that the high LGR5 expression group showed independently better OS for ICC (P = 0.0285). High LGR5 expression is possibly a good prognosis factor in ICC. However, the detailed mechanism of LGR5 in this disease remains unclear, and further analysis is warranted., (Copyright © 2022 Elsevier GmbH. All rights reserved.)