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Exploring methods for assembling functional materials at the molecular level may yield functional expressions derived from the assembly method. This study developed novel switchable molecular assemblies characterized by abrupt, complete phase transitions promoted via hydrogen bonding with a chiral carboxylic acid. These assemblies were prepared by aggregating discrete molecules that are unresponsive to external stimuli. Furthermore, enantiopure hydrogen-bond donor (HBD) molecules provide switchable compounds with cooperative and abrupt phase transitions, whereas the racemic mixture of the HBD provides a hydrogen-bonded one-dimensional compound with a broad and incomplete phase transition when structural disordering is observed. This study presents a novel strategy for observing metal-to-metal electron-transfer-coupled spin transitions via hydrogen-bond formation.
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BACKGROUND: The aim of this study was to evaluate factors to predict positive peritoneal cytology, whcih would determine the indication for staging laparoscopy in pancreatic cancer. METHODS: A total of 430 patients that underwent pancreatectomy for resectable and borderline resectable pancreatic cancer were retrospectively reviewed. RESULTS: Among 430 patients, 36 had positive cytology (8.4%). Median survival time in negative cytology was 24.7 months, compared with 15.1 months in positive cytology (p = .004). Factors to predict positive cytology in pancreatic cancer according to multivariate analysis were tumor location (body, tail; OR 2.66; 95% CI: 1.21-5.85; p = .015), tumor size ≥30 mm (OR 2.95; 95% CI: 1.35-6.47; p = .007) and radiographic other-organ invasion (HR 2.79; 95% CI: 1.01-7.67; p = .047). Patients were scored 0 to 3 corresponding with these factors. Rates of positive cytology increases in each score were: score 0: 2.9%, score 1: 6.7%, score 2: 18.3%, score 3: 36.8%. CONCLUSIONS: Tumor location (body or tail), tumor size ≥30 mm, and radiographic other-organ invasions were risk factors for positive cytology in pancreatic cancer. This scoring system might be a useful indicator to perform staging laparoscopy to diagnose positive cytology.
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Estadificación de Neoplasias , Pancreatectomía , Neoplasias Pancreáticas , Humanos , Neoplasias Pancreáticas/patología , Neoplasias Pancreáticas/cirugía , Neoplasias Pancreáticas/mortalidad , Neoplasias Pancreáticas/diagnóstico por imagen , Femenino , Masculino , Estudios Retrospectivos , Anciano , Pancreatectomía/métodos , Persona de Mediana Edad , Laparoscopía/métodos , Adulto , Valor Predictivo de las Pruebas , Anciano de 80 o más Años , Pronóstico , Neoplasias Peritoneales/patología , Neoplasias Peritoneales/cirugía , Neoplasias Peritoneales/mortalidad , Citodiagnóstico/métodos , Invasividad Neoplásica/patología , Tasa de Supervivencia , CitologíaRESUMEN
Two new salts of a mononuclear tripodal Fe(II) complex were prepared, using ClO4- and Cl-. The ClO4- sample (1) remained HS at low temperatures, similar to the previously reported BF4- analogue. Crystallising with the Cl- anion (2) led to a markedly different crystal packing arrangement, and engendered SCO activity. This has been correlated to the lower crystal packing density in 2 and the coordination complex conformational differences arising due to the packing motifs of 1 and 2. Further, solvent ordering effects have been proposed to facilitate spin transition behaviour in 2.
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This work investigated the spin states of the cobalt(II) complexes [Co(L1)2](X)2 (1·X; L1 = 4'-(4-N,N'-diphenylaminophenyl)-2,2':6',2''-terpyridine, X = PF6, BPh4) and [Co(L2)2](X)2 (2·X; L2 = 4'-(4-N,N'-dimethylaminophenyl)-2,2':6',2''-terpyridine, X = PF6, BPh4) in the solid state and in solution. In the solid state, 1·PF6 and 2·PF6, both containing smaller PF6- counter anions, showed gradual spin-crossover. In contrast, 1·BPh4 and 2·BPh4 remained in the high-spin state over the temperature range of 5-400 K due to a lower degree of molecular cooperativity. Each of the cobalt(II) complexes exhibited effects of temperature and concentration on their absorption spectra that were related to the spin states in various organic solvents. This work provides new insights into the spectroscopic properties resulting from the spin states of cobalt(II) complexes in solution.
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Three Fe(III)-based coordination complexes [Fe(dqmp)2](NO3)·H2O (1), [Fe(dqmp)2](BF4)·2CH3COCH3 (2), and [Fe(dqmp)2](ClO4) (3) were synthesized from Fe(NO3)3·9H2O/Fe(ClO4)3·xH2O, NaBF4, and 2,4-dichloro-6-((quinoline-8-ylimino)methyl)phenol (Hdqmp) in methanol/acetone and characterized. The structures of complexes 1-3 were determined via single-crystal X-ray crystallography at 100 K and room temperature, and their magnetic properties in the solid and solution forms were investigated. All complexes showed meridional structures with two tridentate dqmp- ligands coordinated with Fe(III) cations. In the solid state, complex 1 showed an abrupt and complete spin crossover at 225 K, whereas complexes 2 and 3 exhibited an incomplete spin crossover at 135 and 150 K, respectively. In a dimethylformamide solution, the complexes showed counterion-dependent spin transitions. In contrast to the solid state, in solution, complex 1 did not exhibit complete spin crossover. However, complexes 2 and 3 showed more complete spin transitions in solutions than in the solid state. The relaxation times, T1 and T2, for 1 and 2 were determined and both increased with temperature from 220 to 380 K. The T1 of 1 was larger than that of 2 at 380 K, and the T1 values were larger than the T2 values.
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Coexistence and switching between spin-crossover (SCO) and single molecular magnet (SMM) behaviours in one single complex may lead to materials that exhibit bi-stable and stimuli sensitive properties in a wide temperature range and under multiple conditions; unfortunately, the conflict and dilemma in the principle of approaching SCO and SMM molecules make it particularly difficult; at low temperature, low spin (LS) SCO molecules possess highly symmetrical geometry and isotropic spins, which are not suitable for SMM behaviour. Herein, we overcome this issue by using a rationally designed Co(II) mononuclear complex [Co(MeOphterpy)2] (ClO4)2 (1; MeOphterpy = 4'-(4-methoxyphenyl)-2,2':6',2''-terpyridine), the magnetic properties of which reversibly respond to desolvation and solvation. The solvated structure reinforced a low distortion of the coordination sphere via hydrogen bonding between ligands and methanol molecules, while in the desolvated structure a methoxy group flipping occurred, increasing the distortion of the coordination sphere and stabilising the HS state at low temperature, which exhibited a field-induced slow magnetic relaxation, resulting in a reversible switching between SCO and SMM properties within one molecule.
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Graphene oxide (GO) has received increasing attention in the life sciences because of its potential for various applications. Although GO is generally considered biocompatible, it can negatively impact cell physiology under some circumstances. Here, we demonstrate that the cytotoxicity of GO greatly varies depending on the cell adhesion states. Human HCT-116 cells in a non-adhered state were more susceptible to GO than those in an adherent state. Apoptosis was partially induced by GO in both adhered and non-adhered cells to a similar extent, suggesting that apoptosis induction does not account for the selective effects of GO on non-adhered cells. GO treatment rapidly decreased intracellular ATP levels in non-adhered cells but not in adhered ones, suggesting ATP depletion as the primary cause of GO-induced cell death. Concurrently, autophagy induction, a cellular response for energy homeostasis, was more evident in non-adhered cells than in adhered cells. Collectively, our observations provide novel insights into GO's action with regard to cell adhesion states. Because the elimination of non-adhered cells is important in preventing cancer metastasis, the selective detrimental effects of GO on non-adhered cells suggest its therapeutic potential for use in cancer metastasis.
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Grafito , Neoplasias , Humanos , Apoptosis , Grafito/farmacología , Línea Celular Tumoral , Adenosina Trifosfato/farmacología , Óxidos/farmacologíaRESUMEN
PURPOSE: We investigated the potential clinical utility of short-term serial KRAS-mutated circulating cell-free tumor DNA (ctDNA) assessment for predicting therapeutic response in patients undergoing first-line chemotherapy for advanced pancreatic cancer. METHODS: We collected 144 blood samples from 18 patients with locally advanced or metastatic cancer that were undergoing initial first-line chemotherapy of gemcitabine plus nab-paclitaxel (GEM plus nab-PTX). Analysis of KRAS-mutated ctDNA was quantified by digital droplet polymerase chain reaction (ddPCR) as mutant allele frequency (MAF). This study investigated pretreatment KRAS-mutated ctDNA status and ctDNA kinetics every few days (days 1, 3, 5 and 7) after initiation of chemotherapy and their potential as predictive indicators. RESULTS: Of the 18 enrolled patients, an increase in KRAS-mutated ctDNA MAF values from day 0-7 after initiation of chemotherapy was significantly associated with disease progression (P < 0.001). Meanwhile, positive pretreatment ctDNA status (MAF ≥ 0.02%) (P = 0.585) and carbohydrate antigen 19-9 (CA19-9) values above the median (P = 0.266) were not associated with disease progression. In univariate analysis, this short-term increase in ctDNA MAF values (day 0-7) was found to be associated with significantly shorter progression free survival (PFS) (hazard ration [HR], 24.234; range, (2.761-212.686); P = 0.0002). CONCLUSION: This short-term ctDNA kinetics assessment may provide predictive information to reflect real-time therapeutic response and lead to effective refinement of regimen in patients with advanced pancreatic cancer undergoing systemic chemotherapy.
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Ácidos Nucleicos Libres de Células , ADN Tumoral Circulante , Neoplasias Pancreáticas , Humanos , ADN Tumoral Circulante/genética , Proteínas Proto-Oncogénicas p21(ras)/genética , Neoplasias Pancreáticas/tratamiento farmacológico , Neoplasias Pancreáticas/genética , Neoplasias Pancreáticas/patología , Progresión de la Enfermedad , Supervivencia sin Progresión , Biomarcadores de Tumor/genética , Mutación , PronósticoRESUMEN
Ion conductors comprising noncentrosymmetric frameworks have emerged as new functional materials. However, strongly correlated polarity functionality and ion transport have not been achieved. Herein, we report a ferroelectric proton conductor, K2MnN(CN)4·H2O (1·H2O), exhibiting the strong correlation between its polar skeleton and conductive ions that generate anomalous ferroelectricity via the proton-bias phenomenon. The application of an electric field of ±1 kV/cm (0.1 Hz) on 1·H2O at 298 K produced the ferroelectricity (polarization = 1.5 × 104 µC/cm2), which was enhanced by the ferroelectric-skeleton-trapped conductive protons. Furthermore, the strong polarity-proton transport coupling of 1·H2O induced a proton-rectification-like directional ion-conductive behavior that could be adjusted by the magnitude and direction of DC electric fields. Moreover, 1·H2O exhibited reversible polarity switching between the polar 1·H2O and its dehydrated form, 1, with a centrosymmetric structure comprising an order-disorder-type transition of the nitrido-bridged chains.
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Laparoscopic anatomical resection of liver segment II (S2 segmentectomy) using left lateral section-flip up method is introduced to safely and effectively encircle the Glissonean branch of segment II (G2) and to expose the left hepatic vein (LHV). The left lateral section is completely mobilized and then flipped up. After encircling and clamping the G2 root, indocyanine green is intravenously injected and the demarcation line is clearly confirmed by near infrared fluorescence imaging. After exposure of the LHV from the root to this intersegmental plane between segments II/III, residual parenchymal resection is performed using the clamp crushing method. There are two difficulties concerning S2 segmentectomy. The first is encirclement of the G2 root without interfering with the G3. Compared with the conventional front view of the umbilical portion, the view behind the left lateral section contribute to easy confirmation and direct encircle of the G2 root without dividing the G3 and injuring LHV on the same plane. The second difficulty is that the boundary of the visible liver surface between segments II/III does not match the direction of the LHV. This can cause confusion to the operator aiming to perform precise inner parenchymal resection. Our procedure allows easy access to the LHV root and exposure of the peripheral directing hepatic vein. Hepatic vein-guided approaches will likely be helpful in precise performance of inner parts of liver resection.
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Laparoscopía , Neoplasias Hepáticas , Humanos , Venas Hepáticas/cirugía , Neoplasias Hepáticas/cirugía , Hepatectomía/métodos , Laparoscopía/métodosRESUMEN
BACKGROUND: Liver resection offers substantial advantages over open liver resection (OLR) for patients with hepatocellular carcinoma (HCC) in terms of reduced intraoperative blood loss and morbidity. However, there is limited evidence comparing the indications and perioperative outcomes with the open versus laparoscopic approach for resection. This study aimed to compare postoperative outcomes between patients undergoing laparoscopic liver resection (LLR) and OLR for HCC with clinically significant portal hypertension (CSPH). METHODS: A total of 316 HCC patients with CSPH (the presence of gastroesophageal varices or platelet count < 100,000/ml and spleen diameter > 12 cm) undergoing minor liver resection at eight centers were included in this study. To adjust for confounding factors between the LLR and OLR groups, an inverse probability weighting method analysis was performed. RESULTS: Overall, 193 patients underwent LLR and 123 underwent OLR. After weighting, LLR was associated with a lower volume of intraoperative blood loss and the incidence of postoperative complications (including pulmonary complications, incisional surgical site infection, and paralytic ileus) compared to the OLR group. The 3-, 5-, and 7-year postoperative recurrence-free survival rates were 39%, 26%, and 22% in the LLR group and 49%, 18%, and 18% in the OLR group, respectively (p = 0.18). And, the 3-, 5-, and 7-year postoperative overall survival rates were 71%, 56%, and 44% in the LLR group and 76%, 51%, 44% in the OLR group, respectively (p = 0.87). CONCLUSIONS: LLR for HCC patients with CSPH is clinically advantageous by lowering the volume of intraoperative blood loss and incidence of postoperative complications, thereby offering feasible long-term survival.
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Carcinoma Hepatocelular , Hipertensión Portal , Laparoscopía , Neoplasias Hepáticas , Humanos , Carcinoma Hepatocelular/complicaciones , Carcinoma Hepatocelular/cirugía , Neoplasias Hepáticas/complicaciones , Neoplasias Hepáticas/cirugía , Pérdida de Sangre Quirúrgica , Hepatectomía/métodos , Laparoscopía/métodos , Hipertensión Portal/complicaciones , Hipertensión Portal/cirugía , Puntaje de Propensión , Infección de la Herida Quirúrgica/etiología , Estudios Retrospectivos , Tiempo de Internación , Complicaciones Posoperatorias/epidemiología , Complicaciones Posoperatorias/etiología , Complicaciones Posoperatorias/cirugíaRESUMEN
Hepatocellular carcinoma (HCC) has a high rate of recurrence and poor prognosis, even after curative surgery. Multikinase inhibitors have been applied for HCC patients, but their effect has been restricted. This study aims to clarify the clinical impact of SUV420H1/KMT5B, one of the methyltransferases for histone H4 at lysine 20, and elucidate the novel mechanisms of HCC progression. We retrospectively investigated SUV420H1 expression using HCC clinical tissue samples employing immunohistochemical analysis (n = 350). We then performed loss-of-function analysis of SUV420H1 with cell cycle analysis, migration assay, invasion assay and RNA sequence for Gene Ontology (GO) pathway analysis in vitro, and animal experiments with xenograft mice in vivo. The SUV420H1-high-score group (n = 154) had significantly poorer prognosis for both 5-year overall and 2-year/5-year disease-free survival than the SUV420H1-low-score group (n = 196) (p < 0.001 and p < 0.05, respectively). The SUV420H1-high-score group had pathologically larger tumor size, more tumors, poorer differentiation, and more positive vascular invasion than the SUV420H1-low-score group. Multivariate analysis demonstrated that SUV420H1 high score was the poorest independent factor for overall survival. SUV420H1 knockdown could suppress cell cycle from G1 to S phase and cell invasion. GO pathway analysis showed that SUV420H1 contributed to cell proliferation, cell invasion, and/or metastasis. Overexpression of SUV420H1 clinically contributed to poor prognosis in HCC, and the inhibition of SUV420H1 could repress tumor progression and invasion both in vitro and in vivo; thus, further analyses of SUV420H1 are necessary for the discovery of future molecularly targeted drugs.
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Carcinoma Hepatocelular , Neoplasias Hepáticas , Animales , Humanos , Ratones , Carcinoma Hepatocelular/patología , Línea Celular Tumoral , Movimiento Celular/genética , Proliferación Celular/genética , Regulación Neoplásica de la Expresión Génica , Histona Metiltransferasas/genética , Histona Metiltransferasas/metabolismo , Neoplasias Hepáticas/patología , Metiltransferasas/genética , Pronóstico , Estudios RetrospectivosRESUMEN
Two mononuclear Ni(II) complexes (1 and 2) have been found to display color changes upon coordination/decoordination of pyridine, resulting in their structural transformation between square-planar and octahedral geometries as well as a change in their spin state. Compound 1 changes between red (1r) and yellow (1y) upon exposure to or elimination of pyridine, while 2 undergoes a two-step transformation, changing orange 2o (S = 0) â gray 2g' (S = 1) â yellow 2y' (S = 1) depending on the reaction time. The first step (2o â 2g') takes less than 45 min, which is significantly faster than the previously reported reaction time of 1 day for a Ni(II) complex/pyridine vapor system. Compound 2o reacting with pyridine can be easily prepared by dispersing 2g in methanol instead of annealing at high temperatures (130 °C), which can be applied to develop chemical sensors for pyridine utilizing color changes and/or magnetic switching.
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Background: Malignancy patients who need long-term hospitalization can feel loneliness affecting their quality of life. The global COVID-19 pandemic has caused visiting restrictions that could mean patients who might be missing out on family support and palliative care, therefore, need to adapt and change. We used virtual reality (VR) technology with the aim of reducing feelings of loneliness among these patients. Objectives: In a small cohort setting, we aimed to clarify the usefulness of VR viewing for this purpose by text mining interviews with the patients in palliative care after their VR experience, and to clarify the feasibility of this program. Design and Setting/Subjects: Four consecutive Japanese patients in the palliative care unit viewed personalized familiar persons or places through VR goggles, while communicating by telephone. After the VR experience, text mining of the patients' interviews was used to extract the words for the frequency count and co-occurrence analysis. Results: Four clusters were extracted: "relief from the pain of hospitalization by feeling safe and secure with family members nearby," "using VR to regain daily life," "immersive feeling of being in the same space as family," and "loneliness due to the realistic feeling of separation from the family through VR experience." There were no cases of VR sickness. Conclusion: Our results attained by text mining suggest the promising potential of VR imaging of familiar surroundings for patients in palliative care.
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An organic-inorganic hybrid metal halide (OIMH), namely the electron-deficient naphthalene diimide (NDI) and [CoCl4]2- hybrid (1), showed potential as a sensor for ammonia and amines, in addition to magnetic changes upon vapochromism. Crystal 1 exhibited thermosalient behavior such as leaping and movement, at around 130 °C, which could be explained to be associated with the removal of water molecules from the crystal lattice as shown by TGA and DSC. Compound 1 changed from green to black within 5 minutes when exposed to ammonia vapor, which was attributed to the radical formation in the NDI moiety as evidenced by ESR, and this phenomenon was preserved even when other mono- and di-alkylamines were applied. The exposure of 1 to ammonia resulted in a subsequent color alteration, progressing from black to a gradually dark orange after one day (1_NH3_1 day). This transformation was concomitant with the formation of [Co(NH3)6]3+ from [CoCl4]2-, leading to a modification of the magnetic properties from paramagnetic Co(II) (S = 3/2) to diamagnetic Co(III) (S = 0). Based on these findings, compound 1 represents the first example of an OIMH that exhibits thermosalient behaviour, color change, and magnetic conversion upon exposure to ammonia.
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When reacted together with uranyl ions under solvo-hydrothermal conditions, a bis(pyridiniumcarboxylate) zwitterion (L) and tricarballylic acid (H3tca) give the complex [NH4]2[UO2(L)2][UO2(tca)]4·2H2O (1). The two ligands are segregated into different units, an anionic nanotubule for tca3- and a six-fold interpenetrated cationic framework with lvt topology for L. The entangled framework defines large channels which contain the square-profile nanotubules. Complex 1 has a photoluminescence quantum yield of 19% and its emission spectrum shows the superposition of the signals due to the two independent species.
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Right anterior liver sectionectomy (RAS) is a complicated procedure with high incidences of postoperative complications. We report a case of right posterior bile duct (RPBD) stricture after laparoscopic RAS with discussion of the anatomical aspects. A 69-year-old Japanese man had solitary colorectal liver metastasis. A tumor was located near the root of the right anterior Glissonean pedicle. On postoperative day 6, he had cholangitis and imaging studies showed RPBD stricture. Symptoms disappeared following a course of antibiotics and the patient was discharged on postoperative day 21. The RBPD anatomy type of this patient was a supra-portal pattern with a long (18 mm) right biliary duct, which would be close to the right anterior Glissonean bifurcation. A stapling device might have caused its deformation and resulted in its stricture. As the RPBD has variant anatomy, we had to notice that there may be hazardous types for postoperative RPBD stricture.
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Conductos Biliares , Laparoscopía , Neoplasias Hepáticas , Anciano , Humanos , Masculino , Conductos Biliares/cirugía , Constricción Patológica/etiología , Constricción Patológica/cirugía , Hepatectomía/efectos adversos , Hepatectomía/métodos , Laparoscopía/métodos , Neoplasias Hepáticas/cirugíaRESUMEN
BACKGROUND: The prognostic impact of radiographic duodenal invasion (rDI) of pancreatic ductal adenocarcinoma (PDAC) has yet to be fully elucidated. This retrospective study aimed to investigate the prognostic and clinicopathological significance of rDI in patients with PDAC after pancreatoduodenectomy (PD). MATERIALS AND METHODS: We retrospectively analyzed 223 consecutive patients with resectable (R) and borderline resectable (BR)-PDAC that underwent up-front PD between 2002 and 2018. rDI was assessed by preoperative multi-detector row computed tomography. RESULTS: Ninety-three (42%) patients with PDAC had rDI, and all of them had pathological DI (pDI). The rDI(+) group had larger tumor size, BR-PDAC was more common, there was higher serum CA19-9 level, and microscopic lymphovascular invasion was more common than in the rDI(-) group. rDI was associated with significant reduction in overall survival (OS) (P < 0.001) and recurrence-free survival (RFS) (P < 0.001). In multivariate analysis, rDI was an independent prognostic factor in OS [hazard ratio (HR) = 0.52; 95% confidence interval (CI) 0.38-0.73, P < 0.001] and RFS [HR = 0.56; 95% CI 0.40-0.78, P = 0.001]. rDI was also an independent risk factor for early recurrence within 12 months [odds ratio (OR) = 0.36; 95% CI 0.18-0.73, P = 0.005]. rDI had positive correlation with liver recurrence (P = 0.024). CONCLUSION: Biological aggressiveness of PDAC with rDI implies short OS and early recurrence with frequent liver metastasis. Aggressive perioperative chemotherapy is recommended to improve prognosis, especially for R-PDAC patients with rDI.