Effect of remotely connected trialkyl ammonium groups on the dye molecules in the photochemical behavior on the clay nanosheet.

The enhanced emission properties of several cationic dye molecules on the clay surface established as a result of the strong electrostatic interaction and associated molecular flattening leading to either the suppression of non-radiative deactivation processes or the improvement of radiative deactivation processes has been verified, and it is known as surface-fixation induced emission (S-FIE). Here, the differences in the S-FIE properties as well as the self-fluorescence quenching behavior of the dimidium and propidium dyes were compared. Propidium differs from dimidium by the substitution of a propyl (diethyl methylammonium) group at the 5th position instead of the methyl group in dimidium. So, the differences induced by this substitution, which is not even in conjugation with the chromophore part of the dye molecule show a significant impact on the adsorption strength, S-FIE properties, and self-fluorescence quenching behavior. In propidium and dimidium, the suppression of knr was the key factor for emission enhancement on the clay surface. Interestingly, the alkylammonium cation group in the Propidium helped for better adsorption strength as well as to reduce the self-fluorescence quenching behavior on the clay surface as compared to the dimidium. Since the trialkylammonium cation was not in conjugation with the core structure of the molecule and located at a specific distance, it did not interrupt the flattening of the molecule on the clay surface. These results could be beneficial in the construction of efficient photochemical reaction systems, where the molecule having low adsorption strengths can be modified by alkyl ammonium cations, which will not affect molecular planarization.

Effects of Clay Nanosheets on the Photostability of Cationic Porphyrin.

The photodecomposition behavior of cationic porphyrin ZnTMAP4+ (zinc tetrakis-(N,N,N-trimethylanilinium-4-yl) porphyrin) in water and complexed with clay nanosheets was investigated by light irradiation to the Soret band of ZnTMAP4+. The decomposition of ZnTMAP4+ was observed by UV-visible absorption spectroscopy. While the decomposition quantum yield (ϕdec) was 3.4 × 10-4 in water, that was 9.4 × 10-7 on the exfoliated clay nanosheets. It was revealed that the photostability of ZnTMAP4+ was stabilized by the complex formation with clay. When ZnTMAP4+ was intercalated between the stacked clay nanosheets, ϕdec was further decreased to 4.9 × 10-7. The photostability increased by 361 times and 693 times for the exfoliated and stacked state, respectively. These results indicate that the flat clay surface has the potential to control intra- and intermolecular photochemical reactions.

Fluorescence enhancement of benzimidazolium derivative on clay nanosheets by surface-fixation induced emission (S-FIE).

The photophysical behaviors of benzimidazolium derivative [4-(1,3-dimethylbenzimidazol-3-imu-2-yl)-N, N-diphenylaniline (2-(4-(diphenylamino)phenyl)-1,3-dimethyl-1H-benzo[d]imidazol-3-ium)] (BID) in water, organic solvents and on synthetic saponite were investigated. The fluorescence quantum yield (Φf) of BID was 0.91 on the saponite surface under the optimal condition, while that in water was 0.010. Such fluorescence enhancement on the inorganic surface is called "surface-fixation induced emission (S-FIE)". This fluorescence enhancement ratio for BID is significantly high compared to that of conventional S-FIE active dyes. From the values of Φf and the excited lifetime, the non-radiative deactivation rate constant (knr) and radiative deactivation rate constant (kf) of BID on the saponite surface and in water were determined. Results showed that the factors for fluorescence enhancement were both the increase of kf and the decrease of knr on the saponite surface; especially, knr decreased by more than two orders due to the effect of nanosheets.

Structural Transformation of Azonia[5]helicene Photoproduct via Reaction Field Function of Layered Inorganic Material.

In an attempt to generalize "on surface synthesis", which has unique potential in the area of organic synthesis, the focus was placed on layered silicates having a highly flat surface. The photoreaction of (±)-13-bromo-6a-azonia[5]helicene (AHHBr) and (±)-2-bromo-13-methyl-6a-azonia[5]helicene (AHBrMe) in solution and within the layers was examined. In the case of AHBrMe, the photoproduct was different from that in solution. 1H nuclear magnetic resonance (NMR), Fourier transform-infrared spectroscopy (FT-IR), and electrospray ionization-mass spectrometry (ESI-MS) measurements revealed that the photoproduct obtained within the layers was a benzo-perylene molecule with a completely flat lactone structure (AL). This study is the first example of the successful conversion of a chemical reaction path due to the steric effect of the flat surface of layered silicate.

Monolayer Modification of Spherical Amorphous Silica by Clay Nanosheets.

Clay-silica nanocomposite materials (CSiN) were prepared by an electrostatic interaction between negatively charged clay nanosheets and positively charged spherical silica, which was modified with an alkyl ammonium group by silane coupling. By optimization of the preparation conditions, 84% coverage of the silica surface by the clay nanosheets was achieved. Adsorption experiments using cationic porphyrin dyes on the CSiN revealed that the clay nanosheet covers the spherical silica as a single layer and does not detach from the silica surface under aqueous conditions. In addition, it turned out that the cationic porphyrin dye did not penetrate the space between the silica surface and the clay nanosheet. Porphyrin molecules were adsorbed only at the outer surface of the clay nanosheet without molecular aggregation even under the high-density adsorption conditions. By combining spherical silica and clay nanosheets, it is possible to prepare novel hybrid materials where the surface can act as a unique adsorption field for dyes.

Decoration of Gold and Platinum Nanoparticle Catalysts by 1 nm Thick Metal Oxide Overlayer and Its Effect on the CO Oxidation Activity.

Exfoliated M-Al layered double hydroxide (M-Al LDH; M = Mg, Co, Ni, and Zn) nanosheets were adsorbed on Au/SiO2 and calcined to transform LDH into mixed metal oxides (MMOs) and yield Au/SiO2 coated with a thin MMO overlayer. These catalysts showed a higher catalytic activity than pristine Au/SiO2. In particular, the 50% CO conversion temperature decreased by more than 250 °C for Co-Al MMO-coated Au/SiO2. In contrast, the deposition of CoAlOx on Au/SiO2 by impregnation or the deposition of Au on Co-Al MMO-coated SiO2 resulted in a worse catalytic activity. Moreover, the presence of a thick MMO overlayer decreased the catalytic activity, suggesting that the control of the overlayer thickness to less than 1 nm is a requisite for obtaining a high catalytic activity. Moreover, the thin Co-Al MMO overlayer on Au/SiO2 possessed abundant oxygen vacancies, which would play an important role in O2 activation, resulting in a highly active interface between Au and the defect-rich MMO on the Au NP surface. Finally, this can be applied to Pt/SiO2, and the obtained Co-Al MMO-coated Pt/SiO2 also exhibited a much improved catalytic activity for CO oxidation.

Association between postoperative hypotension and acute kidney injury after noncardiac surgery: a historical cohort analysis.

PURPOSE: The extent to which postoperative hypotension contributes to renal injury remains unclear, much less what the harm thresholds might be. We therefore tested the primary hypothesis that there is an absolute hypotensive arterial pressure threshold for acute kidney injury during the initial seven days after noncardiac surgery. METHODS: We conducted a single-centre historical cohort analysis of adults who had noncardiac surgery and had creatinine recorded preoperatively and postoperatively. Our exposure was the lowest postoperative mean arterial pressure, defined as the average of the three lowest postoperative pressure measurements. Our primary analysis was the association between the lowest mean arterial pressure and acute kidney injury, defined according to Kidney Disease: Improving Global Outcomes initiative criteria. Our analysis was adjusted for potentially relevant confounding factors including intraoperative hypotension. RESULTS: Among 64,349 patients analyzed, 2,812 (4.4%) patients had postoperative acute kidney injury. Each 5-mm Hg decrease in the lowest mean arterial pressure was associated with a 28% (97.5% confidence interval [CI], 23 to 32; P < 0.001) increase in the odds of acute kidney injury for lowest mean arterial pressures < 80 mm Hg. Higher lowest pressures were not associated with acute kidney injury (odds ratio, 1.08; 97.5% CI, 0.99 to 1.17; P = 0.04) for each 5-mm Hg decrease in the lowest mean arterial pressure. CONCLUSION: Postoperative hypotension, defined as the lowest postoperative mean arterial pressure < 80 mm Hg, was associated with acute kidney injury after noncardiac surgery. A prospective trial will be required to determine whether the observed association is causal and thus amenable to modification.

RéSUMé: OBJECTIF: Nous ne savons pas dans quelle mesure l'hypotension postopératoire contribue aux lésions rénales, et nous connaissons encore moins les seuils de lésion. Nous avons donc testé l'hypothèse primaire selon laquelle il existerait un seuil absolu de tension artérielle hypotensive pour l'insuffisance rénale aiguë au cours des sept premiers jours suivant une chirurgie non cardiaque. MéTHODE: Nous avons mené une analyse de cohorte historique monocentrique auprès d'adultes ayant bénéficié d'une chirurgie non cardiaque et pour lesquel·les les taux de créatinine avant et après l'opération avaient été enregistrés. Notre exposition était la tension artérielle moyenne postopératoire la plus basse, définie comme la moyenne des trois mesures de tension postopératoire les plus basses. Notre analyse principale a porté sur l'association entre la tension artérielle moyenne la plus basse et l'insuffisance rénale aiguë, définies selon les critères de l'initiative KDIGO (Kidney Disease: Improving Global Outcomes). Notre analyse a été ajustée pour tenir compte des facteurs de confusion potentiellement pertinents, notamment de l'hypotension peropératoire. RéSULTATS: Parmi les 64 349 patient·es analysé·es, 2812 (4,4 %) ont présenté une insuffisance rénale aiguë postopératoire. Chaque diminution de 5 mm Hg de la tension artérielle moyenne la plus faible était associée à une augmentation de 28 % (intervalle de confiance [IC] de 97,5 %, 23 à 32; P < 0,001) des risques d'insuffisance rénale aiguë pour les tensions artérielles moyennes les plus faibles < 80 mm Hg. Des tensions les plus faibles plus hautes n'ont pas été associées à une insuffisance rénale aiguë (rapport de cotes, 1,08; IC 97,5 %, 0,99 à 1,17; P = 0,04) pour chaque diminution de 5 mm Hg de la tension artérielle moyenne la plus faible. CONCLUSION: L'hypotension postopératoire, définie comme la tension artérielle moyenne postopératoire < 80 mm Hg la plus basse, a été associée à une insuffisance rénale aiguë après une chirurgie non cardiaque. Une étude prospective sera nécessaire pour déterminer si l'association observée est causale et donc susceptible d'être modifiée.

Gold/Substituted Hydroxyapatites for Oxidative Esterification: Control of Thin Apatite Layer on Gold Based on Strong Metal-Support Interaction (SMSI) Results in High Activity.

Gold nanoparticles (Au NPs) deposited on various cation- and anion-substituted hydroxyapatites (Au/sHAPs) show oxidative strong metal-support interaction (SMSI), wherein a thin layer of the sHAP covered the surface of the Au NPs by heat treatment in an oxidative atmosphere. Calcination of Au/sHAPs at 300 °C caused a partial SMSI and that at 500 °C gave fully encapsulated Au NPs. We investigated the influence of the substituted ions in sHAP and the degree of the oxidative SMSI on the catalytic performance of Au/sHAPs for oxidative esterification of octanal or 1-octanol with ethanol to obtain ethyl octanoate. The catalytic activity depends on the size of the Au NPs but not on the support used, owing to the similarity of the acid and base properties of sHAPs except for Au/CaFAP. The presence of a large number of acidic sites on CaFAP lowered the product selectivity, but all other sHAPs exhibited similar activity when the Au particle size was almost the same, owing to the similarity of the acid and base properties. Au/sHAPs_O2 with SMSI exhibited higher catalytic activity than Au/sHAPs_H2 without SMSI despite the fact that the number of exposed surface Au atoms was decreased by the SMSI. In addition, the oxidative esterification reaction proceeded even though the Au NPs were fully covered by the sHAP layer when the thickness of the layer was controlled to be less than 1 nm. The substrate can access the surfaces of the Au NPs covered by the thin sHAP layer (<1 nm), and the presence of the sHAP structure in close contact with the Au NPs resulted in significantly higher catalytic activity compared with that for fully exposed Au NPs deposited on the sHAPs. This result suggests that maximizing the contact area between the Au NPs and the sHAP support based on the SMSI enhances the catalytic activity of Au.

Small Bowel Obstruction Due to Axial Torsion of Meckel's Diverticulum: A Case Report and Literature Review.

Meckel's diverticulum (MD) is a commonly encountered congenital gastrointestinal abnormality. Although the frequency of MD-related complications such as inflammation or bleeding is relatively high, small bowel obstruction induced by axial torsion of the MD is rare. Therefore, we herein report such a case along with a review of the literature. A 34-year-old female with right lower quadrant pain, nausea, and vomiting was admitted to our hospital with the diagnosis of adhesive small bowel obstruction due to a cesarean section performed five years previously. A long intestinal tube was placed, and the patient's clinical symptoms and X-ray findings showed relief of the small bowel obstruction. However, she developed severe right lower quadrant pain after contrast examination through the long intestinal tube despite the fact that the contrast agent had smoothly reached the terminal ileum. Blood tests and enhanced computed tomography (CT) showed a remarkable elevation of inflammatory markers, the appearance of ascites, and closed-loop-like and abscess-like appearances near the site of the caliber change. With a diagnosis of internal hernia, the patient underwent emergency laparotomy by means of a midline incision. Purulent ascites was observed within the abdominal cavity. Small bowel obstruction caused by a single band was observed in the right lower quadrant. Further exploration revealed an inflammatory MD with neck torsion and a mesodiverticular band (MDB). Simple mesodiverticular band resection by electrocautery and diverticulectomy by linear stapler were performed. The postoperative course was uneventful, and the patient was discharged on postoperative day 7. In the case of juvenile-onset small bowel obstruction, axial torsion of the MD should be considered as a differential diagnosis. Herein, we report such a difficult diagnostic case and the first English literature review of small bowel obstruction due to axial torsion of the MD.

Mild acute kidney injury after pediatric surgery is not-associated with long-term renal dysfunction: A retrospective cohort study.

BACKGROUND AND STUDY OBJECTIVE: Acute kidney injury (AKI) is a sudden deterioration in renal function and is common in pediatric patients undergoing cardiac and non-cardiac surgery. Few studies have investigated the association of postoperative AKI with kidney dysfunction seen long-term and other adverse outcomes in pediatric patients. The study aimed to determine the association between postoperative AKI (mild AKI vs. no AKI and mild AKI vs. moderate-severe AKI) and chronic kidney dysfunction (CKD) seen long-term in pediatric patients undergoing cardiac and non-cardiac major surgery. DESIGN: Restrospective, cohort study. SETTING: Tertiary care hospital. PATIENTS: This retrospective cohort study included patients aged 2-18 years who underwent cardiac and non-cardiac major surgery lasting >2 h at the Cleveland Clinic Main Campus between June 2005 and December 2020. MEASUREMENTS: Postoperative AKI and CKD seen in long-term were defined and staged according to the Kidney Disease: Improving Global Outcomes criteria. MAIN RESULTS: Among 10,597 children who had cardiac and non-cardiac major surgery, 1,302 were eligible. A total of 682 patients were excluded for missing variables and baseline kidney dysfunction and 620 patients were included. The mean age was 11 years, and 307 (49.5%) were female. Postoperative mild AKI was detected in 5.8% of the patients, while moderate-severe AKI was detected in 2.4%. There was no significant difference in CKD seen in long-term between patients with and without postoperative AKI, p = 0.83. The CKD seen in long-term developed in 27.7% of patients with postoperative mild AKI and 33.3% of patients with postoperative moderate and severe AKI. Patients without postoperative AKI had an estimated 1.09 times higher odds of having CKD seen in long-term compared with patients who have postoperative mild AKI (odds ratio [95% CI] 1.09 [0.48,2.52]). CONCLUSION: In contrast to adult patients, the authors did not find any association between postoperative AKI and CKD seen in long-term in pediatric patients.

Intra-operative hypertension and myocardial injury and/or mortality and acute kidney injury after noncardiac surgery: A retrospective cohort analysis.

BACKGROUND: Whether intra-operative hypertension causes postoperative complications remains unclear. OBJECTIVE: We sought to assess whether there is an absolute systolic hypertensive threshold associated with increased odds of a composite of postoperative myocardial injury and mortality, and acute kidney injury. DESIGN: A retrospective cohort analysis using an electronic medical record registry. SETTING: The Cleveland Clinic Main Campus, Cleveland, Ohio, USA, between January 2005 and December 2018. PATIENTS: A total of 76 042 adults who had inpatient noncardiac surgery lasting at least an hour, creatinine recorded preoperatively and postoperatively, and had an available clinic blood pressure within 6 months before surgery. MAIN OUTCOME MEASURES: Univariable smoothing and multivariable logistic regression were used to estimate the probability of each outcome as a function of the highest intra-operative pressure for a cumulative 5, 10, or 30 min. We further assessed whether the relationships between intra-operative hypertension and each outcome depended on baseline systolic blood pressure. RESULTS: The composite of myocardial injury and mortality was observed in 1.9%, and acute kidney injury in 4.5% of patients. After adjustment for confounders, there was little or no relationship between systolic pressure and either outcome over the range from 120 to 200 mmHg. There were also no obvious change points or thresholds above which odds of each outcome increased. And finally, there was no interaction with preoperative clinic blood pressure. CONCLUSIONS: There was no clinically meaningful relationship between intra-operative systolic pressure and the composite of myocardial injury and mortality, or acute kidney injury, over the range from 120 and 200 mmHg.

Associations between intraoperative and post-anesthesia care unit hypotension and surgical ward hypotension.

STUDY OBJECTIVE: To test whether patients who experience hypotension in the post-anesthesia care unit or during surgery are most likely to experience hypotension on surgical wards. DESIGN: A prediction study using data from two randomized controlled trials. SETTING: Operating room, post-anesthesia care unit, and surgical ward. PATIENTS: 550 adult patients having abdominal surgery with ASA physical status I-IV. INTERVENTIONS: Blood pressure measurement per routine intraoperatively, and with continuous non-invasive monitoring postoperatively. MEASUREMENTS: The primary predictors were minimum mean arterial pressure (<60, <65, <70 and < 80 mmHg) and minimum systolic blood pressure (<70, <75, <80, <85 mmHg) in the post-anesthesia care unit. The secondary predictors were intraoperative minimum blood pressures with the same thresholds as the primary ones. Our outcome was ward hypotension defined as mean pressure < 70 mmHg or systolic pressure < 85 mmHg. A threshold was considered clinically useful if both sensitivity and specificity exceeded 0.75. MAIN RESULTS: Minimum mean and systolic pressures in the post-anesthesia care unit similarly predicted ward mean or systolic hypotension, with the areas under the curves near 0.74. The best performing threshold was mean pressure < 80 mmHg in the post-anesthesia care unit which had a sensitivity of 0.41 (95% confidence interval [CI], 0.35, 0.47) and specificity of 0.91 (95% CI, 0.87, 0.94) for ward mean pressure < 70 mmHg and a sensitivity of 0.44 (95% CI, 0.37, 0.51) and specificity of 0.88 (95% CI, 0.84, 0.91) for ward systolic pressure < 85 mmHg. The areas under the curves using intraoperative hypotension to predict ward hypotension were roughly similar at about 0.60, with correspondingly low sensitivity and specificity. CONCLUSIONS: Intraoperative hypotension poorly predicted ward hypotension. Pressures in the post-anesthesia care unit were more predictive, but the combination of sensitivity and specificity remained poor. Unless far better predictors are identified, all surgical inpatients should be considered at risk for postoperative hypotension.

Effects of the Surface Charge Density of Clay Minerals on Surface-Fixation Induced Emission of Acridinium Derivatives.

Surface-fixation induced emission is a fluorescence enhancement phenomenon, which is expressed when dye molecules satisfy a specific adsorption condition on the anionic clay surface. The photophysical behaviors of two types of cationic acridinium derivatives [10-methylacridinium perchlorate (Acr+) and 10-methyl-9-phenylacridinium perchlorate (PhAcr+)] on the synthetic saponites with different anionic charge densities were investigated. Under the suitable conditions, the fluorescence quantum yield (Φf) of PhAcr+ was enhanced 22.3 times by the complex formation with saponite compared to that in water without saponite. As the inter-negative charge distance of saponite increased from 1.04 to 1.54 nm, the Φf of PhAcr+ increased 1.25 times. In addition, the increase in the negative charge distance caused the increase in the integral value of the extinction coefficient and the radiative deactivation rate constant (k f) and the decrease in the nonradiative deactivation rate constant. It should be noted that the 2.3 times increase in k f is the highest among the reported values for the effect of clay. From these results, it was concluded that the photophysical properties of dyes can be modulated by changing the charge density of clay minerals.

"In-water" Dehydration Reaction of an Aromatic Diol on an Inorganic Surface.

The effect of a synthetic saponite surface on the "in-water" dehydration reaction of diol was examined using 4-formyl-1-methylquinolinium salt (MQu+) as a substrate. The equilibrium between aldehyde (MQu+-Aldehyde) and diol (MQu+-Diol) was affected by the surrounding environment. The equilibrium behavior was observed by 1H nuclear magnetic resonance (NMR) and UV-vis absorption measurements. Although MQu+ was completely in the form of MQu+-Diol in water, the equilibrium almost shifted to the MQu+-Aldehyde side when MQu+ was adsorbed on the saponite surface in water. In addition, the MQu+-Aldehyde ratio depended on the negative charge density of saponite. The factors that determine MQu+-Aldehyde: MQu+-Diol ratio were discussed from the thermodynamic analysis of the system. These data indicate that the electrostatic interaction between the charged saponite surface and MQu+ stabilized the aldehyde side enthalpically and destabilized it entropically. The major reason for these results is considered to be the difference in adsorption stabilization between MQu+-Aldehyde and MQu+-Diol on saponite surfaces.

Does local anesthetic temperature affect the onset and duration of ultrasound-guided infraclavicular brachial plexus nerve block?: a randomized clinical trial.

BACKGROUND: Infraclavicular brachial plexus nerve block is a commonly performed anesthesiology technique in the upper extremity. Local anesthetics may be administered at different temperatures for both neuraxial and peripheral nerve blocks. We aimed to evaluate the effects of the temperature of the local anesthetic at the time of administration on the onset and duration of sensory and motor blocks in infraclavicular brachial plexus nerve block. METHODS: A total of 80 patients undergoing elective upper extremity surgery were randomly assigned to one of the following groups using a computer-based randomization software; low temperature (4 °C) (Group L, n = 26), room temperature (25 °C) (Group R, n = 27) and warmed (37 °C) (Group W, n = 27). A 1:1 mixture of 2% lidocaine and 0.5% bupivacaine was used as local anesthetic. Infraclavicular brachial plexus nerve block was performed under ultrasound guidance in all patients preoperatively. The onset and duration of sensory and motor blocks were recorded. RESULTS: Each group had different onset of motor (p < 0.001) and sensory (p < 0.001) blocks. The duration of motor block was similar between groups (p = 221). However, a significant difference was found in the duration of sensory block between group L (399.1 ± 40.8 min) and group R (379.6 ± 27.6 min) (p = 0.043). There was no complication related to nerve block procedure. CONCLUSIONS: The administration of the local anesthetic at lower temperatures may prolong the onset of both motor and sensory blocks in infraclavicular brachial plexus nerve block.

Laparoscopic resection of a metachronous secondary lymph node metastasis in the mesentery of the ileum after surgery for sigmoid colon cancer with ileum invasion: a case report.

BACKGROUND: Extended excision of the permeation organ neighborhood is often performed in locally invasive colon cancer, and it is reported to have a survival benefit. In addition, some cases of secondary lymph node metastases in a permeation organ were reported. However, they are reports of synchronous secondary lymph node metastases, not metachronous secondary lymph node metastases. To the best of our knowledge, there are no cases of metachronous secondary lymph node metastases after the resection of a primary colorectal cancer in PubMed. CASE PRESENTATION: The case was a 67-year-old man who underwent colonoscopy because of weight loss. Sigmoid colon cancer with all circumference-related stenosis was found by examination, and the patient was transferred to our hospital for the purpose of scrutiny and treatment. The small intestine ileus caused by the invasion of sigmoid colon cancer developed after the transfer. Laparoscopic high anterior resection and extended excision of small intestine segmental resection was performed after the intestinal tract decompression with a nasal ileus tube. Histopathological analysis revealed a pathological diagnosis of pT4b (ileal submucosal invasion) N0 (0/11) M0 f Stage II, tub2, ly1, v2, PN0. Although adjuvant chemotherapy with capecitabine after the operation was planned for half a year, treatment was suspended in the first course by the patient's self-judgment. No recurrence was observed for a year after the operation, but metastasis recurrence in the para-aortic lymph node was found by a computed tomography (CT) one and a half years after the operation. 18 F-fluorodeoxyglucose (FDG) positron emission tomography revealed that FDG was accumulated only in the para-aortic lymph node. Laparoscopic metastasis lymphadenectomy was performed due to the diagnosis of metachronous metastasis to the para-aortic lymph node alone. Intraoperative findings revealed that lymph node metastasis occurred in the mesentery of the ileum. No adjuvant treatment was done after the secondary operation, and he is still alive with no recurrence 1 year and 9 months after the operation. CONCLUSIONS: We report a rare case of a laparoscopic resection of a metachronous secondary lymph node metastasis in the mesentery of the ileum after surgery for sigmoid colon cancer with ileum invasion.

Performance of the Hypotension Prediction Index with non-invasive arterial pressure waveforms in non-cardiac surgical patients.

An algorithm derived from machine learning uses the arterial waveform to predict intraoperative hypotension some minutes before episodes, possibly giving clinician's time to intervene and prevent hypotension. Whether the Hypotension Prediction Index works well with noninvasive arterial pressure waveforms remains unknown. We therefore evaluated sensitivity, specificity, and positive predictive value of the Index based on non-invasive arterial waveform estimates. We used continuous hemodynamic data measured from ClearSight (formerly Nexfin) noninvasive finger blood pressure monitors in surgical patients. We re-evaluated data from a trial that included 320 adults ≥ 45 years old designated ASA physical status 3 or 4 who had moderate-to-high-risk non-cardiac surgery with general anesthesia. We calculated sensitivity and specificity for predicting hypotension, defined as mean arterial pressure ≤ 65 mmHg for at least 1 min, and characterized the relationship with receiver operating characteristics curves. We also evaluated the number of hypotensive events at various ranges of the Hypotension Prediction Index. And finally, we calculated the positive predictive value for hypotension episodes when the Prediction Index threshold was 85. The algorithm predicted hypotension 5 min in advance, with a sensitivity of 0.86 [95% confidence interval 0.82, 0.89] and specificity 0.86 [0.82, 0.89]. At 10 min, the sensitivity was 0.83 [0.79, 0.86] and the specificity was 0.83 [0.79, 0.86]. And at 15 min, the sensitivity was 0.75 [0.71, 0.80] and the specificity was 0.75 [0.71, 0.80]. The positive predictive value of the algorithm prediction at an Index threshold of 85 was 0.83 [0.79, 0.87]. A Hypotension Prediction Index of 80-89 provided a median of 6.0 [95% confidence interval 5.3, 6.7] minutes warning before mean arterial pressure decreased to < 65 mmHg. The Hypotension Prediction Index, which was developed and validated with invasive arterial waveforms, predicts intraoperative hypotension reasonably well from non-invasive estimates of the arterial waveform. Hypotension prediction, along with appropriate management, can potentially reduce intraoperative hypotension. Being able to use the non-invasive pressure waveform will widen the range of patients who might benefit.Clinical Trial Number: ClinicalTrials.gov NCT02872896.

Ethnic Differences in Analgesic Efficacy and Safety of Liposomal Bupivacaine Among Asian and Caucasian Surgical Patients: A Retrospective Matched-Cohort Analysis.

BACKGROUND: Extended-release local anesthetics allow for prolonged analgesia after a single administration. Although Asians demonstrate different pain thresholds than Caucasians, whether they have different postoperative local anesthetic analgesic effects has not been elucidated. OBJECTIVE: We aimed to compare the postoperative analgesic efficacy of liposomal bupivacaine on Asian and Caucasian adults, and the incidence of local anesthetic systemic toxicity (LAST) syndrome. METHODS: We conducted a retrospective, assessor-blinded cohort study of adult patients who received liposomal bupivacaine for surgery between 2012 and 2018. Asians and Caucasians were matched in a 1:1 ratio by clinical characteristics and surgery type. The primary outcome was pain management, defined as average pain score and opioid consumption during the initial 72 postoperative hours. The secondary outcome was the incidence of LAST syndrome. Reviewers were blinded to the ethnicity of the patient. RESULTS: After 1:1 propensity score matching, 130 Asians and 129 Caucasians were analyzed. All confounding variables were balanced, except for higher body mass index in the Asian group. Pain scores were lower (adjusted mean difference of -0.50 [97.5% CI, -0.98, -0.01]; superiority p = 0.011) and opioid consumption was not greater (geometric means ratio, 0.61 [97.5% CI, 0.36, 1.04]; non-inferiority p ＜ 0.001) in Asian patients compared to Caucasian patients. Only one Caucasian patient was judged as having a potential case of LAST syndrome. The length of hospital stay and the incidence of additional complications were not different between the groups. CONCLUSION: Asian adults receiving liposomal bupivacaine as part of multimodal perioperative analgesia demonstrated lower pain scores compared to matching Caucasians, despite not having greater opioid consumption.

Hypotension Prediction Index for Prevention of Hypotension during Moderate- to High-risk Noncardiac Surgery.

BACKGROUND: The Hypotension Prediction Index is a commercially available algorithm, based on arterial waveform features, that predicts hypotension defined as mean arterial pressure less than 65 mmHg for at least 1 min. We therefore tested the primary hypothesis that index guidance reduces the duration and severity of hypotension during noncardiac surgery. METHODS: We enrolled adults having moderate- or high-risk noncardiac surgery with invasive arterial pressure monitoring. Participating patients were randomized to hemodynamic management with or without index guidance. Clinicians caring for patients assigned to guidance were alerted when the index exceeded 85 (range, 0 to 100) and a treatment algorithm based on advanced hemodynamic parameters suggested vasopressor administration, fluid administration, inotrope administration, or observation. Primary outcome was the amount of hypotension, defined as time-weighted average mean arterial pressure less than 65 mmHg. Secondary outcomes were time-weighted mean pressures less than 60 and 55 mmHg. RESULTS: Among 214 enrolled patients, guidance was provided for 105 (49%) patients randomly assigned to the index guidance group. The median (first quartile, third quartile) time-weighted average mean arterial pressure less than 65 mmHg was 0.14 (0.03, 0.37) in guided patients versus 0.14 (0.03, 0.39) mmHg in unguided patients: median difference (95% CI) of 0 (-0.03 to 0.04), P = 0.757. Index guidance therefore did not reduce amount of hypotension less than 65 mmHg, nor did it reduce hypotension less than 60 or 55 mmHg. Post hoc, guidance was associated with less hypotension when analysis was restricted to episodes during which clinicians intervened. CONCLUSIONS: In this pilot trial, index guidance did not reduce the amount of intraoperative hypotension. Half of the alerts were not followed by treatment, presumably due to short warning time, complex treatment algorithm, or clinicians ignoring the alert. In the future we plan to use a lower index alert threshold and a simpler treatment algorithm that emphasizes prompt treatment.

Optically Transparent Colloidal Dispersion of Titania Nanoparticles Storable for Longer than One Year Prepared by Sol/Gel Progressive Hydrolysis/Condensation.

The molecular catalyst sensitized system (MCSS), where an excited molecular catalyst adsorbed on a semiconductor such as TiO2 injects electrons to the conduction band of the semiconductor leading to hydrogen evolution/CO2 reduction coupled with an oxidation of water on the molecular catalyst, has been one of the most probable candidates in the approach to artificial photosynthesis. For a full utilization of visible light, however, a serious light scattering of the aqueous suspension of TiO2 in the visible region, which is generally experienced, should be avoided. Here, we report a preparation of optically transparent colloidal dispersion of TiO2 by the sol/gel reaction of TiCl4 through progressive hydrolysis/condensation under the basic condition without any calcination processes. The TiO2 nanoparticles (TiO2(NPs)) obtained were characterized as an amorphous particle (∼10-15 nm) having a microcrystal domain of anatase within several nm by XRD, Raman spectroscopies, XRF, XAFS, TG/DTA, and HRTEM, respectively. The energy-resolved distribution of carrier electron traps in TiO2(NPs) as a fingerprint of TiO2 was characterized through reversed double-beam photo-acoustic spectroscopy to have a close similarity to that of TiO2(ST-01) as well as the observation of carrier traps by transient absorption spectroscopy. Though the powder TiO2(NP) itself was not dispersed well in aqueous solution, the wet TiO2(NPs) as prepared before being dried up provided a completely transparent aqueous dispersion under the acidic condition (1 M HCl). Addition of methanol enabled the colloidal dispersion (TiO2(NPs, MeOH/H2O, 0.1 M HCl)) to keep the optical transparency for longer than 1 year (550 days), which is the first example of TiO2 dispersion storable for such a long period. TiO2(NPs, MeOH/H2O) exhibited a moderate photocatalytic reactivity of H2 evolution with a quantum yield of ∼2.6% upon 365 nm light irradiation. An optically transparent thin film of TiO2(NPs, MeOH/H2O) was also successfully prepared on a glass plate to exhibit an enhanced hydrophilicity upon UV light irradiation.