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The aim of this paper is to examine the association between physical and cognitive function and stumbling and falling in elderly workers by conducting work-related questionnaire surveys and physical and cognitive function measurements. A total of 611 men and 121 women aged 40–69 years who participated in physical function measurements between June 2017 and June 2021 were included in the study. The general physical function measurements of upper and lower limb muscle strength, dynamic and static balance, and agility and cognitive function included grip strength, Repeated Rise Test, Trail Making test (TMT), and Three-Meter Time Up Go Test (TUG). We also asked the men and women about their experience of falling and stumbling. Logistic regression analysis showed significant odds ratios (OR) for the associations between stumbling in men and age (OR: 1.98), mental burden (OR: 2.44), frequency of field work (OR: 1.74), seated stepping test count (OR: 0.95), and TMTB time (OR: 0.99). Significant ORs were found between falling in men and age (OR: 2.55), mental burden (OR: 2.40), exercise habits (OR: 2.55), and smoking (OR: 2.00). Significant ORs were found between stumbling in women and d_TUG (OR: 1.59) and mental burden (OR: 6.42). The study suggests that there may be an association between cognitive and physical decline and stumbling and falling in elderly workers.

Labor and social security attorneys (LSSAs) are involved in various positions in harmonizing work with disease treatment; however, their qualification requirements do not include knowledge about the same. Expectations of their involvement in harmonizing work with disease treatment are insufficient. This study aimed to identify the competencies expected of the labor and social security LSSAs in harmonizing work with disease treatment.In step 1, semi-structured interviews were conducted with LSSAs in this field. In step 2, a draft competency list was created based on the interview results. In step 3, the Delphi method was used to conduct a questionnaire survey among LSSAs who had over 10 consultation cases on harmonizing work with disease treatment, and they were asked about the level of importance (how important they thought it was to promote harmonizing work with disease treatment) and level of achievement (how much they had achieved). We also asked them about the competencies they considered necessary and added them as additional items in the draft. In step 4, the results of the previous step were presented to the participants who had given valid answers in step 3, and they were asked whether they would adopt the items as competencies. Items with an agreement rate of 80% or higher were considered competency items. Additionally, we asked them about the level of importance and level of achievement of the additional items created in step 3.In step 1, 24 LSSAs participated, and in step 2, a draft competency list of six major items, 18 medium items, and 71 minor items was created. In step 3, 49 LSSAs participated and 41 cooperated (response rate: 83.6%). Five items were selected for the draft competency list to be newly added. In step 4, 30 LSSAs cooperated (response rate: 73.1%). None of the items had an agreement rate of less than 80%, and over 40% of the items had an agreement rate of 100%. As a result, six major items, 18 medium items, and 76 minor items were selected for the competency list.This study identified the competencies expected of labor and social security LSSAs in harmonizing work with disease treatment. The results of this study can be used as a reference for developing a systematic training curriculum for LSSAs in this field in the future.

This study presents a paper-based thin-layer optical cuvette for absorption spectroscopy with a pneumatically driven pump for the introduction of an aqueous sample. The three major components, a sample reservoir, an open-channel as an optical path and a pneumatic pump, are patterned in polypropylene paper using an electronic cutting machine. When sealed with transparent tape, the patterned paper serves as the side walls of the paper-based cuvette with an integrated pneumatic pump. Due to the reduced pressure inside the open-channel caused by the depression of the pump with a finger, aqueous samples spotted onto the reservoir are introduced into the open-channel of the paper-based cuvette. We demonstrated that the paper-based cuvettes are compatible with conventional spectrophotometers for absorption spectroscopic measurements and capable of quantifying the concentrations of various colored dyes in aqueous samples.

The triphasic extraction system with two extract phases can be used to separate two materials simultaneously into each phase. In this article, a possible mutual separation of Fe(II) and Fe(III) was studied using the cyclohexane/water/ionic liquid (IL) triphasic extraction system for Fe speciation. For Fe(II) and Fe(III) extraction, 2,2'-bipyridine (bpy) and tri-n-octylphosphine oxide (TOPO) were selected as extractants, respectively. It was suggested that [FeII(bpy)3]2+ and FeIII(TOPO)43+·3Tf2N- were extracted into the IL (1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, C4mimTf2N) phase and the cyclohexane phase, respectively, and both of the extractants also acted as masking agents. On simultaneous separation using the triphasic system, Fe(II) and Fe(III) were quantitatively extracted into the IL phase and the cyclohexane phase, respectively, and their mutual separation was achieved.

Carbon nanodots (CNDs) prepared from glutamic acid or glutathione in an electric furnace were characterized by capillary electrophoresis. Two major peaks were detected in the electropherograms by capillary zone electrophoresis, corresponding to anionic and less-charged CNDs. The effective electrophoretic mobility of the anionic CND formed from glutamic acid was almost identical over neutral to weakly alkaline pH range, and the CND would not contain significant amount of amino group. On the other hand, the effective electrophoretic mobility tended to decrease with decreasing pH at weakly acidic pH conditions, suggesting the functional groups of carboxylate moiety on the anionic CNDs. Dodecyl sulfate ion was added in the separation buffer to give anionic charge to the less-charged CND by adsorption. However, the anionic charge induced was little, and the dodecyl sulfate ion was not likely adsorbed on the less-charged CND and the CND would be hydrophilic.

Water-soluble carbon nanodots (CND) were synthesized under microwave irradiation from glutamic acid or glutamic acid-boric acid mixture. The CNDs were collected in an aqueous solution through size fractionation by centrifugal filtration. The CNDs thus prepared were subjected to characterization by capillary electrophoresis (CE). A peak signal of anionic substance was detected in the electropherogram, and it was found to be a major component of the CNDs. The effective electrophoretic mobility of the major component was almost identical over the pH range between 6.7 and 11.6, suggesting that the functional group of amine or boric acid moiety was not included in the CNDs. The effective electrophoretic mobility decreased at an acidic pH of less than 5, and it was suggested that carboxylate moiety was included in the CNDs. A signal of less-charged CNDs was also detected in the electropherogram, and the CNDs were characterized by a CE format of micellar electrokinetic chromatography. Two or four peaks were detected just after the electroosmotic flow; the less-charged CNDs were thus hydrophilic. The affinity interaction was also examined between the major anionic CNDs and a hydrophobic pairing cation. The peak signal of the major anionic CNDs broadened, and its theoretical number of plates decreased in the presence of tetrabutylammonium ion in the separation buffer. A small portion of the anionic CNDs were a little hydrophobic at different degrees, and their effective electrophoretic mobility decreased by the hydrophobic interaction, resulting in peak broadening of the anionic CNDs.

AIM Labor and social security attorneys (LSSAs) are involved in the field of occupational mental health. However, little attention has been paid to the involvement of LSSAs in this field. This study investigated the occupational mental health competencies that are expected of LSSAs. SUBJECTS AND METHODS Our investigation utilized the Delphi method. In Step 1, we conducted semi-structured interviews with LSSAs and then created an initial list of competencies based on the interviews and a previous investigation. In Step 2, we recruited LSSAs with 10 or more cases related to occupational mental health. They completed a questionnaire assessing the importance of their work (how important they felt it was to conduct work related to mental health) and level of achievement (how much they felt they had achieved). The respondents were also asked to provide additional competencies (not listed on the questionnaire) if they regarded them as necessary for their work, and these were later added to the list of proposed competencies. In Step 3, we presented the results of Step 2 to the same respondents and asked them to rate their agreement with the proposed competencies. Items with agreement of 80% or higher were set as competencies. We also asked LSSAs about the level of importance of their work and their perceived level of achievement with regard to the additional items created in Step 2. Items for which the level of achievement fell below the median were extracted even if the level of importance of the work fell at or above the median. RESULTS We recruited 8 LSSAs in Step 1 and created a list of 68 preliminary competencies in 20 fields. We recruited 57 LSSAs in Step 2, and 45 LSSAs completed the survey (response rate: 78.9%). Seven competencies were added to the list as a result. We recruited 34 LSSAs in Step 3 (response rate: 75.6%) . Two items with an agreement rate of less than 80% were removed, resulting in 73 competencies in 20 fields. One of the items with an agreement rate of 100% was "The plan is based on the merits and disadvantages (risks) for both labor and management." CONCLUSIONS This study identified the competencies required of LSSAs in the field of occupational mental health. Our findings suggest that specifying these competencies will enable efficient training of LSSAs.

The synergistic extraction of trivalent lanthanoid (Ln(III)) ions with 4-isopropyltropolone (Hipt) and 1,10-phenanthroline (phen) in o-dichrolobenzene (DCB) was investigated. The synergistic effect in DCB is more significant than that in toluene, and the polynuclear complexes found in toluene are not formed in DCB. Based on the 3-dimensional equilibrium analysis, the extracted species for La(III), Eu(III), and Lu(III) are found to be ion-pairs, such as Ln(ipt)2phen·ClO4 and Ln(ipt)2(phen)·ClO4 in the presence of NaClO4 as a salt, and the extraction constants of the respective species were determined. The simultaneous extraction of different lanthanoids in the present extraction system was demonstrated. The separation factors between lighter lanthanoids were larger than those with 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester, an excellent extractant for the separation of lanthanoid ions, in decane.

Ten-eleven translocation (TET) enzymes are implicated in DNA demethylation through dioxygenase activity, which converts 5-methylcytosine to 5-hydroxymethylcytosine (5-hmC). However, the specific roles of TET enzymes and 5-hmC levels in head and neck squamous cell carcinoma (HNSCC) have not yet been evaluated. In this study, we analyzed 5-hmC levels and TET mRNA expression in a well-characterized dataset of 117 matched pairs of HNSCC tissues and normal tissues. 5-hmC levels and TET mRNA expression were examined via enzyme-linked immunosorbent assay and quantitative real-time PCR, respectively. 5-hmC levels were evaluated according to various clinical characteristics and prognostic implications. Notably, we found that 5-hmC levels were significantly correlated with tumor stage (P = 0.032) and recurrence (P = 0.018). Univariate analysis revealed that low levels of 5-hmC were correlated with poor disease-free survival (DFS; log-rank test, P = 0.038). The expression of TET family genes was not associated with outcomes. In multivariate analysis, low levels of 5-hmC were evaluated as a significant independent prognostic factor of DFS (hazard ratio: 2.352, 95% confidence interval: 1.136-4.896; P = 0.021). Taken together, our findings showed that reduction of TET family gene expression and subsequent low levels of 5-hmC may affect the development of HNSCC.

Carcinoma ex pleomorphic adenoma (CXPA) is a malignant tumor of the salivary gland that arises from pleomorphic adenoma (PA). Squamous cell carcinoma (SCC) is extremely rare in the salivary glands. We report two cases of acantholytic SCC (ASCC) ex PA. Case 1 involved a 72-year-old female, and case 2 involved a 67-year-old male. Histologically, both cases involved PA, and salivary duct carcinoma (SDC) components, which were positive for androgen receptor (AR) and gross cystic disease fluid protein (GCDFP)-15 but negative for HER2, were seen in the intracapsular regions. The invasive components consisted of ASCC, which were positive for cytokeratin 5/6 and p63 but negative for AR and GCDFP-15. The SDC and ASCC components were positive for the epidermal growth factor receptor. In both cases, the cytoplasmic localization or decreased expression of E-cadherin was observed in the ASCC. In the early phase, CXPA might emerge as SDC, and it might change into SCC as it invades beyond the capsule due to changes in microenvironment. Also, the aberrant expression of E-cadherin is related to acantholysis in SCC.

Objective Depth of invasion (DOI) in oral carcinoma has been integrated into the primary tumor categories in the current tumor-node-metastasis staging (8th edition). However, there is no standard modality to determine DOI preoperatively. The aims of the present study were to evaluate the accuracy of a preoperative measurement of DOI using ultrasonography (US) for superficial oral tongue carcinomas, and to correlate the values obtained with histologically determined DOI measurements. Methods We retrospectively analyzed the records of 56 patients with oral tongue carcinoma who underwent intraoral US preoperatively, followed by curative surgery at the Shizuoka Cancer Center Hospital in Japan. For the measurement of DOI with US, our unique technique (water balloon method) was evaluated. Results The histologically measured tumor size (maximum diameter) showed a distribution of 7.0 to 40.0 mm (mean, 18.6 mm). The correlation between the US-obtained and histologically obtained DOIs was significant (r = 0.867; P 5 mm were 92.3% and 70.6%, respectively. Conclusion Intraoral US provides sufficient accuracy for the measurement of tumor DOI in oral tongue carcinoma and is complementary in assessing superficial lesions. Level of evidence 4. Laryngoscope, 128:2778-2782, 2018.

BACKGROUNDBow hunter’s syndrome or stroke (BHS) is characterized by rotational vertebrobasilar insufficiency elicited by rotation of the neck. It is caused by dynamic and reversible occlusion of the vertebral artery (VA). Reversible symptoms of rotational vertebrobasilar insufficiency are described as bow hunter’s syndrome, although brain infarction is rarely reported as bow hunter’s stroke.OBSERVATIONSA 70-year-old man experienced repeated cerebellar infarctions three times in the posterior inferior cerebellar artery (PICA) distribution of the nondominant right VA connecting the basilar artery. The onset of symptoms indicating cerebellar infarcts and the patient’s head position changes were unrelated. Dynamic digital angiography (DA) revealed that the nondominant right VA was occluded by an osteophyte from the C4 vertebral body, and the right PICA branches were shown to be passing through the distal right VA from the left VA. These findings were observed when the patient’s head was tilted to the right. An arterio-arterial embolic mechanism was suggested as the cause of repeated cerebellar infarctions.LESSONSTransient nondominant VA occlusion has been rarely reported as a cause of BHS when the head is tilted. To confirm the diagnosis of BHS, additional head tilt is recommended when performing dynamic DA in patients with a cervical osteophyte.

Background In patients with average risk of bleeding, second-look endoscopy does not reportedly reduce bleeding after gastric endoscopic submucosal dissection. However, effectiveness of second-look endoscopy for patients with a high risk of bleeding, such as those who are taking antithrombotic agents, is unclear. Hence, this study aims to clarify the effectiveness of second-look endoscopy for patients with antithrombotic therapy. Methods We studied 142 consecutive patients with 173 gastric epithelial neoplasms who were routinely taking antithrombotic agents and were treated by endoscopic submucosal dissection at Tonan Hospital between November 2013 and December 2019. They were classified into two groups: those with second-look endoscopy (SLE group, 69 patients with 85 lesions) and those without second-look endoscopy (non-SLE group, 73 patients with 88 lesions). The incidence of post-endoscopic submucosal dissection bleeding was compared between the SLE and non-SLE groups. Results There were no statistical differences in the rate of patients undergoing single antiplatelet therapy, single anticoagulant therapy, and multiple therapy between the SLE and non-SLE groups (SLE group vs. non-SLE group; 32 [46.4%], 16 [23.2%], and 21 [30.4%] patients vs. 37 [50.7%], 20 [27.4%], and 16 [21.9%] patients, respectively; p = 0.50). Post-endoscopic submucosal dissection bleeding incidence was 21.7% (15/69) and 21.9% (16/73) in the SLE and non-SLE groups, respectively, and did not significantly differ between the two groups (p = 0.98). Conclusions For patients taking antithrombotic agents, the incidence of post-endoscopic submucosal dissection bleeding was not reduced by second-look endoscopy.

Aim: To determine the effects of alcohol consumption and smoking on the onset of hypertension in a long-term longitudinal study. Methods: 7511 non-hypertensive male workers were enrolled. This cohort study was performed over an 8-year period using the results of the annual workers-health screening. The end-point was defined as systolic blood pressure ≥ 140 mmHg, diastolic blood pressure ≥ 90 mmHg, or use of antihypertensive drugs. For alcohol consumption, weekly alcohol intake (g ethanol/week) was estimated (1 “gou” = 22 g ethanol). Annual survey data were analyzed by pooled logistic regression that included alcohol consumption, smoking, age, body mass index, job schedule types, habitual exercise, and blood test measurements into the statistical model. Results: A significant positive dose–response relationship between alcohol consumption and onset of hypertension was observed, with synergistic health effects present. Compared with abstainers and nonsmokers, the adjusted odds ratios (95% confidence interval) for the onset of hypertension were: 1.51 (1.27–1.79) for 154 g ethanol/week and nonsmokers, and 1.81 (1.54–2.11) for 154 g ethanol/week and smokers. An interaction between alcohol and smoking was confirmed. Conclusions: This study provided information useful to the prevention of hypertension. By reducing alcohol consumption and smoking simultaneously, the risk of hypertension may be considerably lowered.

The co-use of two neutral ligands, tri-n-octylphosphine oxide (TOPO) and dicyclohexano-18-crown-6 (DC18C6), for ion-pair extraction of divalent strontium (Sr2+) with bis(trifluoromethanesulfonyl)imide anion (Tf2N-) showed unique synergistic effect. The extracted species in use of a single ligand is Sr(TOPO)32+·2Tf2N- or Sr(DC18C6)2+·2Tf2N-, whereas the co-use resulted in extraction enhancement based on additional formation of Sr(DC18C6)(TOPO)2+·2Tf2N- and Sr(DC18C6)(TOPO)22+·2Tf2N-.

The third-phase formation behavior in ionic liquid (IL) extraction system using trioctylphosphine oxide (TOPO) was investigated. In the use of a relatively less-lipophilic IL, such as 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (C4mimTf2N), the third phase was formed between the aqueous phase and the IL phase. The third phase seems to have a relatively high lipophilicity compared to the IL phase. The main components of the third phase were suggested as being (H3O)TOPO+, IL anion (Tf2N-), IL cation (C4mim+) and free TOPO. In addition, the third phase showed an extraction concentration ability for the Fe(III)-thiocyanato complex.

Ionic liquid (IL) chelate extraction behavior of trivalent Group 13 metals including aluminum(III), gallium(III) and indium(III) with 8-quinolinol (HQ) was investigated using three 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (CnmimTf2N, n = 2, 4 and 8) ILs. Although the three extraction systems showed similar extraction selectivity among the metals, the extractability order for the metals among the extraction systems was C8mimTf2N > C4mimTf2N > C2mimTf2N, which was the same as the order of hydrophobicity in the IL cation. Only the neutral 1:3 complex species was extracted in use of more-hydrophobic C8mimTf2N, whereas use of less-hydrophobic C4mimTf2N and C2mimTf2N resulted in competitive extraction of neutral 1:3 and cationic 1:2 complexes. For each of the metals, in addition, similar extraction constants were obtained in these three extraction systems.

Loss of heterozygosity (LOH) on chromosome 18q23 is associated with significantly decreased survival in head and neck cancer. In agreement with such tumor suppressive roles, the loss of function of genes located in this region can be achieved through LOH and promotor hypermethylation. In this study, the methylation status of promoters of 18q23 genes in 243 head and neck cancer patients was assessed by quantitative methylation-specific PCR. Promoter methylation was then compared to various clinical characteristics and patient survival. GALR1 and SALL3 promoter methylation correlated with reduced disease-free survival (log-rank test, p = 0.018 and p = 0.013, respectively). Furthermore, based on multivariate Cox proportional hazards analysis, these methylation events were associated with poor disease-free survival, with hazard ratios of 1.600 (95% confidence interval: CI, 1.027&ndash, 2.493, p = 0.038) and 1.911 (95% CI, 1.155&ndash, 3.162, p = 0.012), respectively. By comparison, GALR1 and SALL3 methylation were not prognostic for overall survival in The Cancer Genome Atlas (TCGA) cohort. Our findings suggest that the methylation status of 18q23 genes could serve as important biomarkers for the prediction of clinical outcomes in well-annotated head and neck squamous cell carcinoma cohorts. GALR1 and SALL3 methylation could thus help to facilitate risk stratification for individualized treatment.

We herein report a very rare case of combined small-cell carcinoma (SmCC) of the hypopharynx, with a squamous cell carcinoma (SqCC) element. A 74-year-old man presented with a 3-month history of throat pain and hoarseness. On hypopharyngoscopy, a tumor was identified in the right anterior wall of the piriform sinus and, following examination of a biopsy sample, the lesion was diagnosed as SqCC. Total laryngectomy with bilateral neck dissection was performed and the malignancy was diagnosed as combined SmCC. One month after surgery, concomitant chemoradiotherapy with cisplatin and etoposide was administered. Immunohistochemically, the SmCC element was positive for CD56 and Ki-67 (50.2%), whereas the SqCC element was positive for cytokeratin 34βE12 and Ki-67 (47.5%). Furthermore, the SmCC element was positive for KIT and platelet-derived growth factor α (PDGFRα), while the SqCC element was positive for epidermal growth factor receptor (EGFR) and PDGFRα. By genetic analysis, a silent mutation in the PDGFRα gene was recognized. The expression of KIT, PDGFRα and EGFR in this case provided evidence that combined SmCC may be a candidate for molecular-targeted therapy, although further investigations are required.

The electrocatalytic activity of an N,N-diethylaniline-grafted carbon (DEA/PFC) electrode was utilized to improve the sensitivity in the cathodic detection of free chlorine. Voltammetric curves showed a well-defined cathodic peak of free chlorine on DEA/PFC, lowering the overlap with that of dissolved oxygen. Amperometric measurements were applied for the determination of free chlorine for a concentration range of 4 orders of magnitude. The results showed that measurements of the amperometric response with DEA/PFC can be used as the basis for a simple, accurate, and rapid method to determine free chlorine.

We report on the detection and subsequent X-ray monitoring of the new Galactic black hole candidate MAXI J1535-571 with the MAXI/GSC. Afterthe discovery on 2017 September 2 made independently with MAXI and the Swift/BAT, the source brightened gradually, and in a few weeks, reached the peak intensity of ~5 Crab, or ~1.6 x 10^{-7} erg cm^{-2} s^{-1} in terms of the 2--20 keV flux. On the initial outburst rise, the X-ray spectrum was described by a power-law model with a photon index of ~2, while after a hard-to-soft transition which occurred on September 18, the spectrum required a disk blackbody component in addition. At around the flux peak, the 2-8 keV and 15-50 keV light curves showed quasi-periodic and anti-correlated fluctuations with an amplitude of 10--20%, on a time scale of ~1-day. Based on these X-ray properties obtained with the MAXI/GSC, we discuss the evolution of the spectral state of this source, and give constraints on its system parameters., Comment: Submitted to Publications of the Astronomical Society of Japan on Apri 3 2018, Accepted by PASJ on July 21 2018

The long gamma-ray burst GRB 161017A was detected by Fermi and Swift, and its afterglow was observed by the MITSuME 50-cm optical telescope promptly about 50 s after the burst. Early optical observations revealed that the optical lightcurve exhibits a plateau and rebrightening in the early afterglow phase about 500 and 5000 s after the trigger, respectively. By investigating the behavior of the spectral and temporal flux variation, it was found that the plateau and re-brightening cannot be explained in the context of the simple standard afterglow model. These observational features can be explained with two independent refreshed shocks, which indicate the long-acting central engine. We evaluated the physical parameters of the subsequent shells, and we then determined the kinetic energy ratio of the two colliding shells to the leading shell to be roughly 1 and 8, respectively. In addition, two prominent X-ray flares about 200 s after the trigger may be signatures of delayed ejections of the energetic jets responsible for the refreshed shocks. Such late activity of the central engine and X-ray flares play a crucial role in understanding the mechanisms for jet formation and photon emission.

We report on the photoluminescent (PL) properties of carbon nanodots (CNDs) doped with nitrogen and sulfur obtained by the pyrolytic carbonization of amino acids as precursors. Prepared CNDs exhibit stable PL emission under a wide variety of aqueous conditions. The results also provided the way to tune a PL intensity of CNDs by varying the amount of heteroatoms in precursors with a binary mixture of amino acids. The PL quantum yields of the obtained CNDs were determined to be from 0.079 to 0.571.

A photoluminescent detection method for nitrite with high selectivity and sensitivity using carbon nanodots (CNDs) is demonstrated. The selectivity of nitrite is accomplished by a highly specific diazotization reaction between nitrite and p-phenylenediamine (p-PDA). In the presence of nitrite, p-PDA easily reacts to form the diazonium cation in the acidic aqueous solution. By alkalization of the reaction mixture, diazonium cation of p-PDA was converted to an aryl radical to form aggregated CNDs, which causes the change in the photoluminescent intensity of CNDs. In the present method, nitrite can be selectively detected down to 1 μM over several anions, such as nitrate, perchlorate, sulfate, fluoride, chloride, and bromide at mM levels.

Molecular encapsulation of anionic porphyrins in NH2-terminated polyamidoamine (PAMAM) dendrimers and the interfacial behavior of the dendrimer-porphyrin associates were studied at the polarized water|1,2-dichloroethane (DCE) interface. Formation of the ion associates was significantly dependent on the pH condition and on generation of dendrimers. 5,10,15,20-Tetrakis(4-sulfonatophenyl)porphyrin (ZnTPPS4-) associated with the positively charged fourth-generation (G4) PAMAM dendrimer was highly stabilized in acidic aqueous solution without protolytic demetalation in a wide range of pH values (pH > 2). In contrast to the zinc(II) complex, the free base porphyrin (H2TPPS4-) was readily protonated under acidic conditions even in the presence of the dendrimers. In addition, the J-aggregates of diprotonated species, (H4TPPS2-) n, were preferably formed on the dendrimer. The interfacial mechanism of the dendrimer-porphyrin associates was analyzed in detail by potential-modulated fluorescence (PMF) spectroscopy. PMF results indicated that the dendrimers incorporating porphyrin molecules were transferred across the positively polarized water|DCE interface via adsorption step, whereas the transfer responses of the porphyrin ions released from the dendrimers were observed at negatively polarized conditions. A negative shift of the transfer potential of porphyrin ions compared to the intrinsic transfer potential was apparently observed for each ion association system. The ion association stability between the dendrimer and the porphyrin molecules could be estimated from a negative shift of the transfer potential. ZnTPPS4- exhibited relatively strong interaction with the higher generation dendrimer, whereas H2TPPS4- was less effectively associated with the dendrimers. © 2014 American Chemical Society.

Copper(I) ions are generally unstable in aqueous solution and readily disproportionate to copper(II) and copper(0). In this work, copper(I) is formed and stabilized under aerobic conditions by the addition of glutathione (GSH) which acts as a reducing and complexing agent. The extraction of Cu(I) with heterocyclic bidentate amines such as 2,9-dimethyl-1,10-phenanthroline (dmp), 2,9-dimethyl-4,7-diphenyl- 1,10-phenanthroline, and 2,2’-biquinoline has been studied in the presence of GSH.The formation of the Cu(I)-GSH complex in the aqueous solution was confirmed by spectrophotometry under aerobic conditions.Time-course measurements of the absorbance indicated that the Cu(I)-GSH complex retained stability toward re-oxidation by air for at least 6 h in the presence of a 10-fold excess of GSH at pH 5-7.The quantitative extraction of copper(I) was accomplished with 5.0 × 10−4 M dmp in chloroform or 1,2-dichloroethane in the presence of 5.0 × 10−4 M GSH and 0.10 M ClO4− at pH 3-6. The extracted species was found to be Cu(dmp)2ClO4 by the substoichiometric extraction method.

e17556 Background: The standard of care for oropharyngeal squamous cell carcinoma (OPSCC) is surgical (S) or non-surgical (NS) approach including chemoradiation (CRT). However, CRT is associated with significant long-term toxicity. Human papillomavirus (HPV) status are associated with improved prognosis for patients (pts) with OPSCC. The aim of this study was to explore the most promising treatment strategy with maintaining survival outcomes while improving QOL for locally advanced resectable HPV-positive OPSCC. Methods: A retrospective analysis of 96 pts with locally advanced resectable HPV-positive OPSCC in Shizuoka Cancer Center between 2004 and 2018 was performed. p16 immunohistochemistry was used to determine HPV tumor status. Clinical characteristics, acute and late toxicities, nutritional support, and survival were compared by treatment modalities. In pts who received S, surgical procedure and histological findings of the surgical specimens were additionally compared between pts who underwent upfront surgery (US) and those who did induction chemotherapy followed by surgery (ICT-S). Results: The median age was 62 years, with the majority having tonsil and base of the tongue as primary site. Thirty-six pts (38%) were current smokers, and 39 (41%) were former smokers. As an initial treatment, 62 (64.6%) and 34 (35.4%) pts underwent S and NS, respectively. Aspiration pneumonia more frequently occurred in NS (41.2%) than in S (8.1%) (p < 0.01). Nutritional support by gastrostomy tube or total parenteral nutrition was required in 20 pts (58.8%) of NS, compared with 15 pts (24.2%) of S (p < 0.01). S showed a trend toward longer overall survival (OS) than NS [HR = 0.204, p = 0.052], while progression free survival (PFS) was comparable between the groups. Of all S, 48 (50.0%) and 14 (14.6%) underwent US and ICT-S, respectively. Transoral surgery was performed in 78.6% of ICT-S, compared with 20.8% of US (p < 0.01). Histological examination of the surgical specimens revealed that positive surgical margins, involvement of ≥ 2 regional lymph nodes, and positive extracapsular extension were present in 7.1, 35.7, and 35.7% of ICT-S, compared with 31.3, 58.3, and 45.8% of US, respectively (N.S.). Pathologic complete response in the primary site and lymph nodes occurred in 43 % of ICT-S. Both OS and PFS was comparable between the groups. Conclusions: Our results suggest the impact of surgical approach on reduced long-term toxicity for HPV-positive OPSCC. ICT followed by surgery might be promising novel treatment strategy.

Covalent grafting of chromotropic acid (CA) moiety to a glassy carbon electrode was performed by electrochemical reduction of the corresponding diazonium cation generated in situ. Grafted electrodes were subjected to the electrochemical detection of multivalent cations using Fe(CN)6 3-/4- as an electrochemical probe molecule. In the absence of metal cations, redox reaction of the anionic probe was depressed by electrostatic repulsion between the probe and negatively charged CA moieties on the electrode surface. Binding of tetravalent cations such as Zr(IV) and Hf(IV) and trivalent cations such as Al(III) and lanthanide(III) to the CA moiety on the electrode surface resulted in an increase in the current intensity of the probe due to a decrease in electrostatic repulsion. Highly selective detection of the tetravalent cations was achieved in the micromolar concentration range at pH 1.0. © The Japan Society for Analytical Chemistry.

金沢大学理工研究域物質化学系, Phenylboronic acid (PBA) was covalently grafted to the surface of glassy carbon (GC) electrodes using electrochemical reduction of in situ generated diazonium cation. The grafting of GC surfaces was controlled by varying both the concentration of precursor 3-aminophenylboronic acid and the number of potential cycling during the grafting procedure. Cyclic voltammetry (CV) and eletrochemical impedance spectroscopy (EIS) were used to confirm the grafting of the PBA group to the GC surface and formation of multilayer. The barrier properties of the grafted GC electrodes were studied in the presence of a redox probe such as Fe (CN)63 - / 4 - by CV. Additionally, the resultant PBA multilayer on the GC electrode was applied for glucose detection utilizing the EIS technique in the presence of a redox probe molecule. Then, the complexation ability of the grafted layers with glucose was also confirmed as an increase of total impedance at non-faradic EIS measurement. © 2010 Elsevier B.V. All rights reserved.

Ion-pair extraction of boric acid with salicyl alcohol (H2sal) has been studied using several organic cations such as trioctylmethylammonium chloride (TOMAC1), tetrahexylammonium bromide (Ph 4PBr), and tetraphenylphosphonium bromide (Ph 4PBr) in various solvents. The extractability of boric acid was strongly dependent on the organic cations and solvents used and decreased in the order TOMAC1 > Hex 4NBr>> Ph 4PBr in almost all solvents for which the order was o-dichlorobenzene > chlorobenzene > toluene > 1,2-dichloroethane > hexane > chloroform > methyl isobutyl ketone for TOMAC1. The extracted species was found to be TOMA + B(sal) 2 in toluene from equilibrium analysis.

Selective synergism for the extraction of lanthanoids(III) (Ln) with β-diketones such as 2-thenoyltrifluoroacetone, 2-naphthoyltrifluoroacetone, and benzoylacetone has been investigated in the presence of trioctylphosphine oxide as a hydrophobic neutral ligand in 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide as an ionic liquid. The extractability of heavier Ln was remarkably enhanced, resulting in a significant improvement in the separation of Ln. It was found that the present synergism is ascribed to the formation of cationic ternary complexes, followed by ion exchange into the ionic liquid.