Improvement of the quantitativeness of the thermal desorption-GC/MS method and development of polystyrene certified reference material for the quantification of decabromodiphenyl ether (BDE 209) by using isotope dilution mass spectrometry.

A polystyrene (PS) certified reference material (CRM) for the analysis of decabromodiphenyl ether (BDE 209) was issued. PS disk was prepared by injection molding of the mixture of versine PS and BDE 209. The certification of the PS CRM was conducted by two analytical methods with different sample preparation methods using isotope dilution mass spectrometry (IDMS). The certified value, wCRM, was 978 mg/kg, and this value coincided with the regulation value of BDE 209 in the Restriction of Hazardous Substances directive (1000 mg/kg). The uncertainties related to certification, uwmean, inhomogeneity, uhom, and long- and short-term instability, usts and ults, respectively, were evaluated based on the mass fraction of BDE 209. The uwmean, uhom, usts, and ults were 0.0265, 0.0046, 0.0061, and 0.0099 (relative), respectively, and the expanded uncertainty for this CRM was determined as 57 mg/kg (coverage factor is 2). Additionally, the quantitative capability of the thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS) method was evaluated. In TD-GC/MS, the analytical values of the developed CRM obtained by the external and internal standard methods with matrix-free calibrants were out of the range of the wCRM (almost 10% larger or smaller), whereas those with matrix-matched calibrants agreed with the wCRM. In contrast to these results, the analytical values obtained by TD-GC/MS using IDMS were consistent with the wCRM no matter if matrix-free or matrix-matched calibrants were used. These results indicated that, for quantification of BDE 209 in PS, the trueness and precision of TD-GC/MS can be enhanced by applying IDMS without matrix-matched calibrants.

The formation of cariogenic plaque to contemporary adhesive restorative materials: an in vitro study.

The research exploiting the ability of dental materials to induce or prevent secondary caries (SC) development still seems inconclusive. Controlling bacterial adhesion by releasing bacteriostatic ions and improving the surface structure has been suggested to reduce the occurrence of SC. This paper analyses the impact of five distinctively composed dental materials on cariogenic biofilm formation. Forty-five specimens of three composites (CeramX Spectra ST, Admira Fusion, Beautifil II) and two glass-ionomers (Fuji II LC, Caredyne Restore), respectively, were incubated in bacterial suspension composed of Streptococcus mutans, Lactobacillus acidophilus, Streptococcus mitis, Streptococcus sanguinis, and Streptococcus salivarius at pH 7.0 and 5.5. Coverslips were used as a control. Adhered bacteria were collected after 2, 4, 6, 12, 24, and 48 h and analyzed using quantitative polymerase chain reaction (qPCR). Fluoride leakage was measured at each collection. The specimens' surface topography was assessed using interferometry. In the present study, surface roughness seemed to have a partial role in bacterial adhesion and biofilm formation, together with chemical composition of the materials tested. Despite differences in fluoride leakage, biofilm accumulation was similar across materials, but the number of adhered bacteria differed significantly. A release of other ions may also affect adhesion. These variations suggest that certain materials may be more prone to initiating secondary caries.

Erbium-doped-fiber-based broad visible range frequency comb with a 30 GHz mode spacing for astronomical applications.

We have realized a comb system with a 30 GHz mode spacing, 62 % available wavelength coverage in the visible region, and nearly 40 dB spectral contrast by combining a robust erbium-doped-fiber-based femtosecond laser, mode filtering with newly designed optical cavities, and broadband-visible-range comb generation using a chirped periodically-poled LiNbO3 ridge waveguide. Furthermore, it is suggested that this system produces a spectrum with little change over 29 months. These features of our comb will contribute to fields requiring broad-mode-spacing combs, including astronomical observations, such as exoplanet exploration and the verification of the cosmic accelerating expansion.

Facile synthesis of sulfinate esters from aryl iodides via direct oxidation of thioesters.

A practical method to synthesize sulfinate esters from aryl iodides is disclosed. Direct oxidation of thioesters prepared by copper-catalyzed C-S formation of aryl iodides realized the efficient synthesis of sulfinate esters. Due to the good accessibility of aryl iodides, a wide variety of sulfinate esters were prepared from easily available starting materials such as carboxylic acids and anilines.

Inhibition of tooth demineralization caused by Streptococcus mutans biofilm via antimicrobial treatment using hydrogen peroxide photolysis.

OBJECTIVES: An antimicrobial technique utilizing hydroxyl radicals generated by the photolysis of 3% H2O2 has been developed recently. The present study aimed to evaluate the effect of H2O2 photolysis treatment on tooth demineralization caused by Streptococcus mutans biofilm. MATERIALS AND METHODS: To induce tooth demineralization, S. mutans biofilm was allowed to form on the maxillary first molars collected from Wistar rats via 24-h culturing. The samples were immersed in 3% H2O2 and irradiated with 365-nm LED (H2O2 photolysis treatment). Viable bacterial counts in the biofilm were evaluated immediately after treatment and after an additional 30-h culturing by colony counting. The acidogenicity of the biofilm, re-established 30 h after treatment, was assessed by measuring the pH. The effect of H2O2 photolysis treatment on tooth demineralization was assessed by measuring the depth of the radiolucent layer in micro-CT images. RESULTS: H2O2 photolysis significantly reduced viable bacterial counts in the biofilm to 3.7 log colony forming units (CFU)/sample, while the untreated group had 7.9 log CFU/sample. The pH of the biofilm re-established after treatment (6.6) was higher than that of the untreated group (5.3). In line with the pH measurement, the treatment group had a significantly lower depth of radiolucent layer in dentin than the untreated group. CONCLUSIONS: H2O2 photolysis treatment was effective not only in killing the biofilm-forming S. mutans but also in lowering the acidogenicity of the biofilm. Thus, this technique could inhibit tooth demineralization. CLINICAL RELEVANCE: H2O2 photolysis can be applicable as a new dental caries treatment.

Fitness Trade-Offs between Phage and Antibiotic Sensitivity in Phage-Resistant Variants: Molecular Action and Insights into Clinical Applications for Phage Therapy.

In recent decades, phage therapy has been overshadowed by the widespread use of antibiotics in Western countries. However, it has been revitalized as a powerful approach due to the increasing prevalence of antimicrobial-resistant bacteria. Although bacterial resistance to phages has been reported in clinical cases, recent studies on the fitness trade-offs between phage and antibiotic resistance have revealed new avenues in the field of phage therapy. This strategy aims to restore the antibiotic susceptibility of antimicrobial-resistant bacteria, even if phage-resistant variants develop. Here, we summarize the basic virological properties of phages and their applications within the context of antimicrobial resistance. In addition, we review the occurrence of phage resistance in clinical cases, and examine fitness trade-offs between phage and antibiotic sensitivity, exploring the potential of an evolutionary fitness cost as a countermeasure against phage resistance in therapy. Finally, we discuss future strategies and directions for phage-based therapy from the aspect of fitness trade-offs. This approach is expected to provide robust options when combined with antibiotics in this era of phage 're'-discovery.

Putative Mechanisms Underlying the Beneficial Effects of Polyphenols in Murine Models of Metabolic Disorders in Relation to Gut Microbiota.

The beneficial effects of polyphenols on metabolic disorders have been extensively reported. The interaction of these compounds with the gut microbiota has been the focus of recent studies. In this review, we explored the fundamental mechanisms underlying the beneficial effects of polyphenols in relation to the gut microbiota in murine models of metabolic disorders. We analyzed the effects of polyphenols on three murine models of metabolic disorders, namely, models of a high-fat diet (HFD)-induced metabolic disorder, dextran sulfate sodium (DSS)-induced colitis, and a metabolic disorder not associated with HFD or DSS. Regardless of the model, polyphenols ameliorated the effects of metabolic disorders by alleviating intestinal oxidative stress, improving inflammatory status, and improving intestinal barrier function, as well as by modulating gut microbiota, for example, by increasing the abundance of short-chain fatty acid-producing bacteria. Consequently, polyphenols reduce circulating lipopolysaccharide levels, thereby improving inflammatory status and alleviating oxidative imbalance at the lesion sites. In conclusion, polyphenols likely act by regulating intestinal functions, including the gut microbiota, and may be a safe and suitable therapeutic agent for various metabolic disorders.

[Left Main Coronary Artery-to-left Atrium Fistula with Aneurysmal Dilatation:Report of a Case].

Coronary artery fistula (CAF) is a relatively rare disease, many of which are asymptomatic and are not indicated for surgery. However, CAF's patients with angina, heart failure due to shunt, and fistula hemangiomas are usually indicated for surgical treatment. A 49-year-old woman with severe congestive heart failure was found to have a fistula from the main trunk of the left coronary artery to the left atrium, and a fistula aneurysm. This patient had heart failure due to shunt blood flow, and also had a fistula aneurysm, so surgical treatment was indicated. During surgery, the fistula aneurysm was incised and the origin and opening of the fistula were closed without any problems. The postoperative course is good, and as of three years after the operation, the patient is being followed up at an outpatient clinic without recurrence of shunt flow and heart failure.

Phototriggered Spatially Controlled Out-of-Equilibrium Patterns of Peptide Nanofibers in a Self-Sorting Double Network Hydrogel.

Out-of-equilibrium patterns arising from diffusion processes are ubiquitous in nature, although they have not been fully exploited for the design of artificial materials. Here, we describe the formation of phototriggered out-of-equilibrium patterns using photoresponsive peptide-based nanofibers in a self-sorting double network hydrogel. Light irradiation using a photomask followed by thermal incubation induced the spatially controlled condensation of peptide nanofibers. According to confocal images and spectroscopic analyses, metastable nanofibers photodecomposed in the irradiated areas, where thermodynamically stable nanofibers reconstituted and condensed with a supply of monomers from the nonirradiated areas. These supramolecular events were regulated by light and diffusion to facilitate the creation of unique out-of-equilibrium patterns, including two lines from a one-line photomask and a line pattern of a protein immobilized in the hydrogel.

Impact of adhesive primer and light-curing on polymerization kinetics of self-adhesive resin cement in association with free radical reaction.

This study analyzed the impact of adhesive primer and light-curing on the polymerization kinetics of urethane dimethacrylate-based self-adhesive resin cement combined with free radical reaction. Specimens were prepared by mixing the cement paste with or without adhesive primer. Subsequently, specimens were light-cured or set without light-curing. The degree of conversion (DC), Vickers hardness (Hv), and free radical concentrations were repeatedly measured up to 168 h after the curing initiation. Irrespective of the curing procedures, DC, Hv, and free radical concentration rapidly increased during the initial 30 min of curing. The specimens cured with adhesive primer and/or light-curing generally showed higher values of DC, Hv, and radical concentration than those set by chemical curing alone, especially during the initial polymerization phase. Kinetic analysis using a linear mixed model revealed that the adhesive primer had a higher coefficient estimate than light-curing, indicating that the former had a higher impact on the polymerization. Additionally, the adhesive primer alleviated the Hv reduction caused by water and air during the initial polymerization phase, although light-curing hardly prevented the polymerization inhibition. Therefore, we suggest that application of adhesive primer is beneficial to achieve higher degree of conversion and better mechanical properties of self-adhesive resin cements by enhancing free radical reactions.

Susceptibility of Pseudomonas aeruginosa veterinary isolates to Pbunavirus PB1-like phages.

In recent years, antimicrobial-resistant Pseudomonas aeruginosa strains have increased in the veterinary field. Therefore, phage therapy has received significant attention as an approach for overcoming antimicrobial resistance. In this context, we isolated and characterized four Pseudomonas bacteriophages. Phylogenetic analysis showed that the isolated phages are novel Myoviridae Pbunavirus PB1-like phages with ØR12 belonging to a different clade compared with the other three. These phages had distinct lytic activity against 22 P. aeruginosa veterinary isolates. The phage cocktail composed from the PB1-like phages clearly inhibited the occurrence of the phage-resistant variant, suggesting that these phages could be useful in phage therapy.

Arbitrary control of the diffusion potential between a plasmonic metal and a semiconductor by an angstrom-thick interface dipole layer.

Localized surface plasmon resonances (LSPRs) are gaining considerable attention due to the unique far-field and near-field optical properties and applications. Additionally, the Fermi energy, which is the chemical potential, of plasmonic nanoparticles is one of the key properties to control hot-electron and -hole transfer at the interface between plasmonic nanoparticles and a semiconductor. In this article, we tried to control the diffusion potential of the plasmonic system by manipulating the interface dipole. We fabricated solid-state photoelectric conversion devices in which gold nanoparticles (Au-NPs) are located between strontium titanate (SrTiO3) as an electron transfer material and nickel oxide (NiO) as a hole transport material. Lanthanum aluminate as an interface dipole layer was deposited on the atomic layer scale at the three-phase interface of Au-NPs, SrTiO3, and NiO, and the effect was investigated by photoelectric measurements. Importantly, the diffusion potential between the plasmonic metal and a semiconductor can be arbitrarily controlled by the averaged thickness and direction of the interface dipole layer. The insertion of an only one unit cell (uc) interface dipole layer, whose thickness was less than 0.5 nm, dramatically controlled the diffusion potential formed between the plasmonic nanoparticles and surrounding media. This is a new methodology to control the plasmonic potential without applying external stimuli, such as an applied potential or photoirradiation, and without changing the base materials. In particular, it is very beneficial for plasmonic devices in that the interface dipole has the ability not only to decrease but also to increase the open-circuit voltage on the order of several hundreds of millivolts.

Video-Based Pulse Rate Variability Measurement Using Periodic Variance Maximization and Adaptive Two-Window Peak Detection.

Many previous studies have shown that the remote photoplethysmography (rPPG) can measure the Heart Rate (HR) signal with very high accuracy. The remote measurement of the Pulse Rate Variability (PRV) signal is also possible, but this is much more complicated because it is then necessary to detect the peaks on the temporal rPPG signal, which is usually quite noisy and has a lower temporal resolution than PPG signals obtained by contact equipment. Since the PRV signal is vital for various applications such as remote recognition of stress and emotion, the improvement of PRV measurement by rPPG is a critical task. Contact based PRV measurement has already been investigated, but the research on remotely measured PRV is very limited. In this paper, we propose to use the Periodic Variance Maximization (PVM) method to extract the rPPG signal and event-related Two-Window algorithm to improve the peak detection for PRV measurement. We have made several contributions. Firstly, we show that the newly proposed PVM method and Two-Window algorithm can be used for PRV measurement in the non-contact scenario. Secondly, we propose a method to adaptively determine the parameters of the Two-Window method. Thirdly, we compare the algorithm with other attempts for improving the non-contact PRV measurement such as the Slope Sum Function (SSF) method and the Local Maximum method. We calculated several features and compared the accuracy based on the ground truth provided by contact equipment. Our experiments showed that this algorithm performed the best of all the algorithms.

Evaluation of supercritical fluid extraction for the determination of neonicotinoid pesticides in green onion.

A supercritical fluid extraction (SFE) method was presented for the determination of neonicotinoid pesticides in green onion. We optimized the SFE parameters, namely the pressure, temperature, type and concentration of the modifier solvent, and extraction time, by testing on the incurred green onion applied with four commercial neonicotinoid formulations at the harvesting stage. The analytical values of the four neonicotinoids, obtained by 5 min dynamic SFE with a 25% (v/v) methanol/supercritical carbon dioxide mixture at 80 °C and 25 MPa, were in good agreement with those obtained by solid-liquid extraction using a homogenizer. This latter homogenization method is employed as a Japanese official method for the analysis of pesticide residues in food. The SFE-to-homogenization analytical value ratios were in the range 98.8-100.0%. Spike-and-recovery testing with spiked green onion was also performed by optimized SFE. The ratios of the analytical-to-spiked concentrations for six neonicotinoids obtained by the SFE method were 96.1-102.1% for 0.4 mg/kg and 93.9-104.1% for 4.0 mg/kg spiking levels. These values satisfied the Japanese validation guidelines for the testing method of pesticides in food. These results indicate that SFE is applicable for the analysis of neonicotinoids in green onion and enables automatic extraction with a small amount of solvent.

An Incremental Sit-to-Stand Exercise for Evaluating Physical Capacity in Older Patients with Type 2 Diabetes.

Exercise is recommended for older patients with type 2 diabetes mellitus (T2DM), and increased physical activity contributes to better management of their condition. The conventional exercise test with treadmill or cycle ergometer (CE) for assessing physical capacity, such as peak oxygen uptake (VO2) and anaerobic threshold (AT), is not always usable for older patients with T2DM. The incremental sit-to-stand (ISTS) exercise is an incremental exercise test using external signals to control the sit-to-stand rate in a given time frame and can be performed in a small space using only a chair. This study aimed to examine the validity of the physical capacity assessment during the ISTS exercise, based on the relationships between the ISTS performance, peak VO2, AT on ISTS exercise and CE test, in older patients with T2DM. Twenty-two patients with T2DM (10 men, 12 women; mean age, 68.0 years; range, 61-77 years) performed ISTS exercise (according to an existing protocol) and CE test in a randomized manner. Peak VO2, AT, and completion time were determined for the ISTS exercise and CE test. Peak VO2 during ISTS exercise was significantly associated with that during the CE test (r = 0.89, p < 0.01). The completion time on the ISTS exercise was significantly associated with peak VO2 (r = 0.80, p < 0.01) and AT on the ISTS exercise (r = 0.78, p < 0.01). The ISTS exercise is a useful tool to determine the physical capacity and estimate peak VO2 and AT in older people with T2DM.

Evaluation of pressurized liquid extraction for the determination of neonicotinoid pesticides in green onion.

A pressurized liquid extraction (PLE) method was presented for the determination of six neonicotinoid pesticides, acetamiprid, clothianidin, dinotefuran, imidacloprid, thiacloprid, and thiamethoxam in green onion. The critical parameters of PLE, e.g. extraction solvent, temperature, pressure, number of cycles, and static extraction time, were optimized by test on the spiked green onion with six neonicotinoids and the incurred green onion applied with four commercial neonicotinoid insecticide formulations (acetamiprid, dinotefuran, imidacloprid, and thiamethoxam). As a result, the recoveries of six neonicotinoids obtained by one cycle PLE with acetonitrile at 140 °C and 50 bar for 10 min were 94.7-99.5%. These results were acceptable according to the validation guideline for testing method of agricultural chemicals in food by Ministry of Health, Labour, and Welfare in Japan. PLE was also validated by the test on the incurred green onion. The analytical values of four neonicotinoids obtained by PLE were good agreement with those obtained by solid-liquid extraction with homogenizer, which is employed for Japanese official method for the analysis of pesticide residues in food (the ratios of analytical values obtained by PLE to those obtained by solid-liquid extraction were 99.7-101.2%). These results indicate that PLE is applicable for the determination of neonicotinoids in green onion.

Evaluation of the impact of matrix effects in LC/MS measurement on the accurate quantification of neonicotinoid pesticides in food by isotope-dilution mass spectrometry.

The use of isotope-labeled internal standards is the most widely accepted approach to overcome the matrix effects on quantification of pesticides in food by LC/MS. We evaluated the impact of the matrix effects on quantification of six neonicotinoid pesticides, acetamiprid, clothianidin, dinotefuran, imidacloprid, thiacloprid, and thiamethoxam, in food by using deuterated internal standards. The calibration curves for each pesticide were obtained by using matrix-free and matrix-matched calibration solutions with blank brown rice, carrot, and green onion extracts. For brown rice and carrot, the matrix effects were not observed. In contrast, the slopes of calibration curves for each pesticide were influenced by presence of green onion extracts in calibration solutions (variability of the slopes was 4-9%), because the ratios of peak area for native pesticide to those for internal standards were influenced by matrix. The spike-and-recovery test with green onion was also performed. The analytical values obtained by using matrix-free calibration solution were biased from the spiked concentration, whereas those obtained by using matrix-matched calibration solution were comparable to the spiked concentration. These results indicate that matrix-matched calibration solution should be used for accurate quantification of neonicotinoid pesticides in food by LC/MS using deuterated internal standards.

Validity and reproducibility of an incremental sit-to-stand exercise test in healthy middle-aged individuals.

[Purpose] We aimed to evaluate the validity and reproducibility of the incremental sit-to-stand exercise test for aerobic fitness evaluation in healthy middle-aged individuals. [Participants and Methods] Thirteen healthy middle-aged individuals randomly underwent the incremental sit-to-stand exercise and cycle ergometer tests, and the peak oxygen uptake was measured during both tests. Pearson's correlation coefficients were used to assess the strength of the association between the peak oxygen uptake measured during the aforementioned tests. Intraclass correlation coefficients with 95% confidence intervals for peak oxygen uptake obtained during the first, second, and third incremental sit-to-stand exercise tests were used to determine the reproducibility of this test. [Results] The peak oxygen uptake measured during the incremental sit-to-stand exercise test was strongly associated with that measured during the cycle ergometer test (r=0.86). The intraclass correlation coefficients (95% confidence intervals) used to verify the association of the peak oxygen uptake between the first and the second incremental sit-to-stand exercise tests and between the second and third incremental sit-to-stand exercise tests were 0.92 (0.66-0.99) and 0.96 (0.82-0.99), respectively. [Conclusion] The incremental sit-to-stand exercise test is a valid and reproducible tool to evaluate aerobic fitness in healthy middle-aged individuals.

Factors associated with functional rehabilitation outcomes of non-operative treatment for hip fractures: a retrospective study.

[Purpose] Limited data are available regarding the outcomes of non-operative treatment for hip fractures. We investigated the factors associated with functional rehabilitation outcomes in patients undergoing non-operative treatment for hip fractures. [Participants and Methods] We investigated 57 patients with hip fractures who underwent non-operative treatment. We retrospectively analyzed medical or rehabilitation outcomes and functional outcomes (assessed using the Functional Independence Measure tool). We examined the association between functional outcomes and other factors and compared the medical and rehabilitation outcomes between mobile and immobile patients at the time of discharge. [Results] Of the 57 patients investigated, 15 (26.3%) were mobile at discharge. We observed a significant association between the Functional Independence Measure subscores (Motor and Cognitive) and serum albumin levels. Serum albumin levels and the Functional Independence Measure subscores (Motor and Cognitive) were significantly higher in mobile than in immobile patients. [Conclusion] We observed that functional outcomes at discharge in patients undergoing non-operative treatment for hip fractures were associated with serum albumin ratios and the Functional Independence Measure-Cognitive score.

Imaging-Based Study on Control Factors over Self-Sorting of Supramolecular Nanofibers Formed from Peptide- and Lipid-type Hydrogelators.

Multicomponent self-assembly is a fascinating strategy for the construction of smart soft materials. Among them, supramolecular hydrogels comprising self-sorting nanofibers have recently attracted significant attention owing to their rationally incorporated stimulus responsiveness. However, there have been limited investigations of the crucial factors that control the self-sorting phenomena. Here, we describe an imaging-based approach to evaluate the factors that control the formation of self-sorting nanofibers from peptide- and lipid-type hydrogelators. We screened a small library of hydrogelators with distinct chemical properties by direct visualization of their self-assembly behavior by using confocal laser scanning microscopy. Our systematic research identified two important factors that influence the self-sorting behavior of nanofibers: (i) the surface charge of the hydrogelators; and (ii) the hydrophobicity of the side chain on the peptide-type hydrogelators. We determined that the same net/surface charge on the hydrogelators and side chains with a lower hydrophobicity on the peptide-type hydrogelators were preferred. These findings, in combination with the previously reported kinetic factors, were used to design and successfully prepare a three-component orthogonal self-assembly composed of supramolecular nanofibers from peptide- and lipid-type hydrogelators and a cationic organorhodium complex. Our findings would be beneficial for the design of intelligent soft materials based on self-sorting phenomena.