Reusable Magnetite Nanoparticle (Fe3O4 NP) Catalyst for Selective Oxidation of Alcohols under Microwave Irradiation.

Iron oxide nanoparticles (NPs) are nontoxic and abundant materials which have long been investigated as reusable catalysts in oxidation reactions, but their use so far has been hampered by a low selectivity. Here, unsupported iron oxide NPs have been found to successfully catalyze the microwave-assisted oxidation of primary and secondary alcohols to their respective aldehydes and ketones with a high selectivity when N-methylmorpholine N-oxide was used as the terminal oxidant. The crystalline phase and size of the iron-based catalyst have a drastic effect on its activity, with small magnetite (Fe3O4) NPs being the optimal catalyst for this reaction. The nanocatalyst could be easily recovered by magnetoseparation and successfully recycled four times without any need for special pretreatment or reactivation step and with a minimal loss of activity. The subsequent loss of activity was attributed to the transition from magnetite (Fe3O4) to maghemite (γ-Fe2O3), as confirmed by X-ray diffraction, Fourier transform infrared, and X-ray absorption near-edge spectroscopy. The nanocatalyst could then be reactivated by the high-temperature microwave treatment and used again for the microwave-assisted oxidation reaction.

Regioselective Propargylic Suzuki-Miyaura Coupling by SciPROP-Iron Catalyst.

The iron-catalyzed Suzuki-Miyaura cross-coupling of secondary propargyl electrophiles with lithium organoborates has been established. A propyl-bridged bulky bisphosphine ligand, SciPROP-TB, cooperated with the bulky TIPS substituent at the alkyne terminal position to achieve the cross-coupling reaction with exclusive propargylic selectivity. The reaction features high functional group compatibility, regioselectivity, and yield with a broad substrate scope. The reaction of an optically active chiral propargyl bromide proceeds with complete racemization, supporting a mechanism involving propargyl radical formation.

Longitudinal relationship between screen-based sedentary behavior and nutrient intake in Japanese children: an observational epidemiological cohort study.

BACKGROUND: Concerns regarding the impact of screen-based sedentary behavior on health have been increasing. Therefore, the present study investigated the longitudinal relationship between multiple screen time and nutrient intake in children and adolescents. METHODS: The present study was conducted utilizing 3 years longitudinal data. Study subjects were 740 Japanese children aged between 6 and 12 years at baseline and between 9 and 15 years in the follow-up. Screen-based sedentary behavior was assessed using screen time, including television (TV) viewing, personal computer (PC) use, and mobile phone (MP) use. The main outcomes were the intakes of nutrients. Mixed effect multivariate linear regression analyses were used to examine the longitudinal relationship between screen-based sedentary time and nutrient intake. Covariates included in the multivariable analysis consisted of sex, age, solitary eating, skipping breakfast, staying up late, and body weight status, as confounders, and physical inactivity, as mediator. RESULTS: In boys, a longer total screen time longitudinally correlated with higher intake of energy and lower intakes of protein, dietary fiber, minerals, and vitamins. In girls, longer total screen time longitudinally associated with higher intake of sucrose and lower intakes of protein, minerals, and vitamins. In boys, a longer TV viewing time was associated with higher intake of sucrose and lower intakes of protein, minerals, and vitamins. In girls, a longer TV viewing time was associated with higher intake of carbohydrates and lower intakes of protein, fat, minerals, and vitamins. In boys, relationships were observed between a longer PC use time and higher intakes of energy as well as lower intakes of protein, minerals, and vitamins. Relationship was observed between longer PC use time and lower intakes of minerals in girls. An increased MP use time was associated with higher intakes of energy, and lower intakes of protein, sucrose, dietary fiber, minerals, and vitamins in boys. A longer MP use time was associated with higher intakes of fat, and salt as well as lower intakes of carbohydrates, protein, minerals, and vitamins in girls. CONCLUSIONS: The present results revealed that longer screen-based sedentary behaviors were longitudinally associated with nutrient intake in children and adolescents. Future study is needed to elucidate these relationships.

Association between animal protein intake, oral frailty and calf circumference in middle-aged and older adults: a cross-sectional analysis from the Shika study.

OBJECTIVE: To investigate the relationship between oral frailty (OF), nutrient intake and calf circumference (CC) in middle-aged and older adults. DESIGN: Cross-sectional study. SETTING: Residents of four model districts of Shika town, Ishikawa Prefecture, Japan, using data from November 2017 to February 2018. PARTICIPANTS: One hundred and ninety-four residents aged ≥50 years in four model districts of Shika town. The OF total score ≥3 was defined as OF. Participants were divided into OF and non-OF groups and divided into the low-CC/kg and the high-CC/kg groups. OUTCOME MEASURES: The primary outcome is to use a two-way analysis of covariance to analyse the interaction between the two CC/kg groups and the two OF groups on nutrition intake. The secondary outcome is to use multiple regression analysis to investigate the nutrients significantly related to CC/kg when stratified by OF, with age, sex, body mass index, drinking status, smoking status and regular exercise as input covariates. RESULTS: A two-way analysis of covariance revealed a significant interaction between the two CC/kg groups and the two OF groups on animal protein intake (p=0.039). Multiple comparisons using the Bonferroni analysis revealed a significantly lower animal protein intake in the OF group than in the non-OF group with a low CC/kg (p=0.033) but not in the group with a high CC/kg. The multiple regression analysis stratified by OF revealed a positive correlation between animal protein intake and CC/kg (p=0.002). CONCLUSIONS: The present results revealed a significantly lower animal protein intake in the OF group than in the non-OF group in the low-CC/kg group, but no such difference was observed in the high-CC/kg group. Further longitudinal studies are needed to elucidate this relationship.

Dual Catalysis of Gold Nanoclusters: Photocatalytic Cross-Dehydrogenative Coupling by Cooperation of Superatomic Core and Molecularly Modified Staples.

Thiolate-protected gold nanoclusters (AuNCs) have attracted significant attention as nano-catalysts, revealing a superatomic core and gold-thiolate staples as distinct structural units. Here, we demonstrate the unprecedented dual catalytic activity of thiolate-protected [Au25 (SR)18 ]- nanoclusters, involving both photosensitized 1 O2 generation by the Au13 superatomic core and catalytic carbon-carbon bond formation facilitated by Au2 (SR)3 staples. This synergistic combination of two different catalytic units enables efficient cross-dehydrogenative coupling of terminal alkynes and tertiary aliphatic amines to afford propargylamines in high yields of up to 93 %. Mixed-ligand AuNCs bearing both thiolate and alkynyl ligands revealed the intermediacy of the alkynyl-exchanged AuNCs toward both photosensitization and C-C bond-forming catalytic cycles. Density functional theory calculations also supported the intermediacy of the alkynyl-exchanged AuNCs. Thus, the use of ligand-protected metal nanoclusters has enabled the development of an exceptional multifunctional catalyst, wherein distinct nanocluster components facilitate cooperative photo- and chemo-catalysis.

Distinct associations between dietary omega-3 and omega-6 fatty acids intake with chronic kidney disease in adults with and without diabetes: A cross-sectional study.

OBJECTIVE: We explored the relationship of dietary intake of fatty acids with chronic kidney disease (CKD) according to glycemic status in Japanese people. METHODS: A total of 1031 participants aged ≥40 y were included in this population-based, cross-sectional study. A validated self-administered diet history questionnaire was used to measure the dietary intakes of fat and fatty acids, including omega-3 and omega-6 polyunsaturated fatty acids. CKD was defined as estimated glomerular filtration rate < 60 mL/min/1.73 m2 and diabetes as the use of antidiabetic medication, fasting plasma glucose ≥ 126 mg/dL, or hemoglobin A1c of ≥6.5%. Urine biomarkers of kidney injury (liver-type fatty acid-binding protein, ß2-microglobulin, and albumin) were also examined. RESULTS: The mean age of the participants was 62.5 ± 11.2 y, and 482 (46.8%) of them were men. Overall, 177 (17.2%) participants had CKD. In the multivariable model, low omega-3 intake (odds ratio = 0.109; 95% CI, 0.019-0.645) and high omega-6-to-omega-3 ratio (odds ratio = 2.112; 95% CI, 1.167-3.822) were associated with CKD in participants with diabetes but not in those without. In selected participants with diabetes, a substantial trend of urinary liver-type fatty acid-binding protein and ß2-microglobulin level elevation along with an increase in the dietary ratio of omega-6 to omega-3 was observed. CONCLUSIONS: Low dietary omega-3 intake and high omega-6-to-omega-3 ratio were associated with CKD in middle-aged and older Japanese people with diabetes but not in those without diabetes. These results may provide insight into the more tailored approaches for dietary polyunsaturated fatty acids to prevent CKD.

Higher Intake of Vegetable Protein and Lower Intake of Animal Fats Reduce the Incidence of Diabetes in Non-Drinking Males: A Prospective Epidemiological Analysis of the Shika Study.

Although nutrient intake and alcohol consumption are both closely associated with the incidence of diabetes, their interrelationships remain unclear. Therefore, we herein have investigated the interrelationships among nutrient intake, alcohol consumption, and the incidence of diabetes using longitudinal data. This study included 969 residents ≥40 years living in Japan. In 2011 and 2012, a baseline study was conducted using questionnaires on basic demographics, diabetes, nutrient intake, and lifestyle habits. In 2018 and 2019, a follow-up study was performed using questionnaires and medical records on diabetes. Two-way analysis of covariance (two-way ANCOVA) was used to test the interactions of drinking habits and diabetes incidence on nutrients intake. The prospective relationship between nutrient intake at baseline and the incidence of diabetes in the follow-up stratified by drinkers and non-drinkers was evaluated using multiple logistic regression analysis. Interactions were observed for vegetable protein intake (p = 0.023) and animal fat intake (p = 0.016) in males. Vegetable protein intake negatively correlated with the incidence of diabetes in non-drinkers (odds ratio (OR): 0.208; 95% confidence interval (95% CI): 0.046-0.935; p = 0.041). Furthermore, animal fat intake positively correlated with the incidence of diabetes in non-drinkers (OR: 1.625; 95% CI: 1.020-2.589; p = 0.041). Therefore, vegetable protein and animal fat intakes in combination with drinking habits need to be considered for the prevention of diabetes.

Association between Bone Mineral Density and Oral Frailty on Renal Function: Findings from the Shika Study.

The association between oral frailty (OFr) and body action has been investigated, but its association with systemic function remains unclear. Therefore, this cross-sectional study examined the association between OFr with decreased bone mineral density (BMD) and renal function in residents of Shika town, Ishikawa Prefecture, Japan aged ≥40 years. This study included 400 inhabitants. The OFr total score was assessed using three oral domains in the Kihon Checklist (a self-reported comprehensive health checklist), the number of teeth, and brushing frequency per day. Measurements were the estimated glomerular filtration rate (eGFR) and the osteo-sono assessment index (OSI). Using a two-way analysis of covariance (p = 0.002), significantly lower OSI was indicated in the eGFR < 60 and OFr group than in the eGFR of < 60 and non-OFr group after adjusting for age, body mass index, and drinking and smoking status as confounding factors. Multiple logistic regression analysis confirmed this relationship (p = 0.006). Therefore, lower BMD seems to be associated with lower renal function only when accompanied by OFr. Further longitudinal studies are needed to confirm these results.

Relationships among Depressive Symptoms, Body Weight, and Chronic Pain: A Cross-Sectional Analysis of the Shika Study.

Although depression and body weight have individually been associated with chronic pain (CP), it currently remains unclear whether the combination of depressive symptoms (DS) and being underweight/overweight is related to CP. Therefore, we herein investigated the relationships among depression, body mass index (BMI), and CP in community-dwelling middle-aged and elderly individuals. Participants comprised 2216 inhabitants of Shika town in Ishikawa prefecture, Japan, including 1003 males (mean age of 68.72 years, standard deviation (SD) of 8.36) and 1213 females (mean age of 69.65 years, SD of 9.36). CP and DS were assessed using a CP questionnaire and Geriatric Depression Scale-15, respectively. The Breslow-Day test indicated that DS positively correlated with lumbar/knee pain in the BMI < 25 group, but not in the BMI ≥ 25 group. Furthermore, lumber/knee pain was related to a higher BMI. These results were confirmed by a logistic analysis with age, sex, BMI, solitary living, the duration of education, no exercise/hobbies, smoking history, alcohol intake, and medical treatment for diabetes, hyperlipidemia, or hypertension as confounding factors. The present study indicates the importance of considering DS and BMI in the prevention of CP. Further studies are needed to clarify the causal relationships among depression, BMI, and CP.

Relationship between Vitamin Intake and Resilience Based on Sex in Middle-Aged and Older Japanese Adults: Results of the Shika Study.

Epidemiological studies reported that resilience, generally regarded as the ability to manage stress in the face of adversity, correlates with mental health in middle-aged and older adults. Currently, there is limited information on eating habits that affect resilience. Therefore, this cross-sectional study investigated the relationship between vitamin intake and resilience based on sex in community-dwelling middle-aged and older individuals in Shika town, Ishikawa Prefecture, Japan. A total of 221 participants (106 men and 115 women) aged 40 years or older were included in the analysis. We assessed vitamin intake and resilience using a brief-type self-administered diet history questionnaire (BDHQ) and the resilience scale (RS), respectively. A two-way analysis of covariance (ANCOVA) revealed that higher intakes of ß-carotene and vitamin K were associated with higher RS in women, but not in men. Furthermore, a multiple logistic regression analysis stratified by sex showed that ß-carotene and vitamin K were significant independent variables for RS only in women. The present study suggests that higher intakes of ß-carotene and vitamin K were associated with higher resilience among middle-aged and older women. The results obtained demonstrate that ß-carotene and vitamin K intakes may enhance resilience by strengthening stress tolerance.

Bone Strength of the Calcaneus Is Associated with Dietary Calcium Intake in Older Japanese Men, but Not Women.

The relationship between calcium intake and bone strength in older Asian individuals, including Japanese, is controversial; therefore, we herein investigated this relationship in older Japanese populations. We performed a cross-sectional analysis of 314 participants older than 65 years who voluntarily participated in a medical examination and responded to questionnaires. The osteo-sono assessment index (OSI) measured at the right calcaneus using a quantitative ultrasonic device was used as an indicator of bone strength. The daily dietary intake of calcium was assessed using a brief-type self-administered diet history questionnaire. A two-way analysis of covariance revealed a significant interaction between sex and calcium intake on the OSI (p < 0.01). A multiple regression analysis showed a positive correlation between calcium intake and the OSI in males (p < 0.01), but not females (p = 0.27). In females, grip strength divided by body weight positively correlated with the OSI (p = 0.04). The present results suggest that a higher calcium intake contributes to bone strength in older Japanese males. Although a higher grip strength may contribute to bone strength in females, the potential of estrogen as a confounding factor needs to be considered.

Hypertension and Low Body Weight Are Associated with Depressive Symptoms Only in Females: Findings from the Shika Study.

Although the relationship between hypertension and depression is influenced by several physiological factors, including body weight and other lifestyle factors, such as eating behavior, the specific involvement of depression in hypertension remains unclear. Therefore, this epidemiological study examined the role of body weight in the relationship between hypertension and depressive symptoms among the middle-aged and elderly living in the community of Shika town. In total, 1141 males and 1142 females with mean ages of 69.09 and 70.61 years, respectively, participated this study. Physiological factors, including blood pressure, body mass index (BMI), and lifestyle, were investigated in a medical check-up in Shika town. Depressive symptoms were evaluated using the Geriatric Depression Scale 15 (GDS-15). A two-way analysis of covariance exhibited a significant interaction between the two hypertensive groups and body size groups on GDS in females. The post hoc Bonferroni method showed that in the hypertensive groups, GDS was significantly higher in the underweight group (BMI < 18.5) than in the standard/overweight group; however, this relationship was not observed in the no-hypertensive groups. Multiple regression analysis also verified this relationship. Therefore, it is suggested that the combination of hypertension and being underweight is associated with depressive symptoms only in females.

Association between Dietary Fat Intake and Hyperuricemia in Men with Chronic Kidney Disease.

Despite a close relationship between chronic kidney disease (CKD) and uric acid level, few studies have examined the relationship between uric acid level and fat intake by kidney function status. Therefore, we investigated the association between dietary fat intake and hyperuricemia with and without decreased kidney function in males living in Shika Town, Ishikawa Prefecture, Japan. This study included 361 males with a mean age of 60.7 years. Dietary fat and fatty acid intakes were evaluated using the brief-type self-administered diet history questionnaire. Reduced kidney function was defined as an estimated glomerular filtration rate (eGFR) <60 mL/min/1.73 m2, while hyperuricemia was defined as a serum uric acid level >7.0 mg/dL. A two-way analysis of covariance showed that saturated fatty acid (p = 0.026), monounsaturated fatty acid (p = 0.014), and polyunsaturated fatty acid (p = 0.022) were significantly lower in the high uric acid group than in the normal uric acid group. In multiple logistic analysis stratified by renal function, lipid intake was negatively associated with hyperuricemia in the low eGFR group. These findings suggest that higher dietary lipid/fatty acid intake may be effective in the prevention and treatment of hyperuricemia in men with CKD.

Association between Vitamin Intake and Chronic Kidney Disease According to a Variant Located Upstream of the PTGS1 Gene: A Cross-Sectional Analysis of Shika Study.

Chronic kidney disease (CKD) patients have been advised to take vitamins; however, the effects have been controversial. The individual differences in developing CKD might involve genetic variants of inflammation, including variant rs883484 located upstream of the prostaglandin-endoperoxide synthase 1 (PTGS1) gene. We aimed to identify whether the 12 dietary vitamin intake interacts with genotypes of the rs883484 on developing CKD. The population-based, cross-sectional study had 684 Japanese participants (≥40 years old). The study used a validated, brief, self-administered diet history questionnaire to estimate the intake of the dietary vitamins. CKD was defined as estimated glomerular filtration < 60 mL/min/1.73 m2. The study participants had an average age of 62.1 ± 10.8 years with 15.4% minor homozygotes of rs883484, and 114 subjects had CKD. In the fully adjusted model, the higher intake of vitamins, namely niacin (odds ratio (OR) = 0.74, 95% confidence interval (CI): 0.57−0.96, p = 0.024), α-tocopherol (OR = 0.49, 95% CI: 0.26−0.95, p = 0.034), and vitamin C (OR = 0.97, 95% CI: 0.95−1.00, p = 0.037), was independently associated with lower CKD tendency in the minor homozygotes of rs883484. The results suggested the importance of dietary vitamin intake in the prevention of CKD in middle-aged to older-aged Japanese with minor homozygous of rs883484 gene variant.

Effect of ß3-adrenergic receptor gene polymorphism and lifestyle on overweight Japanese rural residents: A cross-sectional study.

Objectives: The ß3-adrenergic receptor (ADRB3) gene polymorphism has been implicated in obesity. Therefore, the contribution of ADRB3 Trp64Arg polymorphism to obesity-related indicators was investigated, taking into account the lifestyle-related factors in a Japanese rural population. Methods: A total of 600 Japanese adults aged ≥40 years in a population-based cohort study were analyzed. The ADRB3 polymorphism was determined using peripheral blood samples. Associations between genotype and body mass index (BMI), waist circumference (WC), and body fat (BF) percentage were examined, adjusting for lifestyle-related factors, including daily nutrient intake. Results: The frequency of Arg64 allele carriers was 36%. There was no significant difference in BMI, WC, or BF between the groups with or without the Trp64Arg polymorphism. Multivariable logistic regression analysis showed that the Trp64Arg polymorphism was not associated with these three indicators, but lifestyle factors including physical inactivity, higher energy and sodium consumption, and less animal protein intake were significantly related to increased WC and BF percentages. Conclusions: The Trp64Arg polymorphism of ADRB3 gene did not contribute to increased BMI, WC, or BF. However, lifestyle-related factors impacted these indicators in middle-aged and older Japanese individuals living in rural areas.

Relationship between Alcohol Intake and Chronic Pain with Depressive Symptoms: A Cross-Sectional Analysis of the Shika Study.

Although alcohol intake is associated with chronic pain (CP) and analgesia, epidemiological studies have not yet examined the factors affecting the relationship between alcohol intake and CP in detail. Therefore, the present cross-sectional study investigated the relationship between alcohol intake and CP in community-dwelling middle-aged and elderly individuals with/without depressive symptoms. Participants comprised 2223 inhabitants of Shika town in Ishikawa prefecture, located on the Noto Peninsula facing the Sea of Japan, and included 1007 males and 1216 females. CP, depressive symptoms, and alcohol intake were assessed using a CP questionnaire, the Geriatric Depression Scale-15 and the brief-type self-administered diet history questionnaire, respectively. In males without depressive symptoms, mean alcohol intake was significantly higher at 5.70% energy (27.92 g/day) in the CP group than that of 3.75% energy (20.00 g/day) in the non-CP group. The prevalence of low back/knee pain was also significantly higher in males with than in those without depressive symptoms. The present results suggest that long-term alcohol intake is related to CP by reducing the pain threshold and enhancing nociceptive pain as a possible mechanism. However, even a low alcohol intake was associated with psychogenic pain in participants with depressive symptoms. Further studies to investigate the involvement of depressive symptoms and alcohol intake in CP and its prevention are needed.

A retrospective cohort study on the association between poor sleep quality in junior high school students and high hemoglobin A1c level in early adults with higher body mass index values.

BACKGROUND: Few epidemiological studies have been performed to clarify the association between glucose metabolism disorders in early adults (20 years old) and physiological and environmental factors, including body mass index (BMI) in junior high school days. Therefore, we examined the association between hemoglobin A1c (HbA1c) level and body size (BMI) in early adulthood and lifestyles, including sleep habits and BMI in junior high school days in Shika town, a small town in Japan, by conducting a retrospective cohort study. METHODS: We examined the HbA1c levels and body size (BMI) of 99 early adults who turned 20 years old between 2016 and 2020 and were residing in Shika town, Ishikawa Prefecture. We obtained the information on lifestyles and living environment factors, including BMI, from a questionnaire survey conducted among the subjects during their junior high school days (13-15 years old) from 2009 to 2013. RESULTS: No correlations were observed between the HbA1c levels and the BMI values of the early adults. A two-way analysis of covariance (with the HbA1c levels and BMI values of the early adults as main factors) of the body size and lifestyle habits of the junior high school students revealed that "sleep quality in junior high school" was significantly poorer in the high HbA1c group than in the low HbA1c group in the early adults with high BMI values only. This result was also supported by the logistic regression analysis result. CONCLUSIONS: The present results indicate that poor sleep quality in junior high school was associated with the high HbA1c levels of the early adults with higher BMI values, which suggests that good sleep quality in junior high school prevents the development of hyperglycemia. However, the present study did not find any relationship between early-adult BMI and HbA1c level.

Iron-catalysed enantioselective carbometalation of azabicycloalkenes.

The first enantioselective carbometalation reaction of azabicycloalkenes has been achieved by iron catalysis to in situ form optically active organozinc intermediates, which are amenable to further synthetic elaborations. The observed chiral induction, along with the DFT and XAS analyses, reveals the direct coordination of the chiral phosphine ligand to the iron centre during the carbon-carbon and carbon-metal bond forming step. This new class of iron-catalysed asymmetric reaction will contribute to the synthesis and production of bioactive molecules.

Relationship between Vitamin Intake and Health-Related Quality of Life in a Japanese Population: A Cross-Sectional Analysis of the Shika Study.

Although epidemiological studies revealed a relationship between psychosocial states, such as depressive symptoms, and nutritional intake, limited information is currently available on vitamin intake. The Short Form-36 Health Survey (SF-36) is not limited to a specific disease, it is constructed based on a universal concept of health and is used to evaluate the Quality of life (QOL). A three-component scoring method was developed for "Physical component score (PCS)", "Mental component score (MCS)", and "Role/social score (RCS)". Collectively, these summary scores are called the "QOL summary score", which is regarded as a more detailed health summary score. In the present study, we aimed at epidemiologically examine the relationship between vitamin intake and QOL in middle-aged and elderly population in 3162 residents in Japan. In women, a multiple regression analysis showed a positive correlation between all vitamin intake and PCS scores, and between vitamin B6, folic acid, vitamin C, and MCS scores. In consideration of depression as MCS of SF-36 and chronic pain as PCS, an insufficient vitamin intake may affect QOL in women; however, a causal relationship has not yet been demonstrated.