Direct synthesis of phenanthrenyl triflates from 1-biphenylyl-2-diazo-2-aryl ketones and triflic anhydride.

A strategy for direct synthesis of phenanthrenyl triflates from 1-biphenylyl-2-diazo-2-aryl ketones and triflic anhydride is described. The reaction of 1-biphenylyl-2-diazo-2-aryl ketones with triflic anhydride proceeded smoothly in the presence of 2,6-di-tert-butylpyridine under mild conditions to produce phenanthrenyl triflates in high to excellent yields. The phenanthrenyl triflate products were demonstrated to be utilized as coupling partners in various coupling reactions. The proposed mechanism involves an intramolecular Friedel-Crafts reaction of a vinyl cation intermediate formed in situ.

Influence of Chewing Gummy Jelly Containing Aroma Compound on Psychological Stress and Autonomic Nervous System Activity: A Randomized Crossover Trial.

The aim of this randomized crossover trial was to clarify the effects of chewing gummy jelly containing a compound of decanoic acid, oligonol, methyl cellulose, and citral (DOMAC) on mental stress and autonomic nervous activity in facemask wearers. A placebo gummy jelly was used in conjunction with DOMAC. Eight healthy adults with no tooth loss (mean age: 35±5 yr) were included. The participants were required to chew one DOMAC or placebo gummy jelly for 5 min after wearing a facemask for 20 min in the laboratory, then the other gummy jelly after a washout period. Rate of change in salivary immunoglobulin A (IgA) as a marker of stress was compared between before and after chewing. Additionally, sympathetic and parasympathetic activity was compared at both time points. A significant difference was observed in the percentage change in salivary IgA from that at before wearing a facemask: 127±34% (mean±standard deviation) while wearing a facemask; 46±20% while chewing DOMAC gummies; and 47±26% while chewing placebo gummies (p<0.05). Parasympathetic nervous system activity was 971.2±1040.7 ms2 at 20 min after facemask wearing; 295.0±253.0 ms2 after DOMAC gummy chewing; and 1956.1±2798.0 ms2 after chewing a placebo gummy jelly; with significant differences only being found between 20 min after facemask wearing and after DOMAC gummy chewing (p<0.05). Sympathetic nervous system activity was 1.80±1.83 at 20 min after facemask wearing; 4.06±3.33 after DOMAC gummy chewing; and 4.95±7.02 after chewing a placebo gummy jelly; with significant differences only being found between 20 min after facemask wearing and after DOMAC gummy chewing. These results suggest that chewing gummy jellies containing DOMAC relieves stress caused by facemask wearing and activates sympathetic nervous system activity.

Unsupported nanoporous gold catalyst for highly selective hydroamination of alkynes.

An efficient and highly selective heterogeneous catalyst system for hydroamination of alkynes was developed using unsupported gold nanopores (AuNPore) for the first time. The AuNPore-catalyzed highly regioselective hydroamination of alkynes proceeded smoothly without any additive and solvent under mild conditions (rt-50 °C) to yield Markovnikov imines in satisfactory to excellent yields. No gold leached from AuNPore during the hydroamination of alkynes. Moreover, the catalyst was easily recovered and reused without any loss of catalytic activity. A one-pot, two-step procedure using a single AuNPore catalyst has been devised to produce secondary amines derived from readily available alkynes and anilines with high atom efficiency.

The effect of preoperative rehabilitation on the prevention of postoperative ileus in colorectal cancer patients.

PURPOSE: Previous research suggests that the preoperative rehabilitation of colorectal cancer patients can reduce postoperative ileus. However, the evidence is insufficient and further research is warranted. This study aimed to investigate whether short-term preoperative rehabilitation, both on an outpatient and inpatient basis, can reduce the incidence of postoperative ileus after colorectal cancer surgery. METHODS: This was a retrospective cohort study that drew on data from multicenter electronic medical records. Patients with stage 1-3 colorectal cancer who underwent surgery and postoperative rehabilitation were included. The incidence of postoperative ileus was compared between patients who received short-term preoperative rehabilitation and those who did not. Propensity score adjustment using inverse probability weighting and subgroup analysis by type of surgery was performed. RESULTS: Four thousand seventy-six eligible patients (43.4% female; mean age 75.1 ± 10.9 years) were included; 1914 (47.0%) received short-term preoperative rehabilitation. The preoperative rehabilitation group had a significantly lower incidence of postoperative ileus than the no preoperative rehabilitation group (pre-adjustment: 5.5% vs. 9.9%, p < 0.001; post-adjustment: 5.2% vs. 9.0%, p < 0.001). Therefore, preoperative rehabilitation was significantly associated with a lower incidence of postoperative ileus (OR: 0.554, 95% CI: 0.415-0.739, p < 0.001). In an adjusted analysis of surgery type subgroups, the incidence of postoperative ileus was significantly lower in the preoperative rehabilitation group for all types of surgery. CONCLUSION: Our study showed that short-term preoperative rehabilitation for patients with stage 1-3 colorectal cancer, both with inpatients and outpatients, significantly reduces the incidence of postoperative ileus.

Impact of Frailty Risk on Adverse Outcomes after Traumatic Brain Injury: A Historical Cohort Study.

We evaluated the utility of the Hospital Frailty Risk Score (HFRS) as a predictor of adverse events after hospitalization in a retrospective analysis of traumatic brain injury (TBI). This historical cohort study analyzed the data of patients hospitalized with TBI between April 2014 and August 2020 who were registered in the JMDC database. We used HFRS to classify the patients into the low- (HFRS < 5), intermediate- (HFRS5-15), and high- (HFRS > 15)-frailty risk groups. Outcomes were the length of hospital stay, the number of patients with Barthel Index score ≥ 95 on, Barthel Index gain, and in-hospital death. We used logistic and linear regression analyses to estimate the association between HFRS and outcome in TBI. We included 18,065 patients with TBI (mean age: 71.8 years). Among these patients, 10,139 (56.1%) were in the low-frailty risk group, 7388 (40.9%) were in the intermediate-frailty risk group, and 538 (3.0%) were in the high-frailty risk group. The intermediate- and high-frailty risk groups were characterized by longer hospital stays than the low-frailty risk group (intermediate-frailty risk group: coefficient 1.952, 95%; confidence interval (CI): 1.117−2.786; high-frailty risk group: coefficient 5.770; 95% CI: 3.160−8.379). The intermediate- and high-frailty risk groups were negatively associated with a Barthel Index score ≥ 95 on discharge (intermediate-frailty risk group: odds ratio 0.645; 95% CI: 0.595−0.699; high-frailty risk group: odds ratio 0.221; 95% CI: 0.157−0.311) and Barthel Index gain (intermediate-frailty risk group: coefficient −4.868, 95% CI: −5.599−−3.773; high-frailty risk group: coefficient −19.596, 95% CI: −22.242−−16.714). The intermediate- and high-frailty risk groups were not associated with in-hospital deaths (intermediate-frailty risk group: odds ratio 0.901; 95% CI: 0.766−1.061; high-frailty risk group: odds ratio 0.707; 95% CI: 0.459−1.091). We found that HFRS could predict adverse outcomes during hospitalization in TBI patients.

Hydrogenation of nitriles to primary amines catalyzed by an unsupported nanoporous palladium catalyst: understanding the essential reason for the high activity and selectivity of the catalyst.

An efficient and highly selective heterogeneous catalyst system for nitrile hydrogenation was developed using unsupported palladium nanopores (PdNPore). The PdNPore-catalyzed selective hydrogenation of nitriles proceeded smoothly, without any additives, under mild conditions (low H2 pressure and low temperature) to yield primary amines with satisfactory to excellent yields. Systematic studies demonstrated that the high activity and excellent selectivity of the PdNPore originated from its good Lewis acidity and porous structure. No palladium leached from the PdNPore during the hydrogenation reaction. Moreover, the catalyst was easily recovered and reused without any loss of catalytic activity. A deuterium-hydrogen exchange reaction clearly indicated that the present hydrogenation involves heterolytic H2 splitting on the surface of the PdNPore catalyst.

Association between the number of board-certified physiatrists and volume of rehabilitation provided in Japan: an ecological study.

Objectives: This study aimed to determine the relationship between the number of board-certified physiatrists and the amount of inpatient rehabilitation delivered. Materials and Methods: We analyzed open data from 2017 in the National Database of Health Insurance Claims and Specific Health Checkups of Japan and compared the volume of inpatient rehabilitation services between prefectures to examine regional disparities. We also examined the relationship between the volume of rehabilitation services provided and the number of board-certified physiatrists. Results: The population-adjusted number of inpatient rehabilitation units per prefecture ranged from a maximum of 659,951 to a minimum of 172,097, a disparity of 3.8-fold. The population-adjusted number of board-certified physiatrists was 4.8 in the highest region and 0.8 in the lowest region, a disparity of 5.8-fold. The population-adjusted number of board-certified physiatrists was significantly correlated with the population-adjusted total number of inpatient rehabilitation units (r=0.600, P<0.001). Correlations were between the number of board-certified physiatrists and the number of rehabilitation units in cerebrovascular and orthopedic services, but not in cardiovascular, respiratory, or oncology services. Conclusion: Large regional disparities manifested in the amount of inpatient rehabilitation provided in Japan. An association was found between the number of board-certified physiatrists and rehabilitation units delivered. It may be necessary to train more BCPs in regions with fewer units to eliminate these disparities.

Palladium-Catalyzed Cycloisomerization of 2-Ethynylbiaryls to 9-Methylidene Fluorenes.

A palladium-catalyzed cycloisomerization of 2-ethynylbiaryls to 9-methylidene fluorenes is described for the first time. The cycloisomerization of 2-ethynylbiaryls proceeded smoothly in the presence of weak acid at low temperature to afford 9-methylidene fluorenes in satisfactory to high yields. This new type of cycloisomerization of 2-ethynylbiaryls is operationally simple and scalable and exhibits high functional-group tolerance. Various synthetically useful functional groups, such as halogen atoms, as well as formyl, acetyl, methoxycarbonyl, cyano, and nitro groups, remain intact during the cycloisomerization of 2-ethynylbiaryls.

Three-component addition of terminal alkynes, carboxylic acids, and tert-butyl hypochlorite.

This paper described the unprecedented three-component addition of terminal alkynes, carboxylic acids, and tert-butyl hypochlorite. This new type of addition proceeds smoothly to produce gem-dichloroalkane derivatives in satisfactory to excellent yields via successive two-time additions under mild conditions. The synthetically useful functional groups, such as Cl, Br, CN, and NO2, remained intact in the final products.

Hospital Frailty Risk Score Predicts Outcomes in Chronic Obstructive Pulmonary Disease Exacerbations.

INTRODUCTION: Patients with chronic obstructive pulmonary disease (COPD) are at high risk for frailty and prone to complications after admission for an acute exacerbation. We aim to investigate the association between frailty risk and functional outcomes in patients with acute exacerbations of COPD, using a nationwide database. METHODS: This retrospective cohort study included patients with acute exacerbations of COPD who were admitted by ambulance. We assessed frailty using the Hospital Frailty Risk Score (HFRS) and compared the outcomes between low frailty risk (HFRS < 5) and frailty at risk (HFRS ≥ 5) groups. The primary outcome was prolonged hospitalization (≥30 days). The secondary outcomes were in-hospital mortality, readmission (≤90 days), poor activities of daily living (ADL) at discharge, and difficulty in returning home. RESULTS: There were 3,396 eligible patients (mean age, 75.9 ± 11.2 years; 20.4% female). The rate of frailty at risk patients was 14.0%. Frailty at risk patients were significantly higher rates of prolonged hospitalization (32.9% vs. 17.5%), more in-hospital mortality (16.4% vs. 12.5%), more difficulty in returning home (34.6% vs. 22.9%), and poorer ADL at discharge (8.7% vs. 12.4%) than those of low frailty risk. Multivariate analysis with adjusted covariates showed that HFRS was independently associated with prolonged hospitalization (odds ratio, 2.0; 95% confidence interval, 1.4-2.9). CONCLUSIONS: HFRS can be used to predict the outcome of patients with acute exacerbations of COPD. This finding supports the validity of using the HFRS in clinical practice with patients with acute exacerbations of COPD.

Palladium-Catalyzed Tail-to-Tail Reductive Dimerization of Terminal Alkynes to 2,3-Dibranched Butadienes.

The palladium-catalyzed tail-to-tail reductive dimerization of terminal alkynes is described for the first time. Aromatic terminal alkynes bearing diverse and sensitive functional groups as well as aliphatic terminal alkynes are efficiently transformed to 2,3-dibranched butadienes. The key to achieve a selective tail-to-tail reductive dimerization reaction is to control appropriately the acidity of the reaction solution, which is accomplished by a combined use of pivalic acid and para-toluenesulfonic acid. The tail-to-tail reductive dimerization reaction is proposed to proceed via a cationic alkenyl palladium intermediate under acidic conditions.

Impact of Frailty Risk on Oral Intake and Length of Hospital Stay in Older Patients with Pneumonia: A Historical Cohort Study.

The aim of this study was to examine the association between frailty risk and outcomes in older patients with pneumonia. For this purpose, the JMDC multi-center database was used, and a historical cohort study was conducted to examine the association between the Hospital Frailty Risk Score (HFRS) and oral intake prognosis and length of hospital stay in older patients hospitalized with pneumonia. Patients were classified into low-risk (HFRS < 5), intermediate-risk (HFRS = 5−15), and high-risk (HFRS > 15) groups based on their HFRS scores, and outcomes were defined as the number of days from admission to the start of oral intake and length of hospital stay. A total of 98,420 patients with pneumonia (mean age 82.2 ± 7.2) were finally included. Of these patients, 72,207 (73.4%) were in the low-risk group, 23,136 (23.5%) were in the intermediate-risk group, and 3077 (3.1%) were in the high-risk group. The intermediate- and high-risk groups had a higher number of days to the start of oral intake than the low-risk group (intermediate-risk group: coefficient 0.705, 95% confidence interval [CI] 0.642−0.769; high-risk group: coefficient 0.889, 95% CI 0.740−1.038). In addition, the intermediate- and high-risk groups also had longer hospital stays than the low-risk group (intermediate-risk group: coefficient 5.743, 95% CI 5.305−6.180; high-risk group: coefficient 7.738, 95% CI 6.709−8.766). Overall, we found that HFRS is associated with delayed initiation of oral intake and prolonged hospital stay in older patients with pneumonia. Therefore, evaluation based on HFRS could be helpful in making clinical decisions regarding the selection of feeding strategies and when to discharge older patients with pneumonia.

Chiral Indolizidine Synthesis through the Ir-Catalyzed Asymmetric Hydrogenation of Cyclic Pyridinium Salts.

The Ir-catalyzed asymmetric hydrogenation of cyclic pyridinium salts is presented as a new strategy for the convenient and efficient synthesis of chiral indolizidines. The asymmetric hydrogenation of cyclic pyridinium salts derived from 2-(2-acylphenyl)pyridines proceeded smoothly in the presence of [Ir(cod)Cl]2 and (R)-DM-SegPhos to provide the desired chiral 7,8-benzoindolizidines 6 in high to excellent yields with moderate enantioselectivity (up to 86:14 er) and excellent diastereoselectivity (>20:1 dr). The enantiomeric purity of 6j was increased to 92:8 through recrystallization.

Strategies for Effective Home Modification in Older Adults.

There are various barriers to home modifications to prevent falls among the older population. Several strategies may be necessary to overcome these barriers and implement effective home modifications. The need for home modification should be assessed, which requires a home evaluation by a specialist. In Japan, welfare housing environment coordinators have been trained to provide advice on home modifications suitable for people with disabilities. In addition, in Japan, home assessment and advice on home modification before discharge from acute care hospitals for older people is allowed as a medical reimbursement, and a system for effective home modification is well established. Human resource training and medical policy arrangements on home modifications could improve the cost-effectiveness. In Japan, a system has been established to support the costs of home modification and environmental maintenance. Financial support has reduced the barrier to home modification. Fixed grab bars or shower chairs can be rented, which may be more cost-effective than purchasing them and may shorten the time required for installation. There may be psychological barriers to home modification for older population. Since many older people do not recognize the importance of home modification, promotion to convey the value of home modification may be necessary. Training of staff to engage in home modification, public financial support for modification, and ideas for reducing psychological hesitation may help to reduce the barriers for home modification and to enable effective home modification.

Interweaving Visible-Light and Iron Catalysis for Nitrene Formation and Transformation with Dioxazolones.

Herein, visible-light-driven iron-catalyzed nitrene transfer reactions with dioxazolones for intermolecular C(sp3 )-N, N=S, and N=P bond formation are described. These reactions occur with exogenous-ligand-free process and feature satisfactory to excellent yields (up to 99 %), an ample substrate scope (109 examples) under mild reaction conditions. In contrast to intramolecular C-H amidations strategies, an intermolecular regioselective C-H amidation via visible-light-induced nitrene transfer reactions is devised. Mechanistic studies indicate that the reaction proceeds via a radical pathway. Computational studies show that the decarboxylation of dioxazolone depends on the conversion of ground sextet state dioxazolone-bounding iron species to quartet spin state via visible-light irradiation.

A Strategy for Amide C-N Bond Activation with Ruthenium Catalyst: Selective Aromatic Acylation.

A strategy for amide C-N bond activation with ruthenium catalyst is described for the first time. The in situ formed bis-cycloruthenated complexes were demonstrated to be the key active species with superior oxidative addition ability to an inert amide C-N bond. The direct C-H bond activation of 2-arylpyridines followed by the amide C-N bond activation took place in the presence of a ruthenium precatalyst to produce monoacylation products in moderate to good yields. Synthetically useful functional groups, such as halogen atoms (F and Cl), ester, acetyl, and vinyl, remained intact during tandem C-H/C-N bond activation reactions.

Binary Phase Behavior of 1,3-Distearoyl-2-oleoyl-sn-glycerol (SOS) and Trilaurin (LLL).

This paper reports the precise analysis of the eutectic mixing behavior of 1,3-distearoyl-2-oleoyl-sn-glycerol (SOS) and trilaurin (LLL), as a typical model case of the mixture of cocoa butter (CB) and cocoa butter substitute (CBS). SOS was mixed with LLL at several mass fractions of LLL (wLLL); the mixtures obtained were analyzed for polymorphic phase behavior using differential scanning calorimetry (DSC) and synchrotron radiation X-ray diffractometry (SR-XRD). In melt crystallization with constant-rate cooling, SOS and LLL formed eutectics in their metastable polymorphs, allowing the occurrence of a compatible solid solution at wLLL ≥ 0.925. With subsequent heating, the resultant crystals transformed toward more stable polymorphs, then melted in a eutectic manner. For mixtures aged at 25 °C after melt crystallization, eutectics were found in the extended wLLL region, even at wLLL = 0.975. These results indicate that phase separation between SOS and LLL progressed in their solid solution under stabilization. The crystal growth of the separated SOS fraction may cause fat-bloom formation in compound chocolate containing CB and CBS. To solve this problem, the development of retardation techniques against phase separation is expected.

Structural Study on Fat Crystallization Process Heterogeneously Induced by Graphite Surfaces.

Some inorganic and organic crystals have been recently found to promote fat crystallization in thermodynamically stable polymorphs, though they lack long hydrocarbon chains. The novel promoters are talc, carbon nanotube, graphite, theobromine, ellagic acid dihydrate, and terephthalic acid, among which graphite surpasses the others in the promotion effect. To elucidate the mechanism, we investigated the influence of graphite surfaces on the crystallization manner of trilaurin in terms of crystal morphology, molecular orientation, and crystallographic features. Polarized optical microscopy, cryo-scanning electron microscopy, synchrotron X-ray diffractometry, and polarized Fourier-transform infrared spectroscopy combined with the attenuated total reflection sampling method were employed for the analyses. All the results suggested that the carbon hexagonal network plane of graphite surfaces have a high potential to facilitate the clustering of fat molecules against high thermal fluctuations in fat melt, the fat molecules form a layer structure parallel to the graphite surface, and the clusters tend to grow into thin plate crystals of the ß phase at the temperatures corresponding to low supercooling. The ß' phase also has a larger chance to grow on the graphite surface as supercooling increases.