2-Aryl-3H-1,3-Benzazaphosphole Oxides: Synthesis, Optical Properties, and Excited State Intramolecular Proton Transfer.

Inclusion of a heteroatom to the phosphole ring is a promising strategy to intrinsically modulate the optical properties of phosphole derivatives. We report on a series of 2-aryl-3H-1,3-benzazaphosphole oxides that were efficiently prepared via sequential C-P cross-coupling, dehydrative [3+2] cycloaddition, and ring-oxidation reactions. The inclusion of one nitrogen atom into the benzophosphole framework caused red shifting of the absorption and emission maxima, reflecting the greater stabilization of the LUMO level. 2-(2-Hydroxyphenyl)benzazaphosphole oxide underwent excited state intramolecular proton transfer and emitted a weak fluorescence from the excited state of the N-H tautomer.

Solvent Role of Ionic Liquids in Fundamental Chemical Reaction Dynamics Analyzed by Time-Resolved Spectroscopy.

Ionic liquids (ILs), which are used as solvents for chemical reactions, are different from conventional organic solvents owing to their designability. Physicochemical parameters of the ILs, such as polarity and viscosity, that affect chemical equilibria and reaction kinetics can be tuned by changing the combination of anions and cations or by varying the lengths of the alkyl chains present in the cations. We were interested in knowing how these physicochemical parameters affect fundamental chemical reactions in ILs. Therefore, in this personal account, we investigate our recent work on two different photochemical reactions in ILs, namely excited-state intramolecular proton transfer of hydroxyflavone and photodissociation of aminodisulfide, using time-resolved spectroscopic techniques. Interestingly, the roles of the ILs in these chemical reactions are quite different. The effect of the cationic species of the ILs (i. e., the head groups and number of alkyl carbons) on the solvation environment upon photoexcitation and reaction rate are discussed.

Synthesis and Optical Properties of 1,2,5,10-Tetraphenylanthra[2,3-b]phosphole Derivatives.

1,2,5,10-Tetraphenylanthra[2,3-b]phosphole oxides and 1-methyl-1,2,5,10-tetraphenylanthra[2,3-b]phospholium salts were prepared, and their optical properties were investigated. The substituent at the para position and the fused anthracene moiety were found to exert significant impacts on the fluorescence properties of the P-bridged 2-styrylanthracene skeleton.

Preventing recurrence after surgical repair of pressure injuries in patients with spinal cord injury: Effects of a presurgical and postsurgical wheelchair seating intervention by experts.

OBJECTIVE: Pressure injuries in people with spinal cord injury or dysfunction (SCI/D) are known to have a high recurrence rate. As a countermeasure, we perform surgery after adjusting the wheelchair and cushion with the intervention of a seating expert. The effectiveness of seating interventions in postsurgical recurrence prevention was examined. MATERIALS AND METHODS: In this retrospective analysis, the participants were 19 patients with SCI/D who underwent pressure injury surgical treatment in the gluteal region from 2005 to 2018. The patients with conventional rehabilitation were assigned to Group 1 (n = 8), and those with seating intervention by experts in addition to conventional rehabilitation were assigned to Group 2 (n = 11). The main outcome measure was the presence or absence of recurrence 3 years after the surgery. The recurrence rate was compared between the two groups. RESULTS: The recurrence rates were 18% with seating intervention and 75% without; there was a significant difference (p = 0.025). The recurrence odds ratio was 13.5. CONCLUSION: This study suggests that presurgical seating evaluation and assessment by experts, postsurgical rehabilitation based on presurgical evaluation and assessment, and routine follow-up and seating adjustment according to changes are efficacious for preventing postsurgical pressure injury recurrence in patients with SCI/D.

Experimental observation of the unique solvation process along multiple solvation coordinates of photodissociated products.

Chemical reaction dynamics in solution are closely related to solvation dynamics, and understanding solvent responses remains a crucial issue in chemistry and chemical biology. In this study, we experimentally and computationally investigated the solvation dynamics along different solvation coordinates of the same molecule: the electronically excited state and ground state of the p-aminophenylthiyl radical generated by the photodissociation of bis(p-aminophenyl)disulfide. Time profiles of the peak shifts from the transient absorption and emission spectra after photodissociation were extracted to discuss the solvent reorganization process in various ionic liquids (ILs) with different viscosities. The absorption peak position of the radical followed common solvation dynamics, shifting to a lower energy with time due to reorganization of the surrounding solvent molecules in response to the charge redistribution and molecular volume change caused by photodissociation. On the other hand, the emission band of the radical did not show a meaningful spectral shift with time. It was also found that the solvation time in the ground state was not strongly dependent on the solvent viscosity. These experimental results deviate from the conventional dynamic Stokes shift theory. To discuss the experimental results, non-equilibrium molecular dynamics simulations were conducted. The spectral shift obtained by MD simulations indicated the existence of a large solvation energy change and solvation dynamics around the radical after the photodissociation. On the other hand, the electronic excitation of the radical brought about a relatively smaller solvation energy change, especially at the long delay time after the photodissociation. These differences might be one of the reasons for the unique experimentally observed solvation dynamics.

Experimental and theoretical study on p-aminophenylthyil radical geminate recombination in ionic liquids; analysis using the Smoluchowski-Collins-Kimball equation.

Recombination dynamics of geminate p-aminophenylthiyl (PAPT) radicals produced from the photodissociation of bis(p-aminophenyl) disulfide in ionic liquids (ILs) were investigated by transient absorption spectroscopy. ILs with various cationic species were used to examine the effect of viscosity and polarity on recombination dynamics. Experimentally obtained recombination yields and dynamics were found to be virtually independent of the cation species, despite the viscosity range of the solvent ILs being extensive, spanning from a few tens of mPa s to several hundred mPa s. We applied a theoretical analysis model based on the diffusion equation to the time profiles of the experimentally determined recombination yields of geminate PAPT radicals. The square well potential was incorporated into the diffusion equation to consider the concerted dynamics of solvent cage formation and recombination. A long-time asymptotic expression for the survival probability of the photodissociated products was derived and used to simulate the experimentally obtained time profile of the recombination yield. The time profiles in the range of 20-1000 ps and the final yield were successfully simulated by the asymptotic expression of the square well potential model. The optimized parameters used for the fit, including the mutual diffusion coefficient of the radical pairs, cage radius of the potential well, and well depth, were discussed in terms of the diffusion coefficient conventional theory and the potential mean force estimated from the molecular dynamics simulation for the photodissociation reaction in ILs.

Prevention of denervated muscle atrophy with accelerated nerve-regeneration by babysitter procedure in rat facial nerve paralysis model.

PURPOSE: The "babysitter" procedure is a reconstruction technique for facial nerve complete paralysis and uses the movement source from the healthy facial nerve with a cross-nerve graft. First, an end-to-side neurorrhaphy is performed between the affected facial nerve trunk and hypoglossal nerve for continuously delivering stimuli to the mimetic muscles for preventing the atrophy of mimetic muscles. Despite favorable clinical results, histological and physiological mechanisms remain unknown. This study attempted to establish a model for the "babysitter" procedure and find its efficacy in rats with facial nerve complete paralysis. MATERIALS AND METHODS: A total of 16 Lewis rats were used and divided into 2 groups; cross nerve graft (n = 8) and babysitter groups (n = 8). The facial nerve trunk was transected in both groups. Babysitter group underwent a two-stage procedure. Cross nerve graft group underwent only the transfer of nerve graft from the healthy side to affected side. The animals were assessed physiologically by compound muscle action potential (CMAP), and the regenerated nerve tissues were evaluated histopathologically at 13 weeks after surgery. RESULTS: Facial nucleus stained with retrograde tracers proved the re-innervation of affected facial muscle by the babysitter procedure. In CMAP, the amplitude of babysitter group was significantly higher than that of the cross-facial nerve graft group (p < .05). Histological examination found a significant difference in myelin g-ratio between two groups (p < .05). CONCLUSION: This study investigated the "babysitter" procedure for rat facial nerve palsy. Babysitter procedure shortened the denervation period without mimic muscle atrophy.

One-stage reconstruction by dual-innervated double muscle flap transplantation with the neural interconnection between the ipsilateral masseter and contralateral facial nerve for reanimating established facial paralysis: A report of 2 cases.

The authors developed a one-stage double-muscle reconstruction technique for facial paralysis using a latissimus dorsi (LD) flap and a serratus anterior (SA) flap, which were dually reinnervated by the contralateral facial nerve (FN) and ipsilateral masseter nerve (MN). The procedure was performed for 61-year-old man 3-years after resection of a malignant tumor and a 24-year-old woman 10-years after temporal fracture with facial paralysis. A double-muscle flap comprising left LD and SA flaps was harvested, a 15-cm thoracodorsal nerve (TN) section was attached to the LD flap, and 5-cm and 1-cm sections of the long thoracic nerve (LTN) were attached to the proximal and distal sides of SA flap. The LD flap and SA flap were sutured along the direction of motion of the zygomaticus major and risorius muscles, respectively. The contralateral FN and ipsilateral MN were interconnected by nerve suturing: the medial branch of TN to the distal end of LTN, the proximal end of LTN to the ipsilateral MN, and the buccal branch of contralateral FN to the main trunk of TN. After surgery, good contraction of the transferred flaps resulted in reanimation of a natural symmetrical smile; no complications were observed during the 12-month follow-up period.

Synthesis of 3,5-Disubstituted BODIPYs Bearing N-Containing Five-Membered Heteroaryl Groups via Nucleophilic C-N Bond Formation.

Aromatic substitution reactions were applied to the divergent synthesis of a series of symmetrically and unsymmetrically 3,5-disubstituted BODIPYs bearing N-heteroaryl groups. Furthermore, the effect of N-heteroaryl substituents at the 3- and 5-positions on the optical and photophysical properties of the BODIPY π-electron system was elucidated.

Anion Effect on the Excited-State Intramolecular Proton Transfer of 4'-N,N-Diethylamino-3-hydroxyflavone in Ionic Liquids.

The excited-state intramolecular proton transfer (ESIPT) reaction of 4'-N,N,-diethylamino-3-hydroxyflavone (C2HF) was studied using time-resolved fluorescence measurements in ionic liquids (ILs) of various anions with a fixed cation (1-ethyl-3-methylimidazolium [C2mim]+). C2HF showed an ESIPT reaction from the normal excited state (N*; keto form) to the tautomer excited state (T*; enol form) where both states are emissive. The ESIPT rate and yield were obtained by analyzing the time-resolved fluorescence spectra measured using the optical Kerr gate method. Both the ESIPT rate and yield decreased with increasing hydrogen-bond accepting ability of the anion. According to density functional theory calculations, the complex formation energy between C2HF and the anion became significantly negative with increasing the hydrogen-bond accepting ability of anion. The pseudoequilibrium constant between N* and T* ([T*]/[N*]) in the electronic excited state decreased with increasing hydrogen-bond accepting ability of the anion, while it increased with increasing the alkyl-chain length of alkyl sulfonate. The excitation wavelength dependence of the ESIPT rate and yield was studied for C2HF in [C2mim][C6H13SO3]. The ESIPT yield decreased by nearly a factor of 2 with increasing excitation wavelength from 360 to 425 nm, although the change in the ESIPT rate was small. The solvation heterogeneity due to the alkyl chain in the anion was considered to be the reason for the excitation wavelength dependence.

Anomalous Dependence of Translational Diffusion on the Water Mole Fraction for Solute Molecules Dissolved in a 1-Butyl-3-methylimidazolium Tetrafluoroborate/Water Mixture.

Translational diffusion coefficients of carbon monoxide (CO), diphenylacetylene (DPA), and diphenylcyclopropenone (DPCP) were determined in mixtures of 1-butyl-3-methylimidazolium tetrafluoroborate ([C4mim]BF4) and water using transient grating spectroscopy at different mole fractions of water (xw). While DPA exhibited a larger diffusion coefficient than DPCP at low water mole fractions (xw < 0.7), as observed for conventional liquids and ionic liquids (ILs), it was smaller at high mole fractions (xw > 0.9). The apparent molecular radius of DPA determined using the Stokes-Einstein equation at xw > 0.9 is close to the radius of an IL cluster in a water pool as determined from small-angle neutron scattering experiments (J. Bowers et al., Langmuir, 2004, 20, 2192-2198), suggesting that the DPA molecules are trapped in IL clusters in the water pool and move together. The solvation state of DPCP in the mixture was studied using Raman spectroscopy. Dramatically strong water/DPCP hydrogen bonding was observed at higher water mole fractions, suggesting that DPCP is located near the cluster interfaces. The large diffusion coefficient of DPCP suggests that hopping of DPCP between IL clusters occurs through hydrogen bonding with water.

Prevalence of tinnitus in community-dwelling Japanese adults.

BACKGROUND: Several studies have reported the prevalence of tinnitus among general populations; however, most of these studies were conducted in Europe or the United States. We estimated the prevalence of tinnitus among the general adult population in Japan. METHODS: The subjects were participants in the Takayama Study, a population-based cohort study. In 2002, a total of 14 423 adults (6450 men and 7973 women) aged 45 to 79 years responded to a self-administered questionnaire that inquired about history of tinnitus, which was defined as episodes lasting longer than 5 minutes, excluding those occurring immediately after noise exposure. Respondents were also asked about the loudness and severity of tinnitus. RESULTS: Overall, 11.9% of the subjects reported having tinnitus; the percentage was somewhat higher among men (13.2%) than women (10.8%). The prevalence of tinnitus increased with age in both sexes. Approximately 0.4% of the overall population reported that tinnitus had a severe effect on their ability to lead a normal life. Medical history of hypertension or ischemic heart diseases, use of steroid or antihypertensive medication, and employment as a factory worker or machine operator were associated with tinnitus status in both men and women. CONCLUSIONS: Tinnitus is relatively common in Japan. Although the use of various definitions of tinnitus in different studies makes it difficult to compare prevalence among populations, the present prevalence estimate was similar to those in studies in Europe and the United States.

Excited-State Intramolecular Proton Transfer Reaction and Ground-State Hole Dynamics of 4'-N,N-Dialkylamino-3-hydroxyflavone in Ionic Liquids Studied by Transient Absorption Spectroscopy.

The excited-state intramolecular proton transfer (ESIPT) of 4'-N,N-dialkylamino-3-hydroxyflavone (CnHF) having different alkyl chain lengths (ethyl, butyl, and octyl chains) was investigated in ionic liquids (ILs) by steady-state fluorescence and transient absorption spectroscopy. Upon photoexcitation, CnHF underwent ESIPT from the normal form to the tautomer form, and dual emissions from both states were detected. For C4HF and C8HF, the tautomerization yields determined from the fluorescence intensity ratios increased with the increasing number of alkyl chain carbon atoms in the cation and on reducing the excitation wavelength as reported for C2HF [K. Suda et al., J. Phys. Chem. B. 117, 12567 (2013)]. The transient absorption spectra of CnHF were measured at excitation wavelengths of 360, 400, and 450 nm. The ESIPT rate determined from the induced emission of the tautomer was correlated with the tautomerization yield for C2HF and C4HF. In addition, the recovery of the ground-state bleach was found to be strongly dependent on the excitation wavelength. This result indicates that the solvated state of the molecule before photoexcitation is dependent on the excitation wavelengths. The time constant for the ground-state relaxation was slower than that for the excited state.

Facial nerve regeneration with bioabsorbable collagen conduits filled with collagen filaments: An experimental study.

INTRODUCTION: A bioabsorbable collagen conduit (Renerve™) filled with collagen filaments is currently approved as an artificial nerve conduit in Japan and is mainly used for connecting and repairing peripheral nerves after traumatic nerve injury. However, there are few reports on its applications for reconstructing and repairing the facial nerve. The present study evaluated the efficacy of the conduit on promoting nerve regeneration in a murine model with a nerve defect at the buccal branch of the facial nerve. METHODS: Under inhalational anesthesia and microscopic guidance, the buccal branch of the left facial nerve in an 8-week-old Lewis rat was exposed, and a 7 mm gap was created in the nerve. The gap was then connected with either the nerve conduits (NC group) or an autologous nerve graft (the autograft group). At 13 weeks after the procedure, we compared the histological and physiological regenerations in the both groups. RESULTS: We found compound muscle action potential amplitude is significantly larger in the autograft group (2.8 ± 1.4 mV) than in NC group (1.3 ± 0.5 mV) (p < 0.05). The number of myelinated fibers of the autograft group was higher (3634 ± 1645) than that of NC group (1112 ± 490) (p < 0.01). The fiber diameter of the autograft group (4.8 ± 1.9 µm) was larger than that of NC group (3.8 ± 1.4 µm) (p < 0.05). The myelin thickness of the autograft group was thicker than that of NC group (0.6 ± 0.3 µm vs. 0.4 ± 0.1 µm) (p < 0.05). G-ratio of the autograft group (0.74 ± 0.19) was lower than that of NC group (0.79 ± 0.10) (p < 0.05). CONCLUSION: This study demonstrated the efficacy of collagen nerve conduit for facial nerve reconstruction following nerve injury. However, the effectiveness of the conduit on the promotion of nerve regeneration was inferior to that of the autograft.

Consumption of coffee, green tea, oolong tea, black tea, chocolate snacks and the caffeine content in relation to risk of diabetes in Japanese men and women.

Although the inverse association between coffee consumption and risk of diabetes has been reported numerous times, the role of caffeine intake in this association has remained unclear. We evaluated the consumption of coffee and other beverages and food containing caffeine in relation to the incidence of diabetes. The study participants were 5897 men and 7643 women in a community-based cohort in Takayama, Japan. Consumption of coffee, green tea, oolong tea, black tea and chocolate snacks were measured with a semi-quantitative FFQ in 1992. At the follow-up survey in 2002, the development of diabetes and the time of diagnosis were reported. To assess the association, age, smoking status, BMI, physical activity, education in years, alcohol consumption, total energy intake, fat intake and women's menopausal status were adjusted. Among men who consumed one cup per month to six cups per week and among those who consumed one cup per d or more, the associated hazard ratios were 0.69 (95 % CI 0.50, 0.97) and 0.69 (95 % CI 0.49, 0.98) compared with those who drank little to no coffee, with a P value for trend of 0.32. The hazard ratios for women with the same coffee consumption patterns were 1.08 (95 % CI 0.74, 1.60) and 0.70 (95 % CI 0.44, 1.12), with a P value for trend of 0.03. The association between estimated total caffeine intake and risk of diabetes was insignificant both among men and among women. The results imply that coffee consumption decreased the risk of developing diabetes. The protective effect may exist aside from the influence of caffeine intake.

Heterogeneous Structures of Ionic Liquids as Probed by CO Rotation with Nuclear Magnetic Resonance Relaxation Analysis and Molecular Dynamics Simulations.

The rotational dynamics of carbon monoxide (CO) in ionic liquids (ILs) was investigated by nuclear magnetic resonance (NMR) relaxation measurements and molecular dynamics (MD) simulations. NMR spin-lattice relaxation time measurements were performed for 17O-enriched CO in 10 ILs (four imidazolium-cation-based, four phosphonium-cation-based, and two ammonium-cation-based ILs, all paired with the bis(trifluorosulfonylmethane)imide anion). In combination with previously reported data for five ILs and viscosity data, our results indicated that the obtained rotational relaxation times (τ2R) were much smaller than those predicted using the Stokes-Einstein-Debye (SED) theory. For the same viscosity/temperature values, the τ2R-1 value increased linearly with increasing carbon number of the alkyl group in the cation. The deviation from the SED equation was due to the insensitivity of τ2R to the carbon number, even though a higher carbon number generally leads to higher viscosity values for ILs. To investigate the unique rotational properties of CO in the ILs, MD simulations were performed on five representative ILs (two imidazolium, two phosphonium, and one ammonium) containing CO solutes. From rotational correlation function analyses, the CO rotation mainly occurred in a free rotation-like manner within 1 ps, which explained the relative insensitivity of CO rotation to viscosity. In the subsequent time scale (>1 ps), the minor component of the CO rotation was discriminated among different ILs. It was strongly suggested that, because CO preferably locates in the outer part of the alkyl groups in the cation, the slow CO rotation is correlated with the outer alkyl dynamics, which are decoupled from the whole cation rotation.

Hemodynamic Analysis of a Microanastomosis Using Computational Fluid Dynamics.

BACKGROUND: Technical issues in free flap transfer, such as the selection of recipient vessels and the positioning and method of anastomosis of the vascular pedicle, have been the subject of vigorous debate. Recent developments in computational fluid dynamics (CFD) have enabled the analysis of blood flow within microvessels. In this study, CFD was used to analyze hemodynamics in a microanastomosis. METHODS: In the fluid calculation process, the fluid domain modelizes microvessels with anastomosis. The inlet flow conditions were measured as venous waveform, and the fluid is simulated as blood. Streamlines (SL), wall shear stress (WSS), and oscillatory shear index (OSI) at the anastomosis were visualized and analyzed for observing effects from the flow field. RESULTS: Some flow disruption was evident as the SL passed over the sutures. The maximum recorded WSS was 13.37 Pa where the peak of a suture was exposed in the lumen. The local maximum value of the OSI was 0.182, recorded at the base of the anastomosis on the outflow side. CONCLUSION: In the ideal anastomosis, the SL is disrupted as little as possible by the sutures. The WSS indicated that thrombus formation is unlikely to occur at suture peaks, but more likely to occur at the base of sutures, where the OSI is high. Tight suture knots are important in microanastomosis.

Accelerated outgrowth in cross-facial nerve grafts wrapped with adipose-derived stem cell sheets.

In this study, we devised a novel cross-facial nerve grafting (CFNG) procedure using an autologous nerve graft wrapped in an adipose-derived stem cell (ADSC) sheet that was formed on a temperature-responsive dish and examined its therapeutic effect in a rat model of facial palsy. The rat model of facial paralysis was prepared by ligating and transecting the main trunk of the left facial nerve. The sciatic nerve was used for CFNG, connecting the marginal mandibular branch of the left facial nerve and the marginal mandibular branch of the right facial nerve. CFNG alone, CFNG coated with an ADSC suspension, and CFNG wrapped in an ADSC sheet were transplanted in eight rats each, designated the CFNG, suspension, and sheet group, respectively. Nerve regeneration was compared histologically and physiologically. The time to reinnervation, assessed by a facial palsy scoring system, was significantly shorter in the sheet group than in the other two groups. Evoked compound electromyography showed a significantly higher amplitude in the sheet group (4.2 ± 1.3 mV) than in the suspension (1.7 ± 1.2 mV) or CFNG group (1.6 ± 0.8 mV; p < .01). Toluidine blue staining showed that the number of myelinated fibers was significantly higher in the sheet group (2,450 ± 687) than in the suspension (1,645 ± 659) or CFNG group (1,049 ± 307; p < .05). CFNG in combination with ADSC sheets, prepared using temperature-responsive dishes, promoted axonal outgrowth in autologous nerve grafts and reduced the time to reinnervation.

Corrigendum to "Dedifferentiated fat cells in polyglycolic acid-collagen nerve conduits promote rat facial nerve regeneration" [Regen Ther 11 (2019) 240-248].

[This corrects the article DOI: 10.1016/j.reth.2019.08.004.].