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Quinoidal molecules based on dipyrrolyldiketone boron complexes (QPBs), in which pyrrole units were connected by a partially conjugated system as a singlet spin coupler, were synthesized. QPB, which was stabilized by the introduction of a benzo unit at the pyrrole ß-positions, formed a closed-shell tautomer conformation that showed near-infrared absorption. The deprotonated species, monoanion QPB- and dianion QPB2-, showing over 1000 nm absorption, were formed by the addition of bases, providing ion pairs in combination with countercations. Diradical properties were observed in QPB2-, whose hyperfine coupling constants were modulated by ion-pairing with π-electronic and aliphatic cations, demonstrating cation-dependent diradical properties. VT NMR and ESR along with a theoretical study revealed that the singlet diradical was more stable than the triplet diradical.
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Anion-responsive photofunctional materials have been extensively studied because anions are important for biotic activity and constitute the building blocks of elegant supramolecular architectures. A number of fluorescent anion receptors that can probe anions in their environments have been reported, but the excited states of many of these molecules remain elusive. Studies on excited-state dynamics provide fruitful information for optimizing the emission properties, minimizing the photodegradation and photorelease of anions, and exploring novel photofunctions. In this study, we investigated the excited-state dynamics of an aryl-substituted dipyrrolyldiketone difluoroboron complex, a π-conjugated anion receptor, by time-resolved visible and infrared absorption spectroscopy and emission decay measurements combined with quantum chemical calculations. Anion binding was found to alter the radiative and nonradiative rate constants and the excited-state absorption of the anion receptor. In contrast, the molecular structures and binding abilities were similar in the S0 and S1 states.
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Introduction of electron-donating N,N-dimethylaminophenyl groups in dipyrrolyldiketone BF2 complexes as anion-responsive π-electronic molecules resulted in fascinating fluorescence properties. The fluorescence properties, which depended on the degree of photo-induced electron transfer, could be controlled by solvent polarity, anion binding and protonation.
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Anion-responsive molecules comprising phenanthropyrrole rings were synthesized by oxidative coupling. Spectroscopic and theoretical examinations revealed the effects of the π-extended structures. In the solid state as ion-pairing assemblies, Cl- complexes of π-extended derivatives formed stacked structures composed of Cl- complexes themselves and those formed with countercations using extended π-moieties. Aliphatic anion-responsive molecules and their Cl- complexes, as ion pairs with the triazatriangulenium cation, provided hexagonal columnar structures with liquid-crystalline mesophases.
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One-dimensional photonic crystals (PCs), when operating near the band edge in the dispersion diagram, inherently possess nearly polarization-independent angular selectivity-an angular transmission window around the normal direction with reflection for other angles. However, the incident light is mostly reflected at the PC-air interface due to large impedance mismatch. We show that the reflection may be sufficiently suppressed by utilizing a specially designed antireflection structure consisting of a PC having a different pitch from that of the host PC. The underlying mechanism is that the interfaces of the antireflection PC with the host PC and the air structure are selected such that the transverse impedance has a real value, which is positioned at the center of the thickness of a material film. Moreover, our structure provides a high-throughput wide angular transmission window, including the normal direction in both s and p polarizations. We develop an analytical model that captures the angular selectivity observed in numerical results.
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In Japan, use of a report for providing information from pharmacies to medical institutions called as "tracing report (TR)" is not widespread especially in the field of cancer chemotherapy. Identification of the factors related to submission of TRs could enhance the necessity of TRs. The purpose of this study is to clarify the factors related to submission of TRs regarding cancer chemotherapy through a questionnaire survey. A questionnaire survey was conducted at the live web-based seminar regarding cancer chemotherapy held for pharmacists in January 2023. After the questionnaire survey, the participants were divided into those who had submitted at least one TR regarding cancer chemotherapy within one month before the seminar (TR group) and those who had not (non-TR group). The multivariate analysis was conducted to identify factors related to submission of TRs regarding cancer chemotherapy. Of 118 participants, the responses from 93 pharmacy pharmacists involved in dispensing drugs who agreed to participate in this study and fulfilled all questionnaire were analyzed. TR group included 21 participants and non-TR group included 72. As a result of multivariate analysis, "Years of experience in counseling and following-up with patients undergoing cancer chemotherapy (odds ratio: 4.81, p=0.02)" and "Types of workplaces (odds ratio: 3.79, p=0.02)" significantly increased the incidence of submission of TRs regarding cancer chemotherapy. It was revealed that experience of intervention in cancer chemotherapy cases and an environment in which prescriptions for cancer chemotherapy can be handled on a daily basis are important for submission of TRs regarding cancer chemotherapy.
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Serviços Comunitários de Farmácia , Neoplasias , Farmácias , Farmácia , Humanos , Farmacêuticos , Neoplasias/tratamento farmacológico , Inquéritos e QuestionáriosRESUMO
Hypertension is a major cause of cardiovascular diseases. Several recent studies reported that pharmacists' remote follow-up reduced hypertension patients' blood pressure (BP). This meta-analysis aims to verify whether remote follow-up by pharmacists improves BP levels and reveal the factors that make the intervention effective. The search, conducted using PubMed/Medline, Embase, and Cochrane Library from June to July 2023, targeted articles published between October 1982 and June 2023, using terms including "pharmacist", "hypertension", and "randomized controlled trial (RCT)". The inclusion criteria were: (a) RCTs involving hypertension patients with or without comorbidities, (b) pharmacists using remote communication tools to conduct follow-up encounter during the intervention period, (c) reporting systolic blood pressure (SBP) at baseline and during intervention. SBP was the primary outcome for the meta-analysis. Thirteen studies (3969 participants) were included in this meta-analysis. The mean difference of SBP between intervention group and control group was - 7.35 mmHg (P < 0.0001). Subgroup analyses showed the greater reduction of SBP in the "regularly scheduled follow-up cohort" (- 8.89 mmHg) compared with the "as needed follow-up cohort" (- 3.23 mmHg, P < 0.0001). The results revealed that remote follow-up by pharmacists reduced SBP levels in hypertension patients and scheduled remote follow-up may contribute to the effectiveness.
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Hipertensão , Hipotensão , Humanos , Pressão Sanguínea , Farmacêuticos , Seguimentos , Ensaios Clínicos Controlados Aleatórios como Assunto , Hipertensão/tratamento farmacológicoRESUMO
Wave phenomena can be artificially engineered by scattering from metasurfaces, which aids in the design of radio-frequency and optical devices for wireless communication, sensing, imaging, wireless power transfer and bio/medical applications. Scattering responses vary with changing frequency; conversely, they remain unchanged at a constant frequency, which has been a long-standing limitation in the design of devices leveraging wave scattering phenomena. Here, we present metasurfaces that can scatter incident waves according to two variables-the frequency and pulse width-in multiple bands. Significantly, these scattering profiles are characterized by how the frequencies are used in different time windows due to transient circuits. In particular, by using more than one frequency with coupled transient circuits, we demonstrate variable scattering profiles in response to unique frequency sequences, which can break a conventional linear frequency concept and markedly increase the available frequency channels in accordance with a factorial number of frequencies used. Our proposed concept, which is analogous to frequency hopping in wireless communication, advances wave engineering in electromagnetics and related fields.
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BACKGROUND/AIM: This study aimed to determine the effectiveness of online team-based learning (TBL) and the factors influencing dropouts from online TBL for pharmacists on how to conduct clinical medication reviews for older adults. PARTICIPANTS AND METHODS: All participants were randomly assigned to the TBL or non-TBL group by using a random number sequence table matched by their years of experience working as a pharmacist. The primary outcome was whether the score on the team readiness assurance test (TRAT) in the TBL group differed from that on the second individual readiness assurance test (IRAT) in the non-TBL group. The secondary outcome was to identify factors contributing to dropouts from the online TBL program. RESULTS: The TRAT score in the TBL group was significantly higher than the second IRAT score in the non-TBL group during the first session (p=0.010). There were no differences in TRAT and IRAT scores between groups in two subsequent sessions. Logistic regression analysis revealed that less than 10 years of pharmacy experience was a contributor to dropouts (p=0.039), whereas experience in home-based care prevented dropouts (p=0.026) in our online TBL program. CONCLUSION: This study revealed the short-term usefulness of online TBL on medication reviews for older adults and elucidated the factors related to dropouts. Although instructors should provide positive feedback to participants with insufficient experience in pharmacy practice and home-based care, online TBL has the potential to improve educational effectiveness for community pharmacists during the COVID-19 pandemic.
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Farmacêuticos , Aprendizagem Baseada em Problemas , Humanos , Idoso , Japão , Revisão de Medicamentos , Pandemias , Processos Grupais , Avaliação EducacionalRESUMO
Norcorrole derivatives with 3,4,5-trialkoxyphenyl moieties at the meso positions were synthesized to form various stacking assemblies in single crystals and thermotropic liquid crystals (LCs) depending on aliphatic chain lengths. Triple-decker stacking structures were formed via the interactions between the antiaromatic systems formed for the butoxy and dodecyloxy derivatives in the single-crystal and LC states, respectively. In particular, the LC state exhibited discotic columnar structures comprising triple deckers to exhibit high electric conductivity, as supported by molecular dynamics simulations.
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Deglutition aid foods are used to help patients with dysphagia take oral medications. Yoghurt is occasionally used to help swallow medications; however, its influence on pharmacokinetics is poorly understood. Yoghurt made with Lactococcus cremoris subsp. cremoris FC has a characteristic viscous texture that facilitates bolus formation and deglutition due to its metabolite exopolysaccharide. We assessed yoghurt prepared with L. cremoris FC as a food deglutition aid. We performed a dissolution test using famotidine powder mixed with yoghurt and a food thickener. Famotidine dissolution rates without deglutition-assisting foods and with yoghurt or food thickener were 102.3 ± 1.7, 85.7 ± 4.6, and 46.4 ± 1.1% after 15 min, respectively. Next, we orally administered famotidine powder with water, yoghurt, and food thickener to rats and measured plasma famotidine levels. We observed no significant differences between all test groups. The Tmax of famotidine mixed with a food thickener was significantly lower than that with yoghurt. These results suggest that yoghurt with L. cremoris FC did not remarkably affect the dissolution and pharmacokinetic profiles of famotidine powder. Thus, the administration of famotidine with yoghurt might be a suitable alternative to powder administration as a deglutition aid for patients.
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Deglutição , Famotidina , Ratos , Animais , Famotidina/farmacologia , Solubilidade , Pós/farmacologia , IogurteRESUMO
An 89-year-old man with an intermittent 2:1 second-degree atrioventricular block received a permanent pacemaker (Medtronic Azure XT DR; Medtronic Inc., Minneapolis, MN, USA). Reactive antitachycardia pacing (ATP) was engaged in all transmissions 3â¯weeks later. Intracardiac recordings revealed a far-field R wave (FFRW) oversensing, occurring between atrial waves and premature atrial contractions. This event triggered the delivery of reactive ATP, which induced atrial fibrillation. A 79-year-old man underwent permanent pacemaker implantation for an intermittent complete atrioventricular block. One month after implantation, reactive ATP was initiated. The atrial electrogram of intracardiac recordings revealed one being a spontaneous P wave and the other an oversensed R wave. The criterion for an atrial tachycardia was fulfilled, and the device initiated reactive ATP. As a result, atrial fibrillation was induced by inappropriate reactive ATP. It was difficult to completely avoid inappropriate reactive ATP. Finally, we discontinued reactive ATP. The two cases presented in this study demonstrate the possibility of inappropriate reactive ATP due to FFRW oversensing, with the inappropriate reactive ATP inducing atrial fibrillation. All patients treated with reactive ATP should be carefully assessed for the presence of FFRW oversensing during pacemaker implantation and during the follow-up period. Learning objective: We present two cases of inappropriate reactive ATP caused by far-field R-wave oversensing. Inappropriate reactive ATP has not been previously reported. Therefore, we suggest that all patients provided with a DDD pacemaker should be carefully assessed for the presence of FFRW oversensing during pacemaker implantation and during the follow-up period. Remote monitoring enables very early detection of inappropriate reactive ATP delivery for rapid implementation of preventive measures.
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A new series of π-extended quinone derivatives containing a pyrrole bridge exhibited NH/OH-type tautomerization and anion binding along with deprotonation that induced near-infrared absorption and ion-pairing assemblies.
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Pirróis/química , Quinonas/química , Cristalografia por Raios X , Elétrons , Conformação Molecular , Espectrofotometria UltravioletaRESUMO
This study focused on the use of nonconventional bent-core π-electronic systems, 2,2'-bipyrroles substituted with modified benzoyl units, as building units of stimuli-responsive assemblies. Electric-field-responsive mesophase behaviors were observed in homochiral synclinic ferroelectric smectic C structures comprising the syn conformations. Electric-field application induced changes in the polarized optical microscopy textures with dynamic behaviors derived from the conversion from twisted to untwisted states.
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Multiply aryl-substituted pyrrole-based anion-responsive π-electronic molecules were synthesized. The effects of the introduced aryl moieties on solution-state emissive behaviours were examined, depending on the solvent polarity and anion binding.
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Cardiac pacemakers using rate response technologies represent the effectiveness of increasing the heart rate and cardiac output during exercise. Minute ventilation (MV) sensors are popular and estimate rates using transthoracic impedance by emitting very low amperage short electrical current pulses between the pacemaker lead tip and pulse generator. We present a case of an incomplete pacemaker lead fracture developing inappropriate pacing inhibition due to oversensing caused by the electrical current emitted by the MV sensor. A permanent pacemaker replacement was performed, resulting in no further abnormal findings such as inappropriate pacing inhibition.
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BACKGROUND: Circumferential pulmonary vein (PV) isolation for atrial fibrillation (AF) is occasionally difficult to achieve because electrical breakthrough sites (EBSs) between the left atrium (LA) and PVs cannot be identified during ablation especially in the carina regions. METHODS: The left PVs (Lt.PVs) of 60 AF patients and the right PVs (Rt.PVs) of 37 patients undergoing PV isolation were studied. When PV isolation was not achieved after the initial circumferential PV isolation, atrial pacing was repeatedly performed from the distal coronary sinus (CSd) and high right atrium (HRA), and the time interval from the stimulus to the earliest PV potential (stimulus-PV interval) was measured using circular mapping catheters at each PV until PV isolation was achieved. When PV isolation was achieved via local Radiofrequency (RF) deliveries, those regions were diagnosed as final EBSs. We classified the final EBSs into six segments for each PV (anterior and posterior PV walls of the roof, carina, and bottom) and investigated the relationship between the final EBSs and stimulus-PV intervals. RESULTS: For Lt.PVs, the stimulus-PV intervals during CSd pacing were significantly shorter than during HRA pacing at the Lt.PV anterior carina and bottom (90±28 ms vs. 125±26 ms, P<0.001 and 84±20 ms vs. 148±24 ms, P=0.028, respectively), but there was no significant difference in the Lt.PV roof and any posterior segments. For Rt.PVs, the stimulus-PV interval from both pacing sites exhibited no significant difference between either segment. CONCLUSIONS: This pacing method may help to identify whether EBSs are located in the anterior Lt.PVs. Improved recognition of EBSs through pacing from different sites would be helpful for achieving PV isolation.
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We report a case of atrioventricular (AV) accessory pathway with anterograde decremental conduction property. The δ wave polarity suggested the presence of a right posteroseptal accessory AV pathway. During atrial pacing, Wenckebach-type AV block over the accessory pathway was observed with prolongation of the local AV conduction time without the change in QRS morphology. No retrograde ventriculoatrial conduction was observed. During mapping of the right midseptal area, mechanical conduction block at the level of the proximal input to the accessory pathway was induced repeatedly by catheter manipulation. Radiofrequency energy delivery eliminated the accessory pathway. In this case only the bump phenomenon was the best marker of successful ablation.
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Feixe Acessório Atrioventricular/fisiopatologia , Feixe Acessório Atrioventricular/cirurgia , Adulto , Estimulação Cardíaca Artificial , Eletrocardiografia , Feminino , Sistema de Condução Cardíaco/fisiopatologia , Sistema de Condução Cardíaco/cirurgia , Humanos , Resultado do TratamentoRESUMO
PURPOSE: Left atrial (LA) thrombus was sometimes found by transesophageal echocardiography (TEE) in non-valvular atrial fibrillation (AF), even in the setting of continuous warfarin therapy. A D-dimer cutoff level of 0.50 µg/mL appears to be a useful marker to rule out venous vein thrombosis. This study analyzed the clinical features of patients with LA thrombi who received anticoagulant therapy and whether the D-dimer test is useful to exclude LA thrombus. METHODS: Two hundred twenty-five consecutive patients with AF (149 with paroxysmal and 76 with persistent) were enrolled. All patients received continuous warfarin therapy with the prothrombin time-international normalized ratio (PT-INR) between 1.6 and 3.0 for more than 3 months and TEE was performed. RESULTS: LA thrombi were present in 23 and absent in 202 patients. Age, gender, and PT-INR (1.96 ± 0.59 vs. 1.98 ± 0.53) were not different between the two groups. Persistent AF (65 vs. 30%; p < 0.005), LA diameter (44 ± 5 vs. 40 ± 7 mm; p < 0.005), ejection fraction (57 ± 13 vs. 65 ± 9%; p < 0.005), brain natriuretic peptide levels (203 ± 209 vs. 105 ± 166 pg/mL; p < 0.05), D-dimer (0.55 ± 0.70 vs. 0.16 ± 0.20 µg/mL; p < 0.001), LA appendage flow velocity (33 ± 15 vs. 54 ± 19 cm/s; p < 0.001), CHADS(2) scores (2 ± 1 vs. 1 ± 1; p < 0.005), and CHA(2)DS(2)-VASc scores (3 ± 2 vs. 2 ± 1; p < 0.005) were significantly different in both groups. Although multivariate analysis showed that D-dimer and LA appendage flow velocity were significant independent predictors of LA thrombus, D-dimer levels below 0.5 µg/mL were found in 19 of 23 patients with LA thrombi. CONCLUSION: D-dimer levels below 0.5 µg/mL is not enough to rule out LA thrombus in AF patients with well-controlled anticoagulation.