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1.
PLOS Glob Public Health ; 4(5): e0003156, 2024.
Article in English | MEDLINE | ID: mdl-38696522

ABSTRACT

Poor TB treatment outcomes are observed in patients with type 2 diabetes mellitus (DM) comorbidity and glycemic control throughout treatment may play a role. The objective of this study was to investigate glycemic control longitudinally among Filipino adults undergoing TB treatment using mixed-effects linear and logistic regression. Analyses were conducted in 188 DM-TB patients out of 901 enrolled in the Starting Anti-TB Treatment (St-ATT) cohort, with a median baseline glycosylated hemoglobin (HbA1c) of 8.2% (range 4.5-13.3%). Previous versus new DM diagnosis was associated with higher mean HbA1c (worse glycemic control) during treatment, with a smaller effect amongst those with central obesity (coefficient 0.80, 95% confidence interval [CI] 0.26, 1.57, P = 0.043) than amongst those without central obesity (coefficient 3.48, 95% CI 2.16, 4.80, P<0.001). In those with a new DM diagnosis, central obesity was associated with higher blood glucose (coefficient 1.62, 95% CI 0.72, 2.53, P = 0.009). Of 177 participants with ≥2 HbA1c results, 40% had uncontrolled glycemia (≥2 HbA1c results ≥8%). Of 165 participants with ≥3 HbA1c results, 29.9% had consistently-controlled glycemia, 15.3% had initially-uncontrolled glycemia, and 18.6% had consistently-uncontrolled glycemia. Previous versus new DM diagnosis and glucose-lowering medication use versus no use were associated with having uncontrolled versus controlled glycemia (adjusted odds ratio [aOR] 2.50 95%CI 1.61, 6.05, P = 0.042; aOR 4.78 95% CI 1.61,14.23, P<0.001) and more likely to have consistently-uncontrolled versus consistently-controlled glycemia (adjusted relative risk ratio [aRRR] 5.14 95% CI 1.37, 19.20, P = 0.015; aRRR 10.24 95% CI 0.07, 0.95, P = 0.003). Relapse cases of TB were less likely than new cases to have uncontrolled (aOR 0.20 95%CI 0.06, 0.63, P = 0.031) or consistently-uncontrolled (aRRR 0.25 95%CI 0.07, 0.95, P = 0.042) versus controlled glycemia. Those with long-term DM, suggested by previous diagnosis, glucose-lowering medication use and possibly central obesity, may require additional support to manage blood glucose during TB treatment.

2.
Front Immunol ; 15: 1330796, 2024.
Article in English | MEDLINE | ID: mdl-38665909

ABSTRACT

Introduction: There is no useful method to discriminate between latent tuberculosis infection (LTBI) and active pulmonary tuberculosis (PTB). This study aimed to investigate the potential of cytokine profiles to discriminate between LTBI and active PTB using whole-blood stimulation with Mycobacterium tuberculosis (MTB) antigens, including latency-associated antigens. Materials and methods: Patients with active PTB, household contacts of active PTB patients and community exposure subjects were recruited in Manila, the Philippines. Peripheral blood was collected from the participants and used for whole-blood stimulation (WBS) with either the early secretory antigenic target and the 10-kDa culture filtrate protein (ESAT-6/CFP-10), Rv3879c or latency-associated MTB antigens, including mycobacterial DNA-binding protein 1 (MDP-1), α-crystallin (Acr) and heparin-binding hemagglutinin (HBHA). Multiple cytokine concentrations were analyzed using the Bio-Plex™ multiplex cytokine assay. Results: A total of 78 participants consisting of 15 active PTB patients, 48 household contacts and 15 community exposure subjects were eligible. The MDP-1-specific IFN-γ level in the active PTB group was significantly lower than that in the household contact group (p < 0.001) and the community exposure group (p < 0.001). The Acr-specific TNF-α and IL-10 levels in the active PTB group were significantly higher than those in the household contact (TNF-α; p = 0.001, IL-10; p = 0.001) and community exposure (TNF-α; p < 0.001, IL-10; p = 0.01) groups. However, there was no significant difference in the ESAT-6/CFP-10-specific IFN-γ levels among the groups. Conclusion: The patterns of cytokine profiles induced by latency-associated MTB antigens using WBS have the potential to discriminate between LTBI and active PTB. In particular, combinations of IFN-γ and MDP-1, TNF-α and Acr, and IL-10 and Acr are promising. This study provides the first demonstration of the utility of MDP-1-specific cytokine responses in WBS.


Subject(s)
Antigens, Bacterial , Cytokines , Latent Tuberculosis , Mycobacterium tuberculosis , Tuberculosis, Pulmonary , Humans , Antigens, Bacterial/immunology , Antigens, Bacterial/blood , Male , Latent Tuberculosis/diagnosis , Latent Tuberculosis/immunology , Latent Tuberculosis/blood , Latent Tuberculosis/microbiology , Female , Mycobacterium tuberculosis/immunology , Philippines , Adult , Cytokines/blood , Middle Aged , Tuberculosis, Pulmonary/immunology , Tuberculosis, Pulmonary/blood , Tuberculosis, Pulmonary/diagnosis , Tuberculosis, Pulmonary/microbiology , Young Adult , Bacterial Proteins/immunology
3.
Chemistry ; : e202400916, 2024 Apr 21.
Article in English | MEDLINE | ID: mdl-38644537

ABSTRACT

Upon dibenzo annulation on Thiele's hydrocarbon (tetraphenyl-p-quinodimethane), the quinoid form and the biradical form adopt quite different geometries, and thus are no longer resonance structures. When these two forms can interconvert rapidly due to the small energy barrier (ΔG‡), the equilibrated mixture contains both forms in a ratio that is determined by the energy difference (ΔGo) between the two forms. For a series of tetrakis[5-(4-methoxyphenyl)-2-thienyl]-substituted derivatives, the more stable quinoid form and the metastable biradical form coexist in solution as an equilibrated mixture due to small ΔG‡ (< 15 kcal mol-1) and ΔGo (1-4 kcal mol-1), in which the proportion of the two forms can be regulated by temperature. Since the biradical form can undergo easy two-electron (2e) oxidation to the corresponding dications as well as easy 2e reduction to the dianions, it exhibits very high electrochemical amphotericity. This character with a record-small span for not only the first oxidation and reduction potentials but also the second those, [E1sum ≈ E2sum = E2ox - E2red = ca. 1.4 V], is attained through thermally enhanced conversion to the biradical form from the corresponding quinoid form, the latter of which is less amphoteric due to higher Eox and lower Ered values.

4.
Article in English | MEDLINE | ID: mdl-38575321

ABSTRACT

A novel swine model was developed to investigate the underlying reasons for the failure of aspiration thrombectomy. The model allows direct visualization of the target artery during thrombectomy in vessels of different sizes. The behavior of the target artery undergoing aspiration thrombectomy was recorded with high-resolution digital microscopy and fluoroscopic visualization, providing valuable insight into how the different sizes of treated arteries affect the effectiveness of mechanical thrombectomy.

5.
Arerugi ; 73(2): 180-188, 2024.
Article in Japanese | MEDLINE | ID: mdl-38522932

ABSTRACT

OBJECTIVE: Quality of life (QOL) questionnaires for parents of children with food allergies have been developed in the United States and Europe. However, no original Japanese QOL questionnaire has been developed till date. We aimed to develop an original questionnaire to evaluate the QOL in parents of children with food allergies in Japan. METHODS: We collected QOL-related questions from parents of children with food allergies aged 0-15 years, and created a primary questionnaire. Responses to the primary questionnaire were obtained from the parents again, and question items were reduced using factor analysis to create a secondary questionnaire comprising eight items. In addition to the secondary questionnaire, responses to the Food Allergy QOL Questionnaire-Parent Form (FAQLQ-PF) Japanese version, Parent reported Health-Related QOL in children and adolescents (KINDL) and Health-related QOL (SF-8) were obtained from parents to assess the validity of the secondary questionnaire. RESULTS: A total of 407 parents completed all questionnaires. The secondary questionnaire scores were positively correlated with those of FAQLQ-PF and weakly negatively correlated with the KINDL and SF-8 mental component summary scores. Parents of children with food allergies with ≥3 culprit foods or severe reactions to daily foods, a history of anaphylaxis, and those carrying adrenaline autoinjectors scored higher and had lower QOL. CONCLUSION: The developed original questionnaire is a valid QOL questionnaire for Parents of children with food allergies.


Subject(s)
Anaphylaxis , Food Hypersensitivity , Child , Adolescent , Humans , Quality of Life , Parents , Surveys and Questionnaires
6.
Small ; : e2311557, 2024 Mar 29.
Article in English | MEDLINE | ID: mdl-38553810

ABSTRACT

A liquescent salt consisting of a 7,7,8,8-tetracyanquinodimethane (TCNQ) radical anion and a tetra-n-decylammonium ion, 1+•TCNQ•-, exhibits rapid changes in the short-wave infrared (SWIR) light transparency at 1000-1400 nm upon the application of a one-shot needlestick-stimulus. Radical anion salt 1+•TCNQ•- transforms from a blue solid to a green liquid at 90 °C without decomposition under aerated conditions, and remains in the liquid state upon cooling to 70 °C. After applying pressure with a needlestick on a cover glass at 70 °C, the liquid transforms rapidly into the solid state over a timescale of seconds across a centimeter scale of area. Along with the liquid-solid transition, the SWIR-light transparency at 1200 nm completely switches from the "on" to the "off" states. Experimental results, such as electronic spectra and crystal structure analysis, indicates that the SWIR-light absorption in the solid state is due to the existence of a slipped-stacking π-dimer structure for TCNQ•-. The rapid rearrangement is induced by the formation of the π-dimer structures from the monomers of TCNQ•- and the subsequent generations of the solid-state seed.

7.
Chempluschem ; : e202400132, 2024 Mar 28.
Article in English | MEDLINE | ID: mdl-38548656

ABSTRACT

This study explores the remarkable properties of liquescent open-shell ionic molecular systems, emphasizing the magnetic and photophysical characteristics arising from their associated structures in the condensed state under various conditions. Well-investigated open-shell molecules, namely, phenothiazine, dihydrophenazine, and tetrathiafulvalene radical cations, and bis(malononitriledithiolato)nickel(III) anionic complexes were examined, and the concept of liquescent open-shell ionic molecular systems was devised. Transformations in their associated structures are induced by external stimuli, resulting in significant variations in their physical properties. These experimental findings open new avenues for exploring and applying stimuli-responsive molecule-based materials.

8.
EBioMedicine ; 102: 105073, 2024 Apr.
Article in English | MEDLINE | ID: mdl-38520916

ABSTRACT

BACKGROUND: The current pipeline for new antibiotics fails to fully address the significant threat posed by drug-resistant Gram-negative bacteria that have been identified by the World Health Organization (WHO) as a global health priority. New antibacterials acting through novel mechanisms of action are urgently needed. We aimed to identify new chemical entities (NCEs) with activity against Klebsiella pneumoniae and Acinetobacter baumannii that could be developed into a new treatment for drug-resistant infections. METHODS: We developed a high-throughput phenotypic screen and selection cascade for generation of hit compounds active against multidrug-resistant (MDR) strains of K. pneumoniae and A. baumannii. We screened compound libraries selected from the proprietary collections of three pharmaceutical companies that had exited antibacterial drug discovery but continued to accumulate new compounds to their collection. Compounds from two out of three libraries were selected using "eNTRy rules" criteria associated with increased likelihood of intracellular accumulation in Escherichia coli. FINDINGS: We identified 72 compounds with confirmed activity against K. pneumoniae and/or drug-resistant A. baumannii. Two new chemical series with activity against XDR A. baumannii were identified meeting our criteria of potency (EC50 ≤50 µM) and absence of cytotoxicity (HepG2 CC50 ≥100 µM and red blood cell lysis HC50 ≥100 µM). The activity of close analogues of the two chemical series was also determined against A. baumannii clinical isolates. INTERPRETATION: This work provides proof of principle for the screening strategy developed to identify NCEs with antibacterial activity against multidrug-resistant critical priority pathogens such as K. pneumoniae and A. baumannii. The screening and hit selection cascade established here provide an excellent foundation for further screening of new compound libraries to identify high quality starting points for new antibacterial lead generation projects. FUNDING: BMBF and GARDP.


Subject(s)
High-Throughput Screening Assays , Small Molecule Libraries , Humans , Small Molecule Libraries/pharmacology , Klebsiella pneumoniae , Microbial Sensitivity Tests , Anti-Bacterial Agents/pharmacology , Escherichia coli , Drug Resistance, Multiple, Bacterial
9.
J Neurointerv Surg ; 2024 Feb 28.
Article in English | MEDLINE | ID: mdl-38418227

ABSTRACT

BACKGROUND: The delivery of neuroendovascular devices requires a robust proximal access platform. This demand has previously been met with a 6Fr long sheath (8Fr guide) that is placed in the proximal internal carotid artery (ICA) or vertebral artery segments. We share our experience with the first 0.088 inch 8Fr guide catheter designed for direct intracranial access. METHODS: We retrospectively reviewed a prospectively maintained IRB-approved institutional database of the senior authors to identify all cases where the TracStar Large Distal Platform (LDP) was positioned within the intracranial vasculature, defined as within or distal to the petrous ICA, vertebral artery (V3) segments, or transverse sinus. Technical success was defined as safe placement of the TracStar LDP within or distal to the described distal vessel segments with subsequent complication-free device implantation. RESULTS: Over the 41-month study period from January 2020 to June 2023, 125 consecutive cases were identified in whom the TracStar LDP was navigated into the intracranial vasculature for triaxial delivery of large devices, 0.027 inch microcatheter and greater, for aneurysm treatment (n=108, 86%), intracranial angioplasty/stenting (n=15, 12%), and venous sinus stenting (n=2, 1.6%). All cases used a direct select catheter technique for initial guide placement (no exchange). Posterior circulation treatments occurred in 14.4% (n=18) of cases. Technical success was achieved in 100% of cases. No vessel dissections occurred in any cases. CONCLUSION: The TracStar LDP is an 0.088 inch 8Fr guide catheter that can establish direct intracranial access with an acceptable safety profile. This can be achieved in a wide range of neurointerventional cases with a high rate of technical success.

11.
Small ; 20(2): e2305668, 2024 Jan.
Article in English | MEDLINE | ID: mdl-37670219

ABSTRACT

A liquescent bis(malononitriledithiolato)nickel(III) complex with a bis(methoxyethyl)imidazolium cation, 1[Ni(mnt)2 ], exhibits three-stage thermochromic modulation of transparency/absorption in the short-wave-infrared (SWIR) region (1000-2500 nm), driven by associated structural changes. Upon heating, the electronic spectra of 1[Ni(mnt)2 ] in the SWIR region shift to shorter wavelengths accompanying with the solid-liquid phase transition at 76 °C. Further heating to over 109 °C induces a second transition of the electronic spectra, characterized by a blue-shift of the SWIR absorption in the liquid phase. The results of temperature-dependent electronic spectra and magnetic susceptibility indicated that the thermochromic changes can be attributed to the two-step dissociation of the associated structures of [Ni(mnt)2 ]- , occurring during the solid-liquid phase transition and the shift of dimer-monomer equilibrium in the liquid state. These changes can be visualized using an SWIR imaging camera under appropriate SWIR lights.

12.
J Pediatr Hematol Oncol ; 46(2): e176-e179, 2024 Mar 01.
Article in English | MEDLINE | ID: mdl-38132703

ABSTRACT

Noonan syndrome-related myeloproliferative disorder (NS/MPD) and juvenile myelomonocytic leukemia (JMML) are rare MPDs that occur in young children. We herein report a case of NS/MPD with neonatal onset. The patient had a characteristic appearance and high monocyte count in the peripheral blood and bone marrow. Genetic testing showed the E139D mutation in PTPN11 ; however, the patient did not meet all the diagnostic criteria for JMML, and we thus diagnosed him with NS/MPD. Eight other cases of NS/MPD with neonatal onset are also summarized. The initial presentation varied, and the prognosis was considered poor compared with previous reports of NS/MPD.


Subject(s)
Leukemia, Myelomonocytic, Juvenile , Myeloproliferative Disorders , Noonan Syndrome , Humans , Infant, Newborn , Male , Leukemia, Myelomonocytic, Juvenile/complications , Leukemia, Myelomonocytic, Juvenile/diagnosis , Leukemia, Myelomonocytic, Juvenile/genetics , Mutation , Myeloproliferative Disorders/complications , Myeloproliferative Disorders/genetics , Noonan Syndrome/complications , Noonan Syndrome/genetics , Protein Tyrosine Phosphatase, Non-Receptor Type 11/genetics
13.
Front Neurol ; 14: 1181295, 2023.
Article in English | MEDLINE | ID: mdl-37396754

ABSTRACT

In this review article, we summarized the current advances in rescue management for reperfusion therapy of acute ischemic stroke from large vessel occlusion due to underlying intracranial atherosclerotic stenosis (ICAS). It is estimated that 24-47% of patients with acute vertebrobasilar artery occlusion have underlying ICAS and superimposed in situ thrombosis. These patients have been found to have longer procedure times, lower recanalization rates, higher rates of reocclusion and lower rates of favorable outcomes than patients with embolic occlusion. Here, we discuss the most recent literature regarding the use of glycoprotein IIb/IIIa inhibitors, angioplasty alone, or angioplasty with stenting for rescue therapy in the setting of failed recanalization or instant/imminent reocclusion during thrombectomy. We also present a case of rescue therapy post intravenous tPA and thrombectomy with intra-arterial tirofiban and balloon angioplasty followed by oral dual antiplatelet therapy in a patient with dominant vertebral artery occlusion due to ICAS. Based on the available literature data, we conclude that glycoprotein IIb/IIIa is a reasonably safe and effective rescue therapy for patients who have had a failed thrombectomy or have residual severe intracranial stenosis. Balloon angioplasty and/or stenting may be helpful as a rescue treatment for patients who have had a failed thrombectomy or are at risk of reocclusion. The effectiveness of immediate stenting for residual stenosis after successful thrombectomy is still uncertain. Rescue therapy does not appear to increase the risk of sICH. Randomized controlled trials are warranted to prove the efficacy of rescue therapy.

14.
Front Endocrinol (Lausanne) ; 14: 1175611, 2023.
Article in English | MEDLINE | ID: mdl-37484939

ABSTRACT

Background and objectives: We herein reported ten, female neonates with transient clitoral preputial edema, which was mistaken for clitoromegaly. Although it is well known that the clitoris is prominent in premature, female neonates, there are as of yet no reports of clitoral preputial edema in full-term neonates. The present study was conducted to clarify the clinical course of clitoral preputial edema. Methods: Seventeen, Japanese patients aged < 6 months with suspected clitoromegaly were enrolled, and their clinical course was analyzed retrospectively. Clitoral preputial edema was defined by 1) a normal clitoral glans despite edema; and 2) the absence of established differences of sexual development, such as 21-hydroxylase deficiency. Results: Ten of the 17 patients with suspected clitoromegaly had clitoral preputial edema; eight of the ten patients were full-term, and the remaining two were preterm neonates. The median age at the first visit was 8 days. Edema of the labia minora and labia majora, rugosity of the labia majora, and hymenal polyps often accompanied the clitoral preputial edema. Seven patients were examined at our division during the neonatal period, and three patients were examined in the post-neonatal period. Age at reduction of the clitoral width to < 7 mm ranged from 8 to 74 days in four of the seven neonatal patients. In the three post-neonatal patients, age to reduction in the clitoral width ranged from 107 to 243 days. Conclusions: Transient clitoral preputial edema is often mistaken for clitoromegaly. The key to diagnosing clitoral preputial edema lies in its characteristic appearance and improvement course.


Subject(s)
Clitoris , Edema , Female , Humans , Infant, Newborn , Clitoris/pathology , Disease Progression , Hypertrophy/diagnosis , Retrospective Studies , Vulva/surgery , Diagnosis, Differential , Infant
15.
Angew Chem Int Ed Engl ; 62(35): e202308570, 2023 Aug 28.
Article in English | MEDLINE | ID: mdl-37436067

ABSTRACT

The light-transmissive properties of a solid-state tetrathiafulvalene radical cation-bis(trifluoromethanesulfonyl)imide, 1-C5 ⋅+ ⋅ NTf2 - , underwent instantaneous changes in the short-wave infrared (SWIR) region (1000-2500 nm) upon exposure to solvent vapor or the application of mechanostress at room temperature. The initial solid state of 1-C5 ⋅+ ⋅ NTf2 - exhibited strong absorption in the near-infrared (NIR; 700-1000 nm) and SWIR regions, whereas the absorption in the SWIR region was significantly diminished in the stimulated state induced by dichloromethane vapor. Upon cessation of vapor stimulation, the solid state spontaneously and promptly reverted to its original state, characterized by absorption bands in the NIR/SWIR region. Moreover, the SWIR absorption was absent upon the application of mechanical stress using a steel spatula. The reversal was fast and occurred within 10 s. These changes were visualized using a SWIR imaging camera under 1450-nm light irradiation. Experimental investigations demonstrated that the transparency to the SWIR light in the solid states was modulated through significant structural transformations of the associated radical cations, with transitions between columnar and isolated π-dimer structures under ambient and stimulated conditions, respectively.

16.
Int J Speech Lang Pathol ; : 1-11, 2023 Jun 26.
Article in English | MEDLINE | ID: mdl-37357786

ABSTRACT

PURPOSE: We investigated the association between the time to first post-extubation oral intake, barriers to oral intake, and the rate of activities of daily living (ADL) independence at discharge (Barthel Index score <70). METHOD: Consecutive patients admitted to the intensive care unit, aged ≥18 years, and mechanically ventilated for ≥48 hr were retrospectively enrolled. The time to first oral intake, barriers to oral intake, daily changes, and clinical outcomes were assessed. Multiple logistic regression analysis adjusted for baseline characteristics was used to determine the association between time to first post-extubation oral intake and ADL independence. RESULT: Among the 136 patients, 74 were assigned to the ADL independence group and 62 to the dependence group. The time to first post-extubation oral intake was significantly associated with ADL independence (adjusted p = < 0.001) and was a predictor of ADL independence at discharge. Respiratory and dysphagia-related factors (odds ratio [OR] 0.35; 95% confidence interval [CI] 0.15-0.82, p = 0.015 and OR 0.07; CI 0.01-0.68, p = 0.021, respectively) were significantly associated with the ADL independence at discharge. CONCLUSION: Respiratory and dysphagia-related factors, as barriers to the initiation of oral intake after extubation, were significantly associated with ADL independence at discharge.

17.
Trop Med Health ; 51(1): 9, 2023 Feb 22.
Article in English | MEDLINE | ID: mdl-36814333

ABSTRACT

BACKGROUND: COVID-19 has challenged the under-resourced health systems of low- and middle-income countries, significantly affecting child health. Available published data on Filipino children with COVID-19 infection are limited. This study aims to describe the epidemiological and clinical characteristics of pediatric patients with confirmed COVID-19 in an infectious disease hospital in Manila, Philippines. MAIN TEXT: This cross-sectional study reviewed data on patients ages 0 to 18 years with confirmed COVID-19 infection, admitted to San Lazaro Hospital from January 25, 2020 to January 25, 2022. Demographic data and clinical characteristics obtained from COVID-19 case investigation forms were summarized and compared between severe and non-severe cases. Risk factors for disease severity and mortality were analyzed. Of 115 patients, 64% were males. There were 87 patients (75.7%) with asymptomatic, mild, or moderate disease, and 28 cases (24.3%) with severe or critical illness. The median age of all patients was 10 years (interquartile range: 4-15 years). The majority of patients (40.9%) were adolescents ages 13 to 18 years. Predominant symptoms were fever (73.9%) and cough (55.7%). Patients with severe or critical illness were more likely to experience difficulty of breathing (55.2% vs 44.8%, p < 0.001), and have a longer hospital stay (11 days vs 8 days, p = 0.043). Among all patients, 48.7% had at least one underlying disease; and common infectious co-morbidities were tuberculosis (17.4%), dengue (12.2%), and HIV (4.3%). Having tuberculosis (p = 0.008) or at least one co-morbidity (p < 0.001) was associated with disease severity. Ten patients (8.7%) died; and mortality was higher among those with severe or critical illness (80% vs 20%, p < 0.001). Sepsis (p = 0.020) or having at least one co-morbidity (p = 0.007) was associated with death. CONCLUSION: Children of all ages remain susceptible to COVID-19 infection, and usually present with mild or moderate symptoms. In this study, many adolescents are affected, highlighting the value of COVID-19 vaccination in this age group. Understanding the clinical features of COVID-19 in Filipino children is essential to identifying and optimally managing those at highest risk of severe disease.

18.
J Am Chem Soc ; 145(4): 2596-2608, 2023 Feb 01.
Article in English | MEDLINE | ID: mdl-36606368

ABSTRACT

A series of six dications composed of pure hydrocarbons with one to six non-substituted 9,10-anthrylene units end-capped with two dibenzotropyliums were designed and synthesized to elucidate the electronic properties of huge oligo(9,10-anthrylene) backbones. Their structures were successfully determined by X-ray analyses even in the case of eight planar 14π-electron units, revealing that all dications adopt almost orthogonally twisted structures between neighboring units. Spectroscopic and voltammetric analyses show that neither the significant overlap of orbitals nor the delocalization of electrons between 14π-electron units occurs due to the orthogonally twisted geometry even in solution. As a result, sequential oxidation processes were observed with the reversible formation of multivalent cations with the release of the same number of electrons as the number of anthrylene units. Upon two-electron reduction, a closed-shell butterfly-shaped form was obtained from the dication containing one anthrylene unit, whereas open-shell twisted biradicals were isolated as stable entities in the cases of derivatives containing three to six anthrylene units. Notably, from the derivative with two anthrylene units, a metastable open-shell isomer was obtained quantitatively and underwent slow thermal conversion to the most stable closed-shell isomer (Ea = 23.1 kcal mol-1). There is a drastic change in oxidation potentials between two neutral species (ΔE = 1.32 V in CH2Cl2). Since the present dications were regenerated upon oxidation of the isolated reduction products, these systems may contribute to the development of advanced response systems capable of switching color, magnetic properties, and oxidative properties by using a "cation-capped orthogonal geometry".

19.
Chem Commun (Camb) ; 59(10): 1301-1304, 2023 Jan 31.
Article in English | MEDLINE | ID: mdl-36633220

ABSTRACT

A structurally constrained, double-helical S,C-bridged tetraphenyl-para-phenylenediamine (TPPD) has been synthesized. The stable radical cation of the S,C-bridged TPPD was generated by chemical oxidation, and the electron spin was found to be delocalized over the entire π-conjugated framework. The excellent conformational stability of the neutral molecule facilitated the separation of its enantiomers.

20.
J Am Chem Soc ; 144(48): 21980-21991, 2022 Dec 07.
Article in English | MEDLINE | ID: mdl-36411699

ABSTRACT

Formation of a partially charge-transfer or partially oxidized/reduced state has been one of the most important requirements for the development of highly conducting molecular materials, such as organic metals and superconductors. This requirement has been fulfilled by combining appropriate electron-donor and acceptor molecules to construct multi-component molecular complexes/salts, such as (TTF+0.59)(TCNQ-0.59) and (BEDT-TTF+0.5)2X-, where TTF = tetrathiafulvalene, TCNQ = tetracyanoquinodimethane, BEDT-TTF = bis(ethylenedithio)tetrathiafulvalene, and X = monovalent inorganic anion. Here, we propose a methodology to fulfill this requirement by a single neutral molecule; namely, we have connected two TTF+0.5-type partially oxidized π-skeletons through a boron anion to design a purely organic zwitterionic neutral radical {[(PDT-TTF-Cat)2]+B-}•. This molecule was successfully obtained as air-stable crystals containing solvent tetrahydrofuran (THF) molecules. Measurements of electrical resistivity, magnetic susceptibility, and X-ray diffraction reveal that the partially oxidized state is certainly formed, which enables realization of a 3/4-filled electron band. Furthermore, this system has intramolecular charge degrees of freedom, attributable to the two TTF+0.5 π-skeletons introduced into the molecule. The resulting interplay of intra- and intermolecular charge degrees of freedom (or simply, intra- and intermolecular electronic interactions) has led to multi-step phase transitions and crossover, providing unique strongly correlated electron properties, such as the formation of a three-dimensional charge-ordered dimer-Mott insulating state and its melting triggered by disorder-order transformation of the co-crystallized solvent THF molecules at low temperatures.

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