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2.
PLoS One ; 18(8): e0289927, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-37561779

RESUMO

BACKGROUND: The number of adult patients with childhood-onset chronic diseases is increasing. However, the process of transitioning these patients from child- to adult-centered medical services faces many difficulties. Despite the key role that doctors in the pediatric field are considered to play in transition, few fact-finding surveys about transition have been conducted among these doctors. OBJECTIVE: The aim of this study was to demonstrate the current status and challenges in the transition of patients with childhood-onset chronic diseases by a fact-finding survey of pediatricians and pediatric surgeons at a university hospital. METHODS: A cross-sectional survey was performed using an anonymous self-administered questionnaire. Seventy-six doctors of pediatrics and pediatric surgery (excluding junior residents) in a university hospital were asked to answer an anonymous self-report questionnaire. A multidisciplinary research team selected items related to the transitional process. RESULTS: Sixty (79%) doctors participated, of whom 52 (87%) showed awareness of transition. No doctor answered that "Transition is conducted smoothly." Doctors with shorter pediatric department experience had lower awareness and poorer experience with transition. In contrast to pediatric surgeons, pediatricians explained "job-seeking activities" and "contraceptive methods" to the patient, and reported a higher patient age at which to initiate explanation of transition to the patient and his/her family. Among factors inhibiting transition, 39 (65%) respondents selected "The patient's family members do not desire transition" and 34 (57%) selected "Although a relevant adult healthcare department is available, it will not accept the patient." The medical providers most frequently considered to have responsibility for playing a central role in the transition process were "pediatrician/pediatric surgeon," "medical social worker," and "regional medical liaison office." DISCUSSION: To promote transition, pediatric and adult healthcare departments should share concerns about and cooperate in the establishment of more effective methods of transition, and provide multidisciplinary collaboration to support patients and their families.


Assuntos
Pediatria , Cirurgiões , Humanos , Adulto , Masculino , Feminino , Criança , Estudos Transversais , Atenção à Saúde , Inquéritos e Questionários , Doença Crônica
3.
Inorg Chem ; 62(31): 12272-12282, 2023 Aug 07.
Artigo em Inglês | MEDLINE | ID: mdl-37480022

RESUMO

Four types of bis- and tris(tetra-armed cyclen)s were prepared. 2MF is a bis(tetra-armed cyclen) with electron-rich side arms (three 4-methoxybenzyl groups) and electron-deficient side arms (three 3,5-difluorobenzyl groups), connected by a 4,4'-dimethyl-1,1'-biphenyl moiety. 3MFM is a tris(tetra-armed cyclen) with 4-methoxybenzyl and 3,5-difluorobenzyl groups introduced on both ends and the central cyclen, respectively. 4MFM is a V-shaped analogue of 3MFM. 3FMF is a tris(tetra-armed cyclen) where the aromatic side arms at both ends and the central cyclen of 3MFM are exchanged. The regioselective coordination of silver(I) ions by these ligands is reported. Initially, we added Ag+ ions to a compound (2MF) that consists of tetra-armed cyclen with 4-methoxybenzyl groups as an electron-donating substituent on the aromatic rings and 3,5-difluorobenzyl groups as an electron-withdrawing substituent. 1H NMR and 19F{1H} NMR spectroscopy exhibited that the cyclen with the 4-methoxybenzyl groups formed a complex with Ag+ ions first, followed by the cyclen with the 3,5-difluorobenzyl groups. Next, we employed a compound (3MFM) with three cyclen units, where the cyclen at each end was functionalized with three 4-methoxybenzyl groups, and the central cyclen was functionalized with two 3,5-difluorobenzyl groups. Upon adding Ag+ ions, we observed that the cyclen units at both ends formed complexes with Ag+ ions initially, followed by the central cyclen forming a complex with Ag+ ions. When we used 4MFM, which is a V-shaped compound, the Ag+-induced-1H NMR chemical shift changes are almost the same results as the 3MFM. Furthermore, we synthesized a compound (3FMF) by interchanging the substituents on the cyclen units at the ends and the center. Interestingly, the order of the complex formation was reversed in this compound. These results demonstrated that tuning the electron density on the aromatic side arms through substituents makes it possible to achieve regioselective coordination with Ag+ ions in bis- or tris(tetra-armed cyclen)s.

4.
J Org Chem ; 88(13): 9381-9387, 2023 Jul 07.
Artigo em Inglês | MEDLINE | ID: mdl-37184952

RESUMO

A 14-membered cyclic compound (3) containing amide, amino, and carbamate groups, which was serendipitously obtained in the oily residue after the separation of 4-benzyl-1,4,7,10-tetraazacyldododecane-2,6-dione (2a) and 4,16-dibenzyl-1,4,7,10,13,16,19,22-octaazacyclo-tetracosane-2,6,14,18-tetraone (2b), is reported. The structure of 3 is formally a CO2 insertion between positions 3 and 4 of the 12-membered ring in 2a. The CO2 insertion was confirmed in the synthesis of diethyl 2,2'-(benzylazanediyl)diacetate (1) by the reaction of benzylamine with ethyl bromoacetate using K2CO3 as the base. In addition, the selective synthesis of 3 and ethyl N-benzyl-N-((2-ethoxy-2-oxoethoxy)carbonyl)glycinate (5) and their kinetic behavior are reported. The reaction of 5 with triethylenetetramine afforded a 17-membered macrocycle (7), which was obtained in an 18% yield. Compounds 6 and 8 were prepared from 3 and 7 by introducing benzyl groups to improve their solubility in organic solvents. Titration experiments using 1H NMR showed that both 6 and 8 exhibit Li+ selectivity.


Assuntos
Amidas , Carbamatos , Dióxido de Carbono , Espectroscopia de Ressonância Magnética , Esqueleto
5.
Artigo em Inglês | MEDLINE | ID: mdl-36674179

RESUMO

AIM: We developed the Training Program on Child Abuse Prevention for Citizens (TCAP-C) and tested its effects and acceptability among citizen leaders (CLs). METHODS: Community-based participatory research using a pretest-posttest follow-up design was conducted in Tokyo, Japan from September 2021 to March 2022. Participants completed questionnaires before, upon completion, and one month and three months after TCAP-C. Recognition, knowledge, and behaviors regarding child abuse and community consciousness were collected and compared before and one and three months after TCAP-C, and the degree of satisfaction, understanding, and meaningfulness were collected upon completion. We analyzed data using repeated-measures ANCOVA. RESULTS: A total of 111, 98, 101, and 94 participants completed the questionnaires before, upon completion, and one and three months after TCAP-C, respectively. Overall, the recognition, knowledge, and community consciousness scores significantly improved from before to one month and three months after TCAP-C. Regarding the behaviors, only the behaviors of learning and watching over were significantly improved from before to one month after TCAP-C; however, those behaviors were not different between before and three months after TCAP-C. Furthermore, 95% participants reported being entirely satisfied with TCAP-C, and 85% and 91% reported good understanding and meaningfulness of the program. CONCLUSIONS: TCAP-C is acceptable and can improve CL recognition, knowledge, and community consciousness.


Assuntos
Maus-Tratos Infantis , Pesquisa Participativa Baseada na Comunidade , Criança , Humanos , Aprendizagem , Maus-Tratos Infantis/prevenção & controle , Inquéritos e Questionários
6.
Artigo em Inglês | MEDLINE | ID: mdl-36429671

RESUMO

This study evaluated the efficacy of a brief (four 2-h sessions) group-based resilience-enhancement program focused on emotion regulation in Japan. Mothers (n = 123) of children aged 3-6 years were recruited in two prefectures and allocated with stratified randomization by the prefecture to either a bi-weekly intervention or treatment as usual. Mothers self-reported online at pre/post-intervention and at 2-month follow-up. Analysis of covariance was used to compare groups. At post-intervention and 2-month follow-up, the intervention group mothers showed significant improvements compared to the control group in resilience (p < 0.001/p = 0.001), self-esteem (p = 0.008/p = 0.001), anger control toward the child (p < 0.001/p = 0.012), and positive attribution toward the child's misbehavior (p < 0.001/p = 0.003). The partners of mothers in both groups answered the same questionnaire at the same timepoints without participating in either program; no differences between groups were found. This study was the first randomized controlled trial investigating how a resilience-enhancement program improves maternal resilience, emotion regulation, and cognition toward children and themselves. This preliminary study provides evidence that improving resilience may reduce the risk of child maltreatment. Further research regarding implementing this intervention in the community is warranted.


Assuntos
Maus-Tratos Infantis , Regulação Emocional , Criança , Feminino , Humanos , Japão , Mães/psicologia , Maus-Tratos Infantis/psicologia , Inquéritos e Questionários
7.
J Immunol ; 209(11): 2104-2113, 2022 12 01.
Artigo em Inglês | MEDLINE | ID: mdl-36426984

RESUMO

Although the immunological memory produced by BNT162b2 vaccination against severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) has been well studied and established, further information using different racial cohorts is necessary to understand the overall immunological response to vaccination. We evaluated memory B and T cell responses to the severe acute respiratory syndrome coronavirus 2 spike protein before and after the third booster using a Japanese cohort. Although the Ab titer against the spike receptor-binding domain (RBD) decreased significantly 8 mo after the second vaccination, the number of memory B cells continued to increase, whereas the number of memory T cells decreased slowly. Memory B and T cells from unvaccinated infected patients showed similar kinetics. After the third vaccination, the Ab titer increased to the level of the second vaccination, and memory B cells increased at significantly higher levels before the booster, whereas memory T cells recovered close to the second vaccination levels. In memory T cells, the frequency of CXCR5+CXCR3+CCR6- circulating follicular Th1 was positively correlated with RBD-specific Ab-secreting B cells. For the response to variant RBDs, although 60-80% of memory B cells could bind to the omicron RBD, their avidity was low, whereas memory T cells show an equal response to the omicron spike. Thus, the persistent presence of memory B and T cells will quickly upregulate Ab production and T cell responses after omicron strain infection, which prevents severe illness and death due to coronavirus disease 2019.


Assuntos
COVID-19 , Células B de Memória , Humanos , SARS-CoV-2 , Células T de Memória , Vacina BNT162 , Vacinação
8.
Eur J Immunol ; 52(12): 1961-1971, 2022 12.
Artigo em Inglês | MEDLINE | ID: mdl-36250411

RESUMO

Memory T cell responses have been analyzed only in small cohorts of COVID-19 vaccines. Herein, we aimed to assess anti-SARS-CoV-2 cellular immunity in a large cohort using QuantiFERON assays, which are IFN-γ release assays (IGRAs) based on short-term whole blood culture. The study included 571 individuals receiving the viral spike (S) protein-expressing BNT162b2 mRNA vaccine. QuantiFERON assays revealed antigen-specific IFN-γ production in most individuals 8 weeks after the second dose. Simultaneous flow cytometric assays to detect T cells expressing activation-induced markers (AIMs) performed for 28 randomly selected individuals provided data correlating with the QuantiFERON data. Simultaneous IFN-γ enzyme-linked immunospot and AIM assays for another subset of 31 individuals, based on short-term peripheral blood mononuclear cell culture, also indicated a correlation between IFN-γ production and AIM positivity. These observations indicated the acquisition of T cell memory responses and supported the usability of IGRAs to assess cellular immunity. The QuantiFERON results were weakly correlated with serum IgG titers against the receptor-binding domain of the S protein and were associated with pre-vaccination infection and adverse reactions after the second dose. The present study revealed cellular immunity after COVID-19 vaccination, providing insights into the effects and adverse reactions of vaccination.


Assuntos
COVID-19 , Vacinas , Humanos , Vacinas contra COVID-19 , SARS-CoV-2 , Vacina BNT162 , Leucócitos Mononucleares , COVID-19/prevenção & controle , Imunidade Celular
9.
J Nurs Manag ; 30(8): 4042-4053, 2022 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-36194470

RESUMO

AIM: We aim to identify measures implemented by hospital nursing directors early in the COVID-19 pandemic and enabling factors. BACKGROUND: Managerial factors affect nurses' physical and mental health and willingness to work, especially early in a pandemic. METHOD: We used multiple-case study of 15 hospitals, comparing management approaches by interviewing 28 nursing directors and their assistants from August to December 2020. RESULTS: Hospitals that accepted COVID-19 patients and hospitals that unexpectedly experienced clusters underwent a nursing provision system organization phase, followed by an adjustment phase to maintain nursing organization function. Two factors aided measure implementation: an emergency system and staff protection policies. CONCLUSION: Early epidemic management strategies apply across contexts. The hospital's basic attitude is key to effective implementation of the strategies. IMPLICATIONS FOR NURSING MANAGEMENT: The results suggest that hospitals, nursing directors and nurses can each prepare for future emerging infectious disease epidemics.


Assuntos
COVID-19 , Cuidados de Enfermagem , Humanos , COVID-19/epidemiologia , Pandemias , Hospitais
10.
Arch Womens Ment Health ; 25(6): 1119-1127, 2022 12.
Artigo em Inglês | MEDLINE | ID: mdl-36306037

RESUMO

This study examined the associations between childbirth decisions in women with unintended pregnancies and long-term psychological distress. An online survey of women selected from a representative research panel was conducted in July 2021. Among participants who experienced an unintended pregnancy, the childbirth decision was categorized: (i) wanted birth, (ii) abortion, (iii) adoption, and (iv) unwanted birth. Participants who made childbirth decisions more than 1 year ago were included. ANCOVA was conducted with psychological distress (Kessler 6) as the dependent variable and education, marital status, years from the decision, age of the first pregnancy, economic situation at the unintended pregnancy, and the number of persons consulted at the unintended pregnancy as covariates. Logistic regression analysis was conducted for high distress (K6 ≥ 13) by adjusting the same covariates. A total of 47,401 respondents participated in the study. Women with an experience of unintended pregnancy experienced more than 1 year before the study were analyzed (n = 7162). Psychological distress was the lowest for wanted birth and increased for abortion, adoption, and unwanted birth. In the adjusted model, abortion was associated with lower distress scores than both adoption and unwanted birth. Compared to the wanted birth, adoption and unwanted birth showed significantly higher levels of distress (adjusted odds ratio [aOR] = 2.03 [95% CI 1.36-3.04], aOR = 1.64 [95% CI 1.04-2.58], respectively). Long-term effects on psychological distress differed according to the childbirth decisions in unintended pregnancy. Healthcare professionals should be aware of this hidden effect of unintended pregnancy experience on women's mental health.


Assuntos
Aborto Induzido , Aborto Espontâneo , Angústia Psicológica , Gravidez , Criança , Feminino , Humanos , Gravidez não Planejada , Estudos Transversais , Estudos Retrospectivos , Aborto Induzido/psicologia , Aborto Espontâneo/psicologia
11.
Dalton Trans ; 51(40): 15530-15537, 2022 Oct 18.
Artigo em Inglês | MEDLINE | ID: mdl-36165977

RESUMO

We have prepared new argentivorous molecules (L2 and L3) having different linker lengths between cyclen and anthracene units. The structures of Ag+ complexes with the new ligands were investigated in solution and solid states. The silver(I) ion-induced 1H NMR and UV-vis spectral changes of L2 and L3 showed the presence of 1 : 1 complexes. The solid-state structures of the Ag+ complexes with L2 and L3 are stable 1 : 1 complexes because four aromatic side-arms wrap the Ag+ incorporated in the cyclen unit. A photo-induced electron transfer (PET) effect that depends on the length of the linker connecting the nitrogen atoms of cyclen to the chromophore is also investigated. The result indicates a linear (log) correlation between the donor-chromophore average distances of the optimized structures calculated by DFT calculations and fluorescence intensities (log I), and the PET effect becomes ineffective at about 12 Å in this system.


Assuntos
Ciclamos , Compostos Organometálicos , Antracenos , Ligantes , Modelos Moleculares , Nitrogênio , Compostos Organometálicos/química , Prata/química
12.
J Org Chem ; 87(18): 12434-12440, 2022 09 16.
Artigo em Inglês | MEDLINE | ID: mdl-36026614

RESUMO

A flexible cylindrical cryptand (1b) with two m-phenylene-26-crown-8 ethers has been prepared, and its complexing properties with respect to tetravalent cationic bis-paraquat guests have been investigated. Diffusion-ordered spectroscopy nuclear magnetic resonance (NMR) and titration experiments using cold electrospray ionization mass spectrometry and 1H NMR revealed that 1b has versatile complexing properties with respect to tetravalent cationic guests used despite the guest molecules' length and shape.


Assuntos
Éteres de Coroa , Paraquat , Éteres de Coroa/química , Ligantes , Espectroscopia de Ressonância Magnética , Conformação Molecular , Paraquat/química
13.
Jpn J Nurs Sci ; 19(4): e12494, 2022 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-35661592

RESUMO

AIM: This observational study aimed to describe the rate and degree of difficult experiences with COVID-19 pandemic-related changes (DE) during pregnancy, clarify the relationship between DE and self-compassion of women postnatally, and investigate the influence of compassion from a partner (CP) and compassion from the woman's mother (CM) on this relationship. METHODS: Data from 46 1-month postnatal women in Japan were collected through a self-report questionnaire from October to December 2020. Self-compassion was measured using the Japanese version of the Self-Compassion Scale; DE, CP, and CM were measured using original questions based on prior studies. RESULTS: Almost all participants (97.8%) experienced more than one DE during pregnancy. Data analyses revealed that DE in maternity hospitals (d = 0.76), DE in social support (d = 0.53), and CM (d = 0.64) were associated with self-compassion. A two-way analysis of variance suggested that CM moderated the relationship between self-compassion and DE in preparation for the baby (η2  = 0.11) and the birth plan (η2  = 0.11), whereas CP moderated the relationship between self-compassion and DE in social support (η2  = 0.07). CONCLUSIONS: Our findings suggest that self-compassion negatively correlates with DE in maternity hospitals and social support. Additionally, CM may buffer the influence of DE in preparation for the baby and the birth plan on self-compassion; moreover, CP may buffer the influence of DE in social support on self-compassion. This study highlights the importance of supporting perinatal women to adapt to COVID-19-related changes through cooperation with their families, which may increase self-compassion.


Assuntos
COVID-19 , Feminino , Humanos , Japão/epidemiologia , Pandemias , Gravidez , Autocompaixão , Apoio Social
14.
J Patient Rep Outcomes ; 6(1): 10, 2022 Jan 29.
Artigo em Inglês | MEDLINE | ID: mdl-35092532

RESUMO

BACKGROUND: PedsQL Infant Scales (PedsQL-I) are used to assess parent-reported health-related quality of life for children younger than 2 years. We determined the feasibility, reliability, and validity of the Japanese version of the PedsQL-I. METHODS: A total of 183 participants (parents) with infants aged 1-30 months were recruited from 8 day care centers and one pediatric clinic. Participants completed the PedsQL-I (infants aged 1-18 months), the PedsQL-I and the PedsQL-Toddler version (infants aged 19-30 months), and the Kessler-6 psychological distress scale (all participants). We determined feasibility, internal consistency, test-retest reliability, concurrent validity, convergent and discriminant validity, known-groups validity with regard to acute and chronic illness, and relative and transitional validity with PedsQL-Toddler for the use in infants aged 25-30 months. RESULTS: All subscales were internally consistent (Cronbach's alpha for 1-12 months: 0.88-0.98 and for 13-24 months: 0.85-0.97); test-retest reliability was acceptable (intra-class correlation coefficients > 0.40); and all scales were concurrently valid with the PedsQL-Toddler version (Pearson's product-moment correlation coefficient for the total score = 0.74). The scales' convergent and discriminant validity were acceptable (scaling success rate > 80%). Validation for known-groups showed that the Physical Health Summary score was sensitive to acute and chronic disease, the Psychosocial Health Summary score was sensitive to neither acute nor chronic disease, and the total score was sensitive to acute disease. Relative validity showed a ratio of 1.74 for the squared t values for the total score. CONCLUSIONS: The PedsQL-I is suitable for assessing health-related quality of life in infants aged 1-24 months in prospective studies.

15.
J Pain Symptom Manage ; 63(3): 374-386, 2022 03.
Artigo em Inglês | MEDLINE | ID: mdl-34756955

RESUMO

CONTEXT: In recent times, advance care planning for patients' end-of-life care preferences has attracted much attention worldwide. OBJECTIVES: To develop the Readiness for Advance Care Planning (RACP) Scale. METHODS: Participants included 624 Japanese citizens who were registered with a web-based survey company as of February 2019. Items regarding the process of advance care planning (ACP) were developed based on a literature review and expert panel discussions. The expert panel included nine experts and practitioners in the field of end-of-life care. Construct validity, concurrent validity, internal consistency, and test-retest reliability were evaluated. RESULTS: Initially, 37 items were collected. Examination of the floor effect, item-total, good-poor analysis, and exploratory factor analysis yielded a five-factor model with 28 items. The goodness of fit of the model was GFI = 0.80, CFI = 0.91, and RMSEA = 0.08. The concurrent validity was statistically significant (rs = 0.26-0.45, ps < 0.001). Cronbach's alpha for the overall scale was 0.95. The corresponding values for the subscales ranged from 0.90 to 0.97. The intraclass correlation coefficients indicating test-retest reliability was 0.66 (P < 0.001) for the total scale and ranged from 0.52-0.65 for the five subscales. CONCLUSIONS: The validity and reliability of the scale were generally acceptable. The RACP is an appropriate instrument to evaluate the level of readiness for ACP behaviors among people of various generations at every health stage. More studies are needed to examine the clinical utility of the RACP, both nationally and internationally.


Assuntos
Planejamento Antecipado de Cuidados , Análise Fatorial , Humanos , Psicometria , Reprodutibilidade dos Testes , Inquéritos e Questionários
16.
Chem Commun (Camb) ; 57(83): 10939-10942, 2021 Oct 19.
Artigo em Inglês | MEDLINE | ID: mdl-34596172

RESUMO

We report an exceptional example of Tb(III) luminescence switching using a reversible covalent bond. The antenna and quencher moieties attached to a ligand of a Tb(III) complex undergo acid/base-driven exchange based on the reversible formation of a hemiaminal ether structure to achieve on-off regulation of luminescence.

17.
Front Neurosci ; 15: 712261, 2021.
Artigo em Inglês | MEDLINE | ID: mdl-34616273

RESUMO

Perinatal exposure to Bisphenol A (BPA) at a very low dose may modulate the development of synapses of the hippocampus during growth to adulthood. Here, we demonstrate that perinatal exposure to 30 µg BPA/kg per mother's body weight/day significantly altered the dendritic spines of the grownup rat hippocampus. The density of the spine was analyzed by imaging of Lucifer Yellow-injected CA1 glutamatergic neurons in adult hippocampal slices. In offspring 3-month male hippocampus, the total spine density was significantly decreased by BPA exposure from 2.26 spines/µm (control, no BPA exposure) to 1.96 spines/µm (BPA exposure). BPA exposure considerably changed the normal 4-day estrous cycle of offspring 3-month females, resulting in a 4∼5 day estrous cycle with 2-day estrus stages in most of the subjects. In the offspring 3-month female hippocampus, the total spine density was significantly increased by BPA exposure at estrus stage from 2.04 spines/µm (control) to 2.25 spines/µm (BPA exposure). On the other hand, the total spine density at the proestrus stage was moderately decreased from 2.33 spines/µm (control) to 2.19 spines/µm (BPA exposure). Thus, after the perinatal exposure to BPA, the total spine density in males became lower than that in females. Concerning the BPA effect on the morphology of spines, the large-head spine was significantly changed with its significant decrease in males and moderate change in females.

18.
Inorg Chem ; 60(20): 15159-15168, 2021 Oct 18.
Artigo em Inglês | MEDLINE | ID: mdl-34587442

RESUMO

Bis-argentivorous molecules (La and Lb), which have phenyl and 4,4'-biphenyl groups as linkers, have been prepared. The structures of Ag+ complexes with the new ligands (La and Lb) were investigated in solution and the solid state. The CSI-MS and 1H NMR titration of La and Lb with Ag+ show 1:1 and 1:2 complexes depending on the [Ag+]:[L] ratios. In the solid-state structures, single crystals of La and Lb with 2 equiv of Ag+ were prepared. X-ray crystallography of the silver(I) complexes with La and Lb showed that an intramolecular racemic structure (Δ(δδδδ)Λ(λλλλ) form) and a racemic mixture of Δ(δδδδ)Δ(δδδδ) and Λ(λλλλ)Λ(λλλλ) forms were formed, respectively. The dynamic 1H NMR studies suggest the following: (i) the activation entropies (ΔS⧧) of the side arm rotations in the Ag+ complex with La were all negative, indicating restricted rotation of the side arms due to their shortness, and (ii) the ΔS⧧ values of the Ag+ complexes with Lb were negative only when the side arms of both cyclens rotated simultaneously, and the ΔS⧧ values for the 1:1 and 1:2 complexes were positive when one cyclen side arm was rotated. These values of ΔS⧧ indicate that the biphenyl side arms between the two cyclens are not long enough to rotate the ring freely.

19.
Inorg Chem ; 60(15): 11320-11327, 2021 Aug 02.
Artigo em Inglês | MEDLINE | ID: mdl-34253012

RESUMO

Argentivorous molecules with mono, di, tri, tetra, and penta-oxyethylene chains in aromatic side-arms were prepared (L1-L5). Titration experiments using proton nuclear magnetic resonance and cold electrospray ionization (cold-spray ionization, CSI) mass spectrometry showed that silver ions were trapped in the cyclen moiety and the arranged oxyethylene chains of the side-arms when two equivalents of silver ions were added. The silver complexes formed by adding one equivalent of silver ion to L2-L5 bind alkali metal ions using the oxyethylene chains; alkali metal ion-induced CSI mass spectral changes of L2-L5 were measured in the absence and presence of silver ions to compare the binding properties of the ligand for Li+, Na+, and K+ ions. As a result, the intensity ratios of [L + H + M]2+/[L + H]+ in L1-L3 were almost zero or very low. L4 and L5, which have tetra(oxyethylene) and penta(oxyethylene) chains, respectively, bind a larger size of alkali metal ions. On the other hand, in the presence of silver ions, the ratio for [L + Ag + M]2+/[L + H]+ (M = Li, Na, K) in L2-L5 was increased. The highest [L + Ag + M]2+/[L + H]+ ratios for K+ were observed in L4 and L5, while selectivity for Na+ was observed in the case of L2 and L3. These results indicate that the increased binding ability and selectivity by L2-L5 are due to the arrangement of oxyethylene chains by the conformational change of the aromatic side-arms. The Ag+-induced carbon-13 nuclear magnetic resonance spectral changes suggested that the second and third oxyethylene units, close to the benzene, are involved in the coordination of the second metal ion.

20.
Inorg Chem ; 60(12): 9141-9147, 2021 Jun 21.
Artigo em Inglês | MEDLINE | ID: mdl-34085518

RESUMO

The synthesis of argentivorous molecules (L1 and L2) having two chromophores (4-(anthracen-9-yl)benzyl or 4-(pyren-1-yl)benzyl groups) and two benzyl groups and the fluorescence properties of their silver complexes in a solution and the solid state are reported. A crystallographic approach for the Ag+ complexes with L1 and L2 revealed that the observed fluorescence changes stem from the excimer formation and extinction of fluorescent. Furthermore, binding stabilities of L1 and L2 toward Ag+ ions were estimated by the Ag+-induced UV-vis and PL spectral changes.

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