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Porous liquids (PLs) are attractive materials because of their capability to combine the intrinsic porosity of microporous solids and the processability of liquids. Most of the studies focus on the synthesis of PLs with not only high porosity but also low viscosity by considering their transportation in industrial plants. However, a gap exists between PLs and solid adsorbents for some practical cases, where the liquid characteristics and mechanical stability without leakage are simultaneously required. Here, we fill in this gap by demonstrating a new concept of pore-networked gels, in which the solvent phase is trapped by molecular networks with accessible porosity. To achieve this, we fabricate a linked metal-organic polyhedra (MOPs) gel, followed by exchanging the solvent phase with a bulky liquid such as ionic liquids (ILs); the dimethylformamide solvent trapped inside the as-synthesized gel is replaced by the target IL, 1-butyl-3-methylimidazolium tetrafluoroborate, which in turn cannot enter MOP pores due to their larger molecular size. The remaining volatile solvents in the MOP cavities can then be removed by thermal activation, endowing the obtained IL gel (Gel_IL) with accessible microporosity. The CO2 capacities of the gels are greatly enhanced compared to the neat IL. The exchange with the IL also exerts a positive influence on the final gel performances such as mechanical properties and low volatility. Besides ILs, various functional liquids are shown to be amenable to this strategy to fabricate pore-networked gels with accessible porosity, demonstrating their potential use in the field of gas adsorption or separation.
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It is empirically known that mood changes affect facial expressions and voices. In this study, the authors have focused on the voice to develop a method for estimating depression in individuals from their voices. A short input voice is ideal for applying the proposed method to a wide range of applications. Therefore, we evaluated this method using multiple input utterances while assuming a unit utterance input. The experimental results revealed that depressive states could be estimated with sufficient accuracy using the smallest number of utterances when positive utterances were included in three to four input utterances.
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Depressão , Voz , HumanosRESUMO
Recently, the relationship between emotional arousal and depression has been studied. Focusing on this relationship, we first developed an arousal level voice index (ALVI) to measure arousal levels using the Interactive Emotional Dyadic Motion Capture database. Then, we calculated ALVI from the voices of depressed patients from two hospitals (Ginza Taimei Clinic (H1) and National Defense Medical College hospital (H2)) and compared them with the severity of depression as measured by the Hamilton Rating Scale for Depression (HAM-D). Depending on the HAM-D score, the datasets were classified into a no depression (HAM-D < 8) and a depression group (HAM-D ≥ 8) for each hospital. A comparison of the mean ALVI between the groups was performed using the Wilcoxon rank-sum test and a significant difference at the level of 10% (p = 0.094) at H1 and 1% (p = 0.0038) at H2 was determined. The area under the curve (AUC) of the receiver operating characteristic was 0.66 when categorizing between the two groups for H1, and the AUC for H2 was 0.70. The relationship between arousal level and depression severity was indirectly suggested via the ALVI.
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Nível de Alerta , Transtorno Depressivo Maior , Reconhecimento de Voz , Adulto , Idoso , Depressão/diagnóstico , Transtorno Depressivo Maior/diagnóstico , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Escalas de Graduação Psiquiátrica , Índice de Gravidade de Doença , Adulto JovemRESUMO
The effect of organic ligands on the separation performance of Zr based metal-organic framework (Zr-MOF) membranes was investigated. A series of Zr-MOF membranes with different ligand chemistry and functionality were synthesized by an inâ situ solvothermal method and a coordination modulation technique. The thin supported MOF layers (ca. 1â µm) showed the crystallographic orientation and pore structure of original MOF structures. The MOF membranes show excellent selectivity towards hydrogen owing to the molecular sieving effect when the bulkier linkers were used. The molecular simulation confirmed that the constricted pore apertures of the Zr-MOFs which were formed by the additional benzene rings lead to the decrease in the diffusivity of larger penetrants while hydrogen was not remarkably affected. The gas mixture separation factors of the MOF membranes reached to H2 /CO2 =26, H2 /N2 =13, H2 /CH4 =11.
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We demonstrate a new de novo synthetic methodology to achieve high-temperature-stable compelled composite superhydrophobic porous coordination polymers (PCPs). These new PCPs were achieved based on coordination capabilities of first-row transition metal ions such as Co2+, Ni2+, and Zn2+. The obtained composite PCPs containing a [Zn2M2O]6+ (M = Co or Ni) bimetallic cluster core with open metal sites (OMSs) exhibited distinct isosteric heats of adsorption and surface areas due to the difference in their open metal Lewis acidic sites of solvent-free state. Additionally, these composite PCPs exhibit remarkable superhydrophobic properties with contact angles of 159.3° and 160.8° respectively for Zn-Co and Zn-Ni analogues. This superhydrophobic surface survives even at high temperature for longer time periods. As projected, these new composite PCPs exhibit better surface area and heats of adsorption compared to the PESD-1 (Zn) analogue due to a larger number of OMSs. Moreover, they display selective adsorption toward aromatic solvents such as benzene and toluene over aliphatic solvents such as cyclohexane due to corrugated and terminated aromatic hydrocarbon moieties toward the interactive surface. They also exhibit oil spill cleanup from the water surface in the powder form as well as pellet form up to 385 wt %. This study certainly offers a roadmap for designing and engineering new composite superhydrophobic porous materials for better water and thermal stability along with OMSs. This type of PCP exhibits a wide range of applications especially in catalysis, separation technology, and securing environmental problems such as oil spill cleanup in seawater.
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Design to store gas molecules, such as CO2 , H2 , and CH4 , under low pressure is one of the most important challenges in chemistry and materials science. Herein, we describe the storage of CO2 in the cavities of a porous coordination polymer (PCP) using molecular rotor dynamics. Owing to the narrow pore windows of PCP, CO2 was not adsorbed at 195â K. As the temperature increased, the rotors exhibited rotational modes; such rotations dynamically expanded the size of the windows, leading to CO2 adsorption. The rotational frequencies of the rotors (k≈10-6 â s) and correlation times of adsorbed CO2 (τ≈10-8 â s) were elucidated via solid-state NMR studies, which suggest that the slow rotation of the rotors sterically restricts CO2 diffusion in the pores. This restriction results in an unusually slow CO2 mobility close to solid state (τ≥10-8 â s). Once adsorbed at room temperature, CO2 is robustly stored in the PCP under vacuum at 195-233â K because of the steric hindrance of the rotors. We also demonstrate that this mechanism can be applied to the storage of CH4 .
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The prevalence of the condensed phase, interpenetration, and fragility of mesoporous coordination polymers (meso-PCPs) featuring dense open metal sites (OMSs) place strict limitations on their preparation, as revealed by experimental and theoretical reticular chemistry investigations. Herein, we propose a rational design of stabilized high-porosity meso-PCPs, employing a low-symmetry ligand in combination with the shortest linker, formic acid. The resulting dimeric clusters (PCP-31 and PCP-32) exhibit high surface areas, ultrahigh porosities, and high OMS densities (3.76 and 3.29 mmol g-1, respectively), enabling highly selective and effective separation of C2H2 from C2H2/CO2 mixtures at 298 K, as verified by binding energy (BE) and electrostatic potentials (ESP) calculations.
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Direct use of low pressures of CO2 as a C1 source without concentration from gas mixtures is of great interest from an energy-saving viewpoint. Porous heterogeneous catalysts containing both adsorption and catalytically active sites are promising candidates for such applications. Here, we report a porous coordination polymer (PCP)-based catalyst, PCP-Ru(II) composite, bearing a Ru(II) -CO complex active for CO2 reduction. The PCP-Ru(II) composite showed improved CO2 adsorption behavior at ambient temperature. In the photochemical reduction of CO2 the PCP-Ru(II) composite produced CO, HCOOH, and H2 . Catalytic activity was comparable with the corresponding homogeneous Ru(II) catalyst and ranks among the highest of known PCP-based catalysts. Furthermore, catalytic activity was maintained even under a 5 % CO2 /Ar gas mixture, revealing a synergistic effect between the adsorption and catalytically active sites within the PCP-Ru(II) composite.
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The introduction of reduced-intensity conditioning (RIC) regimens has made possible allogeneic hematopoietic cell transplantation (allo-HCT) in older patients with acute myeloid leukemia (AML). However, the optimal timing of allo-HCT in these patients and its relative risks and benefits when compared with chemotherapies have not been determined. This retrospective study by the Fukuoka Blood and Marrow Transplant Group compared RIC allo-HSCT with non-transplant therapies, the choice based on donor availability, in AML patients in their first complete remission (CR1). The prognostic value of various patient characteristics and disease-specific variables were investigated in 299 patients aged ≥60 years with AML in CR1. Among the 107 patients aged 60-65 years, 54 of whom received allo-HCT and 53 of whom continued chemotherapies; allo-HCT, adverse-risk group, and hematopoietic cell transplantation-comorbidity index were significant predictors of survival outcomes. Among 192 patients aged ≥66 years deemed ineligible for allo-HCT, relapse and Karnofsky performance status after induction therapy were significant predictors of survival outcomes. Findings from this study may facilitate a new standard of care for older AML patients in CR1 who are considered candidates for allo-HCT.
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Análise Citogenética/métodos , Definição da Elegibilidade/métodos , Transplante de Células-Tronco Hematopoéticas/métodos , Leucemia Mieloide Aguda/genética , Leucemia Mieloide Aguda/terapia , Idoso , Feminino , Transplante de Células-Tronco Hematopoéticas/efeitos adversos , Humanos , Leucemia Mieloide Aguda/diagnóstico , Masculino , Pessoa de Meia-Idade , Prognóstico , Indução de Remissão/métodos , Estudos Retrospectivos , Fatores de Risco , Taxa de Sobrevida/tendências , Transplante Homólogo/efeitos adversos , Transplante Homólogo/métodosRESUMO
We propose and validate a simple strategy of vertex connection that can be used for framework design and pore size/type modulation to prepare a mother structure and another 10 highly porous isoreticular frameworks with unprecedented topology. Importantly, the potential accessible pore volumes (57-71%), pore sizes (6.8-11. 2 Å; 17.0-29.0 Å; 12.5-22.8 Å; 11.9-24.5 Å), and the pore shapes of this series of highly porous frameworks were simultaneously and systematically tuned. Interestingly, the pore size of IIa [Zn4O(L(2))2(BDC)0.5]{(CH3)2NH2} decreased a little less than that of IIc [Zn4O(L(2))2(2,6-NDC)0.5]{(CH3)2NH2}; however, its selectivity of CO2 toward CH4 increased by almost two times.
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Compostos Organometálicos/síntese química , Polímeros/síntese química , Zinco/química , Dióxido de Carbono/química , Metano/química , Modelos Moleculares , Compostos Organometálicos/química , Tamanho da Partícula , Polímeros/química , Porosidade , Propriedades de SuperfícieRESUMO
To establish a strategy for designing porous coordination polymers (PCPs) for ammonia capture, the first systematic study on the stability of PCPs against ammonia was conducted. Various types of PCPs were investigated by comparing their powder XRD patterns before and after treatment with ammonia. Among the PCPs tested, ZIF-8, MIL-53(Al), Al-BTB, MOF-76(M) (M=Y or Yb), MIL-101(Cr), and MOF-74(Mg) were stable up to 350 °C under an ammonia atmosphere at ambient pressure. The origin of the stability of PCPs is discussed from the viewpoint of their components, metal cations, and organic linkers. Furthermore, adsorption isotherm measurements show that the adsorptive behavior of PCPs is independent of their stability.
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Amônia/química , Polímeros/química , 2,2'-Dipiridil/química , Adsorção , Complexos de Coordenação/síntese química , Complexos de Coordenação/química , Cobre/química , Compostos Organometálicos/química , Oxigênio/química , Polímeros/síntese química , PorosidadeRESUMO
We demonstrate a new approach to superhydrophobic porous coordination polymers by incorporating an anisotropic crystal morphology featuring a predominant surface that is highly corrugated and terminated by aromatic hydrocarbon moieties. The resulting low-energy surface provides particularly promising hydrophobic properties without the need for postsynthetic modifications or surface processing that would block the porosity of the framework. Consequently, hydrophobic organic molecules and water vapor are able to penetrate the surface and be densely accommodated within the pores, whereas bulk water is repelled as a result of the exterior surface corrugation derived from the aromatic surface groups. This study provides a new strategy for the design and development of superhydrophobic porous materials.
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A family of new porous coordination polymers (PCPs) were prepared by the reaction of an acylamide modified ligand (H3L) and RE(NO)3·xH2O (RE = Y, La, Ce, Nd, Eu, Tb, Dy, Ho, and Tm). PXRD and single-crystal X-ray analyses of them revealed that, besides the La PCP, all other rare earth members gave isomorphous structures. The two types of structural toplogies obtained, although similar, differ in their alignment of acylamide functional groups and structural flexibility. Adsorption experiments and in situ DRIFT spectra showed that rigid frameworks have the typical microporous behavior and poor selective capture of CO2 over C2H4 and C2H6; however, the unique La-PCP with structural flexibility and close-packed acylamide groups has a high selective capture of CO2 with respect to C2H6 or C2H4 at 273 K, especially at the ambient pressure area (0.1-1 bar).
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High selectivity and low-energy regeneration for adsorption of CO(2) gas were achieved concurrently in a two-dimensional Cu(II) porous coordination polymer, [Cu(PF(6))(2)(4,4'-bpy)(2)](n) (4,4'-bpy = 4,4'-bipyridine), containing inorganic fluorinated PF(6)(-) anions that can act as moderate interaction sites for CO(2) molecules.
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Dióxido de Carbono/química , Cobre/química , Hidrocarbonetos Fluorados/química , Compostos Organometálicos/química , Polímeros/química , Adsorção , Ânions/química , Cristalografia por Raios X , Modelos Moleculares , Compostos Organometálicos/síntese química , Porosidade , Propriedades de SuperfícieRESUMO
A 68-year-old man was admitted to our hospital because of left back pain and systemic lymphadenopathy with hypercalcemia. Serum anti-HTLV-1 antibody was positive. Left cervical lymph node (LN) biopsy revealed proliferation of medium-sized to large CD4-positive atypical cells with modest infiltration of CD20 and Epstein-Barr virus (EBV)-encoded RNA dual-positive atypical large cells. Monoclonal integration of HTLV-1 proviral DNA, plus clonal rearrangement of the T-cell receptor chain gene and the immunoglobulin heavy chain gene, were detected in the same LN specimen. Composite lymphoma consisting of adult T-cell leukemia/lymphoma (ATL) and EBV positive diffuse large B-cell lymphoma (DLBCL) was diagnosed. He was successfully treated with aggressive chemotherapy including rituximab and attained remission. However, eight months later, he developed right shoulder pain due to multiple bone invasions with bilateral cervical lymphadenopathy. Biopsies of a bone lesion and cervical LN revealed recurrence of ATL alone. The patient died despite salvage chemoradiotherapy. These findings suggest that ATL-related immunodeficiency might induce EBV-associated DLBCL.
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Protocolos de Quimioterapia Combinada Antineoplásica/uso terapêutico , Linfoma Composto/patologia , Leucemia-Linfoma de Células T do Adulto/patologia , Linfoma Difuso de Grandes Células B/patologia , Idoso , Biópsia , Linfoma Composto/diagnóstico por imagem , Linfoma Composto/tratamento farmacológico , Evolução Fatal , Herpesvirus Humano 4/isolamento & purificação , Humanos , Leucemia-Linfoma de Células T do Adulto/diagnóstico por imagem , Leucemia-Linfoma de Células T do Adulto/tratamento farmacológico , Linfoma Difuso de Grandes Células B/diagnóstico por imagem , Linfoma Difuso de Grandes Células B/tratamento farmacológico , Masculino , Radiografia , RecidivaRESUMO
In this study, the technique associated with the capturing involuntary changes in voice elements caused by diseases is applied to diagnose them and a voice index is proposed to discriminate mild cognitive impairments. The participants in this study included 399 elderly people aged 65 years or older living in Matsumoto City, Nagano Prefecture, Japan. The participants were categorized into healthy and mild cognitive impairment groups based on clinical evaluation. It was hypothesized that as dementia progressed, task performance would become more challenging, and the effects on vocal cords and prosody would change significantly. In the study, voice samples of the participants were recorded while they were engaged in mental calculational tasks and during the reading of the results of the calculations written on paper. The change in prosody during the calculation from that during reading was expressed based on the difference in the acoustics. Principal component analysis was used to aggregate groups of voice features with similar characteristics of feature differences into several principal components. These principal components were combined with logistic regression analysis to propose a voice index to discriminate different mild cognitive impairment types. Discrimination accuracies of 90% and 65% were obtained for discriminations using the proposed index on the training and verification data (obtained from a population different from the training data), respectively. Therefore, it is suggested that the proposed index may be utilized as a means for discriminating mild cognitive impairments.
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Voice-based depression detection methods have been studied worldwide as an objective and easy method to detect depression. Conventional studies estimate the presence or severity of depression. However, an estimation of symptoms is a necessary technique not only to treat depression, but also to relieve patients' distress. Hence, we studied a method for clustering symptoms from HAM-D scores of depressed patients and by estimating patients in different symptom groups based on acoustic features of their speech. We could separate different symptom groups with an accuracy of 79%. The results suggest that voice from speech can estimate the symptoms associated with depression.
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Transtorno Depressivo Maior , Voz , Humanos , Depressão , Transtorno Depressivo Maior/diagnóstico , Fala , AcústicaRESUMO
Spindle-shaped diffuse large B-cell lymphoma (Sp-DLBCL) has been recognized as a rare morphologic variant of DLBCL. However, the biological processes that contribute to the specific features of Sp-DLBCL remain poorly understood. In this study, a combined immunophenotypic and genetic analysis was performed in 10 Sp-DLBCL. First, we investigated several unique markers for anaplasia (CD30, ALK, CD68, and EBER-ISH), mesenchyma (SMA, desmin, and vimentin), and B-cell differentiation (CD10, BCL6, and MUM1). We also performed conventional cytogenetic and fluorescence in situ hybridization studies to look for common chromosomal break points (BCL2, BCL6, and MYC). We found that most Sp-DLBCLs were germinal center B cell-like and that none had any other specific phenotypes or any karyotypic abnormalities. Instead, T cells, CD68-positive macrophages and SMA-positive myofibroblasts were significantly increased in Sp-DLBCL when compared with conventional GCB origin DLBCL cases (n = 10) (P = 0.012, P < 0.001, and P < 0.0001, respectively). To further characterize Sp-DLBCL, we next compared the expression of fibroblast growth factor 2 (FGF2) and transforming growth factor-ß1 (TGFß1) between the two types of DLBCL. Finally, we confirmed that the number of FGF2- and TGFß1-positive stromal cells was markedly increased in Sp-DLBCL and that the difference between these and conventional GCB origin DLBCLs was significant (P < 0.0001 and P = 0.0017, respectively). Thus, T-cell/myofibrohistio-rich stromal alterations in Sp-DLBCL, especially those mediated by TGFß1 and FGF2, may play a role in the transition of lymphoma cells into those with spindle-shaped features.
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Linfoma Difuso de Grandes Células B/patologia , Miofibroblastos/imunologia , Células Estromais/patologia , Linfócitos T/imunologia , Adulto , Idoso , Idoso de 80 Anos ou mais , Aberrações Cromossômicas , Sítios Frágeis do Cromossomo , Feminino , Humanos , Imunofenotipagem , Hibridização in Situ Fluorescente , Linfoma Difuso de Grandes Células B/genética , Linfoma Difuso de Grandes Células B/imunologia , Masculino , Pessoa de Meia-IdadeRESUMO
The AML1/CBFbeta transcription factor complex, a frequent target of chromosomal translocations in leukemia, is essential for the generation of definitive hematopoietic stem cells. Paradoxically, expression of the acute myeloid leukemia-associated AML1-ETO fusion protein in mice results not in leukemia, but in embryonic lethality due to an absence of normal hematopoiesis. To bypass the embryonic lethality, we generated a mouse strain with a conditional AML1-ETO knockin allele that contains a loxP bracketed transcriptional stop cassette 5' to the AML1-ETO fusion site. Activation of this allele in vivo by Cre-mediated recombination resulted in an enhanced replating efficiency of myeloid progenitors, but it did not block their differentiation, nor was it sufficient to induce leukemia. However, induction of cooperating mutations resulted in the development of an acute myeloid disease that mimicked many of the features of human AML1-ETO-expressing leukemia.
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Cromossomos Humanos Par 21/genética , Cromossomos Humanos Par 8/genética , Regulação Neoplásica da Expressão Gênica , Leucemia Mieloide/etiologia , Leucemia Mieloide/genética , Proteínas de Fusão Oncogênica/genética , Proteínas Proto-Oncogênicas , Fatores de Transcrição/genética , Translocação Genética/genética , Doença Aguda , Animais , Proteínas de Ciclo Celular/metabolismo , Divisão Celular/genética , Subunidade alfa 2 de Fator de Ligação ao Core , Citocinas/metabolismo , Primers do DNA/química , Proteínas de Ligação a DNA/fisiologia , Modelos Animais de Doenças , Humanos , Integrases/metabolismo , Leucemia Mieloide/patologia , Camundongos , Camundongos Endogâmicos C57BL , Camundongos Knockout , Camundongos Transgênicos , Mutação/genética , Proteínas de Fusão Oncogênica/metabolismo , Proteína 1 Parceira de Translocação de RUNX1 , Reação em Cadeia da Polimerase Via Transcriptase Reversa , Transdução de Sinais/fisiologia , Fatores de Transcrição/metabolismo , Fatores de Transcrição/fisiologia , Proteínas Virais/metabolismoRESUMO
BACKGROUND: An in vitro elicitation test employing human high-affinity IgE receptor-expressing rat mast cell lines appears to be a useful method for measuring mast cell activation using a patient's IgE and an allergen; however, such cell lines are sensitive to human complements in the serum. We have recently developed a new luciferase-reporting mast cell line (RS-ATL8) to detect IgE crosslinking-induced luciferase expression (EXiLE) with relatively low quantities of serum IgE. METHODS: A total of 30 patients suspected of having egg white (EW) allergy were subjected to an oral food challenge (OFC) test; then, the performances of EW-specific serum IgE (CAP-FEIA), EW-induced degranulation, and EXiLE responses in RS-ATL8 cells were compared using receiver-operating characteristic (ROC) curve analysis. The patients' sera were diluted to 1 : 100, which causes no cytotoxicity when sensitizing the RS-ATL8 cells for the degranulation and EXiLE tests. RESULTS: The area under the ROC curves was highest in the EXiLE test (0.977), followed by CAP-FEIA (0.926) and degranulation (0.810). At an optimal cutoff range (1.648-1.876) calculated from the ROC curve of the EXiLE test, sensitivity and specificity were 0.944 and 0.917, respectively. A 95% positive predictive value was given at a cutoff level of 2.054 (fold increase in luciferase expression) by logistic regression analysis. CONCLUSIONS: In contrast to in vivo tests, the EXiLE test appears to be a useful tool in diagnosing patients suspected of having IgE-dependent EW allergy without the risk of severe systemic reactions.