Comparative study of TDDFT and TDDFT-based STEOM-DLPNO-CCSD calculations for predicting the excited-state properties of MR-TADF.

The time dependent density functional theory (TDDFT) and TDDFT/similarity transformed EOM domain-based local pair natural orbital CCSD (STEOM-DLPNO-CCSD) calculations were explored to estimate their validity in predicting the excited-state properties of multi-resonant thermally activated delayed fluorescence (MR-TADF) materials. Obviously, it was demonstrated that TDDFT calculation is inadequate to provide the quantitative prediction of the lowest singlet excited-state (S1), the lowest triplet excited-state (T1), and ΔEST. On the other hand, TDDFT/STEOM-DNLPNO-CCSD calculation reveals the superior prediction of S1, T1, and ΔEST that are in quantitative agreement with experiments. More importantly, it was found that TD-LC-⎤*HPBE/STEOM-DLPNO-CCSD calculation provides the most accurate prediction of S1, T1, and ΔEST. Accordingly, we suggest that TD-LC-⎤*HPBE/STEOM-DLPNO-CCSD calculation should be utilized to compute the excited-states properties of MR-TADF materials accurately.

Multifunctional Deep-Blue Thermally Activated Delayed Fluorescence Based on an Oxygen-Bridged Boron Acceptor for Highly Efficient Organic Light-Emitting Diodes.

Until now, thermally activated delayed fluorescence (TADF) materials based on bridged boron-based acceptors have been primarily developed as dopants. However, in this study, we synthesized and characterized multifunctional deep-blue TADF materials─t-OBO-DMAC and t-OBO-DPAC─using bridged boron-based acceptors in combination with dimethylacridine or diphenylacridine as donors. These materials serve as both dopants and hosts. Theoretical calculations and experimentally measured photophysical properties of t-OBO-DMAC reveal a smaller singlet-triplet energy difference, higher photoluminescence quantum yield, and more efficient reverse intersystem crossing compared to t-OBO-DPAC. When evaluated as TADF emitters, t-OBO-DMAC and t-OBO-DPAC exhibited maximum external quantum efficiency (EQE) of 14.4 and 7.3% with deep-blue color coordinates of (0.14, 0.11) and (0.15, 0.07), respectively. Both materials were further assessed as hosts in various configurations, including host-only, TADF, phosphorescent, and phosphor-sensitized fluorescence (PSF)-emitting systems. Notably, t-OBO-DMAC demonstrated a high maximum EQE of 13.9% with deep-blue color coordinates of (0.15, 0.07) in a nondoped host-only device. Remarkably, both materials achieved EQEs exceeding 20% in the PSF devices. Our study marks a critical advancement in the field that breaks the conventional boundaries of the dopant and host and demonstrates unprecedented multifunctionalities for advanced organic light-emitting diodes.

Anthracene derivatives with strong spin-orbit coupling and efficient high-lying reverse intersystem crossing beyond the El-Sayed rule.

The attention to materials with hot exciton channel and triplet-triplet fusion (TTF) mediated high-lying reverse intersystem crossing (hRISC) has been raised for their ability to convert non-emissive 'dark' triplets into radiative singlet excitons. This spin conversion process results in high exciton utilization efficiency (EUE) that exceeds the theoretical limits. Notably, it is known that such spin conversion processes from the high-lying excited triplet to the singlet state are facilitated by the orthogonal orbital transition effect governed by the El-Sayed's rule. In this study, an anthracene derivative with indenoquinoline substituent 7,7-dimethyl-9-(10-(4-(naphthalen-1-yl)phenyl)anthracen-9-yl)-7H-indeno[1,2-f]quinoline (2MIQ-NPA) was synthesized and analyzed to investigate whether the hRISC process occurs in these molecules, even when the El-Sayed's rule is not followed. The hRISC channels of the emitter were fully unraveled through DFT calculations and experiments, which were quantitatively subdivided using transient electroluminescence measurements. The results showed that 2MIQ-NPA, which does not follow the El-Sayed's rule and has a relatively strong spin-orbit coupling matrix element of 0.116 cm-1 between the high-lying triplet state of T4 and the lowest singlet state of S1, effectively converted triplet excitons into singlet excitons with an EUE of 64.3%, contributed by a direct hot exciton channel of 19.2% and a TTF-mediated hot exciton channel of 15.1%. Despite the low outcoupling efficiency, the non-doped device with 2MIQ-NPA achieved an excellent device performance with an external quantum efficiency of 7.0%.

Short-term exposure to ambient air pollution and injuries due to external causes according to intentions and mechanisms.

Although injuries are a leading cause of death and affect the life expectancy of individuals who live with disabilities globally, the potential role of air pollution exposure on injuries due to external causes has received little scientific attention, especially compared with that given to the association of air pollution and non-external causes of morbidity and mortality. We investigated the association between emergency department visits for externally caused injuries and short-term exposure to major ambient air pollutants, with focus on the intentions and mechanisms of injuries. We identified 2,049,855 injured patients in Seoul, South Korea between 2008 and 2016 using the National Emergency Database. Daily short-term exposure to air pollution including particles <10 µm (PM10) and <2.5 µm (PM2.5), nitrogen dioxide (NO2), sulfur dioxide (SO2), carbon monoxide (CO), and ozone (O3) was estimated based on hourly concentrations. We employed a time-stratified case-crossover study design using a conditional Poisson regression model adjusted for meteorological variables, influenza epidemics, and holidays. Immediate exposure (lag 0) to most pollutants significantly increased the risk of total injuries (PM2.5, 0.42 %; NO2, 0.68 %; SO2, 1.05 %; CO, 0.57 %; O3, 1.86 % per interquartile range increment), and the associations differed according to the intention and mechanism of injury. Unintentional and assault injuries were significantly associated with air pollution exposure, whereas self-harm injuries showed no association. In mechanism-specific analyses, injuries caused by falls, blunt objects, penetration, traffic accidents, machinery, and slips were associated with specific air pollutants, even in the co-pollutant models. The associations were stronger in injured patients aged <15 years, and in males than in their counterparts. Our results suggest that short-term air pollution exposure might play a role in the risk of externally caused injuries and the association may differ depending on the intention and mechanism of injury, which provide important evidence for injury prevention and air quality strategies.

The Effect of Biomimetic Remineralization of Calcium Phosphate Ion Clusters-Treated Enamel Surfaces on Bracket Shear Bond Strength.

Purpose: To evaluate the remineralization effect of calcium phosphate ion clusters (CPICs) on demineralized enamel surfaces and their effects on bracket shear bond strength. Patients and Methods: Extracted premolars were prepared in resin blocks. The samples in the form of resin blocks were divided into five experimental groups: control group, demineralized group, and groups of CPIC solution treatment for 30, 60, and 90s. The specimens were examined using scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDX), microhardness testing, micro-computed tomography (micro-CT) assessment, shear bond strength (SBS) test, and adhesive remnant index (ARI) score. Results: The SEM images revealed epitaxial growth of enamel and a decrease in the thickness of the demineralized enamel layer when treated with CPIC solution. The EDX analysis revealed an increase in the Ca/P ratio in the CPIC-treated groups. The microhardness value significantly increased when treated with CPICs; however, it showed a lower value than that of the sound enamel groups. As a result of the micro-CT test, radiolucency decreased gradually as the CPIC treatment time increased. The SBS test and ARI score results showed an improvement in bonding stability after treatment with CPICs. Conclusion: We demonstrated an enamel biomodification approach using CPIC solution treatment, which is a promising strategy for enamel remineralization. Specifically, remineralization of demineralized enamel improves the orthodontic bracket SBS.

New design strategy for chemically-stable blue phosphorescent materials: improving the energy gap between the T1 and 3MC states.

A series of Ir- and Pt-based blue phosphorescent materials were theoretically investigated by means of density functional theory (DFT) calculations to improve their chemical stability in the excited state. High energy splitting between the lowest triplet state (T1 state), generally a metal-to-ligand charge transfer state (3MLCT), and the triplet metal-centred state (3MC) can prohibit ligand dissociation and suppress the decomposition reaction from the 3MC state to the dissociated S0. Here, we suggest a new design strategy to improve the chemical stability of blue phosphorescent materials in the excited state. Introducing inter- and intra-ligand interactions in Ir and Pt complexes can dramatically increase the ΔE(3MC-T1) because attractive or repulsive couplings arising from intra- or inter-ligand interactions can effectively prevent the out-of-plane bending vibrational mode in Ir complexes and the ring deformation vibrational mode in Pt complexes. A ΔE(3MC-T1) values of 18.62 kcal mol-1 for an Ir complex and 22.86 kcal mol-1 for a Pt complex from the T1 energy were obtained while the T1 energy was maintained in the blue region. To the best of our knowledge, these are the highest ΔE(3MC-T1) values reported to date. We believe that the present research provides profound insights into the excited state chemical stability of deep blue phosphorescent materials that could be implemented to improve device lifetimes.

A Silane-Based Bipolar Host with High Triplet Energy for High Efficiency Deep-Blue Phosphorescent OLEDs with Improved Device Lifetime.

A high triplet energy host is developed using a silane moiety, 9-(4-(triphenylsilyl)dibenzo[b,d]furan-2-yl)-9H-carbazole (SiDBFCz), is designed through extensive density functional theory (DFT) calculations to obtain appropriate hole and electron injection barriers. The chemical hardness and the charge transport characteristics are comprehensively investigated to realize a bipolar host with high triplet energy over 2.9 eV for deep blue phosphorescent organic light-emitting diodes (PHOLEDs). The synthesized SiDBFCz clearly exhibits the bipolar characteristics especially with emitter molecules doped. An external quantum efficiency over 19 % without any microcavity optimization is achieved thanks to the good charge balance in the SiDBFCz PHOLED. The device lifetime of the SiDBFCz PHOLED is improved more than 1000 %, compared to the unipolar control devices at an initial luminance of 500 cd m-2 . The dramatic enhancement of the operational stability of the deep blue PHOLED is also thoroughly investigated in terms of electrochemical stability of host molecules in charged or excited states. The results clearly indicate that the device lifetime is strongly correlated with the bond dissociation energy and the activation energy for the bond dissociation reaction in triplet excited state.

Design of efficient non-doped blue emitters: toward the improvement of charge transport.

Charge transport and electronic transition properties of a series of newly designed anthracene-based non-doped blue emitters were investigated by density functional theory calculations. For a highly efficient non-doped device, Cz3PhAn-based emitters were designed to suppress the hole and electron reorganization energies required for structural relaxation with respect to the changes of charged states. As a result, the hole hopping rates of triphenylamine (TPA) and phenylbenzimidazole (PBI) substituted Cz3PhAn derivatives (1, 4, and 5-7) were tremendously enhanced as compared to that of Cz3PhAn due to the suppression of the reorganization energy of holes, λ h. Moreover, 1 and 4 emitters showed almost identical hopping rates of holes and electrons, which can possibly lead to a perfect charge balance and high efficiency. The photo-physical properties showed that the emission energy of all 1-10 emitters is in 439-473 nm range. It is expected that our rational design strategy can help develop non-doped blue fluorescent emitters for high efficiency.

Inhibition of acute lethal pulmonary inflammation by the IDO-AhR pathway.

The lung is a prototypic organ that was evolved to reduce immunopathology during the immune response to potentially hazardous endogenous and exogenous antigens. In this study, we show that donor CD4+ T cells transiently induced expression of indoleamine 2,3-dioxygenase (IDO) in lung parenchyma in an IFN-γ-dependent manner early after allogeneic hematopoietic stem cell transplantation (HSCT). Abrogation of host IDO expression by deletion of the IDO gene or the IFN-γ gene in donor T cells or by FK506 treatment resulted in acute lethal pulmonary inflammation known as idiopathic pneumonia syndrome (IPS). Interestingly, IL-6 strongly induced IDO expression in an IFN-γ-independent manner when deacetylation of STAT3 was inhibited. Accordingly, a histone deacetylase inhibitor (HDACi) could reduce IPS in the state where IFN-γ expression was suppressed by FK506. Finally, l-kynurenine produced by lung epithelial cells and alveolar macrophages during IPS progression suppresses the inflammatory activities of lung epithelial cells and CD4+ T cells through the aryl hydrocarbon receptor pathway. Taken together, our results reveal that IDO is a critical regulator of acute pulmonary inflammation and that regulation of IDO expression by HDACi may be a therapeutic approach for IPS after HSCT.

Therapeutic activity of the histone deacetylase inhibitor SB939 on renal fibrosis.

Fibrosis is the final pathological outcome of many chronic kidney diseases and is quite common. Thus, development of effective anti-fibrotic agents is urgently needed. Although histone deacetylases (HDACs) have been reported to be involved in renal fibrosis, current HDAC inhibitors are unsatisfactory anti-fibrosis drugs. Therefore, more potentially relevant anti-renal fibrosis HDAC inhibitors are needed. We initially found that non-cytotoxic concentrations of SB939 (pracinostat) had strong anti-fibrotic activity, drastically decreasing TGF-ß1-induced alpha smooth muscle actin (α-SMA) expression in the NRK renal fibroblast cell line. Similar anti-fibrotic activity of SB939 on epithelial-to-mesenchymal transition (EMT) was confirmed using the HK-2 human renal proximal tubular epithelial cell line. SB939 inhibited Smad-independent TGF-ß signaling involving the MAPK and PI3K/AKT pathways. To evaluate in vivo anti-fibrotic activity, we administered SB939 in a unilateral ureteric obstruction (UUO) model. SB939 treatment markedly inhibited the accumulation of α-SMA and tissue injury. Inflammatory and pro-fibrotic cytokines in the obstructed kidney were also significantly decreased by SB939 treatment. Our results suggest that SB939 might be a promising therapeutic drug for preventing renal fibrosis.

Marital Strain Exacerbates Health Risks of Filial Caregiving: Evidence from the 2005 National Survey of Midlife in the U.S.

This study examined linkages between providing care for a parent (in contrast to not providing any care to other kin or nonkin) and four dimensions of physical health (self-rated health, functional limitations, physical symptoms, chronic conditions), as well as moderation of these linkages by gender and a negative dimension of marital quality--marital strain. Regression models were estimated using telephone and self-administered questionnaire data from 1080 married men and women who participated in the National Survey of Midlife in the U.S. (MIDUS) 2005. Although providing filial care was not found to be a global health risk for all married caregivers, marital strain was a critical factor in determining risk. Contrary to hypothesis, robust gender differences were not in evidence. But among both women and men, caregiving for a parent in the presence of high levels of marital strain was associated with significantly poorer health across all four evaluated outcomes.

Effect of upregulated TLR2 expression from G-CSF-mobilized donor grafts on acute graft-versus-host disease.

Our previous study demonstrated that G-CSF treatment increased the expression of TLR2 in donor grafts; this contributed to rapid engraftment after allogeneic hematopoietic stem cell transplantation (HSCT) in mice. In the current study, we investigated the effects of upregulated TLR2 expression in G-CSF-mobilized donor grafts on acute graft-versus-host disease (GVHD). We found that TLR2 was highly expressed on myeloid cell populations but not T and B cells from the spleens of G-CSF-treated donor mice. After transplantation, the mortality and disease severity in recipients were not significantly different between G-CSF-treated TLR2-/- and wt donor grafts. Although endogenous TLR2 ligand was detected in the serum of both recipients, T cells from TLR2-/- and wt donors have the same ability regarding alloreactivity. Moreover, the blockade of TLR2 signaling in recipients by administering anti-TLR2 blocking antibody after BMT did not lead to a significant difference in acute GVHD compared with control IgG treatment. However, the hematopoietic ability of G-CSF-mobilized lin−c-kit+ HSCs from TLR2-/- donor grafts was lower than that from wt donor grafts. Our results demonstrate that upregulated TLR2 expression in G-CSF-mobilized donor grafts has no effect on acute GVHD, suggesting that TLR2 is a valuable target for increasing HSCT efficiency in order to enhance engraftment without exacerbating acute GVHD.

Filial Caregiving is Associated with Greater Neuroendocrine Dysfunction: Evidence from the 2005 National Survey of Midlife in the U.S.

OBJECTIVES: This study examined associations between providing caregiving for a biological or adoptive parent and clinically-assessed biological risk factors (allostatic load [AL] and its three subscales - inflammatory dysfunction, metabolic dysfunction, neuroendocrine dysfunction), as well as moderation of these associations by gender. METHOD: Regression models were estimated using telephone and self-report data from 962 men and women who participated in the National Survey of Midlife in the U.S. (MIDUS) 2005. RESULTS: Filial caregivers demonstrated higher levels of neuroendocrine dysfunction. No gender difference in biological risks was found. DISCUSSION: Filial caregiving is the most prevalent form of family caregiving and results indicating the presence of greater neuroendocrine dysfunction among filial caregivers in contrast to noncaregivers suggest an important public health concern. Future research needs to continue to examine different relationship types of caregivers and include a range of biological risk measurement to further the understanding of how family caregiving is linked to biological health risks.

Instant visual detection of picogram levels of trinitrotoluene by using luminescent metal-organic framework gel-coated filter paper.

There is an ongoing need for explosive detection strategies to uncover threats to human security including illegal transport and terrorist activities. The widespread military use of the explosive trinitrotoluene (TNT) for landmines poses another particular threat to human health in the form of contamination of the surrounding environment and groundwater. The detection of explosives, particularly at low picogram levels, by using a molecular sensor is seen as an important challenge. Herein, we report on the use of a fluorescent metal-organic framework hydrogel that exhibits a higher detection capability for TNT in the gel state compared with that in the solution state. A portable sensor prepared from filter paper coated by the hydrogel was able to detect TNT at the picogram level with a detection limit of 1.82 ppt (parts per trillon). Our results present a simple and new means to provide selective detection of TNT on a surface or in aqueous solution, as afforded by the unique molecular packing through the metal-organic framework structure in the gel formation and the associated photophysical properties. Furthermore, the rheological properties of the MOF-based gel were similar to those of a typical hydrogel.

The tryptophan metabolite 3-hydroxyanthranilic acid suppresses T cell responses by inhibiting dendritic cell activation.

The generation of tryptophan (Trp) metabolites by indoleamine 2,3-dioxygenase (IDO) is an effective mechanism for T cell suppression. However, the effect of Trp metabolites on dendritic cells (DCs) remains unclear. Here, we investigated whether the tryptophan metabolite 3-hydroxyanthranilic acid (3-HAA) directly inhibits DC activation and is responsible for T cell suppression. We found that 3-HAA treatment significantly reduced IL-12, IL-6, and TNF-α production in bone marrow-derived DCs (BMDCs) stimulated with LPS. Maturation markers CD40, CD80, CD86, and I-A were also significantly reduced. Moreover, treatment with 3-HAA decreased the ability of DCs to stimulate T cell activation and differentiation in vitro and in vivo. Finally, we observed that phospho-JNK and phospho-38 levels were reduced in 3-HAA-treated DC2.4 cells and BMDCs. These results suggest that the tryptophan metabolite 3-HAA suppresses T cell responses by inhibiting DC activation.

Remarkable reinforcement of a supramolecular gel constructed by heteroditopic [18]crown-6-based molecular recognition.

The heteroditopic crown ether-based ligand 1 containing the diazafluorenylimino group as a binding site for the Zn(2+) and Cs(+) was synthesized. The ligand 1 can be gelated in DMSO/water with and without Cs(+) in the presence of the Zn(2+) ion. Interestingly, the remarkable gelation reinforcement of gel 1 occurred with Cs(+) in the presence of Zn(2+), which is due to the formation of a sandwich complex. According to DFT calculations, one Zn(2+) is bound to two diazafluorenylimino moieties in a tetrahedral structure. In addition, one Cs(+) ion is bound to two crown-rings. The Zn(2+)-diazafluorenylimino ligand gel without Cs(+) shows a spherical structure with 250-800 nm diameter, whereas the Zn(2+)-diazafluorenylimino-based ligand gel with Cs(+) shows a fiber structure with 60-70 nm diameter and several micrometers of lengths. The rheological properties of the Zn(2+)-diazafluorenylimino-based ligand gel were strongly dependent on the presence of Cs(+).

Enhancement of the hydrogen storage capacity of Mg(AlH4)2 by excess electrons: a DFT study.

The enhancement of hydrogen storage in complexes of magnesium alanate ([Mg(AlH(4))(2)](n)(-) where n = 2, 3) and their anions was investigated using the B3LYP/6-311++G** method. Hydrogen atoms were chemically absorbed on [Mg(AlH(4))(2)](n)(-) (n = 2, 3) with binding energies of -83 to -91.23 kcal mol(-1). It was determined that a maximum of two hydrogen atoms can be absorbed on [Mg(AlH(4))(2)](n)(-) (n = 2, 3) complexes at 10.51 and 10.21 wt%, respectively. Natural bond order analysis revealed that, in the absence of hydrogen, the excess electron population lies predominantly along the sigma bonds between Mg(2+) atoms, while, upon absorption of the hydrogen atoms, the excess electron population lies on the absorbed hydrogen atoms. The vertical detachment energy showed that the excess electron is strongly bound to [Mg(AlH(4))(2)](n)(-) (n = 2, 3) complexes with energies of 78 to 153 kcal mol(-1). It can be seen from the stabilization energy values that the stability of hydrogen-absorbed complexes with excess electrons was significantly enhanced.

Ligand effects on the stability of thiol-stabilized gold nanoclusters: Au25(SR)18(-), Au38(SR)24, and Au102(SR)44.

We have studied the electrochemical and thermodynamic stability of Au(25)(SR)(18)(-), Au(38)(SR)(24), and Au(102)(SR)(44), R = CH(3), C(6)H(13), CH(2)CH(2)Ph, Ph, PhF, and PhCOOH, in order to examine ligand effects on the stability of thiol-stabilized gold nanoclusters, Au(m)(SR)(n). Aliphatic thiols, in general, have higher electrochemical and thermodynamic stability than aromatic thiols, and the -SCH(2)CH(2)Ph thiol is particularly appealing because of its high electrochemical and thermodynamic stability. The stabilization of Au(m) by nSR for Au(m)(SR)(n) can be rationalized by the stabilization of an Au atom by an SR for the simple molecule AuSR, regardless of interligand interaction and system size and shape. Thiol moieties play a strong role in the electron oxidation and reduction of Au(m)(SR)(n). Accounting for the characteristics of thiol ligands is essential for understanding the electronic and thermodynamic stability of thiol-stabilized gold nanoclusters.

Fluorescent composite hydrogels of metal-organic frameworks and functionalized graphene oxide.

GO MOFs! Azobenzoic acid functionalized graphene (A-GO) can act as a structure-directing template that influences hydrogel formation together with metal-organic frameworks (MOFs). Zn(2+) MOFs of pyridine derivatives work as framework linkers between the A-GO sheets (MOF-A-GO, see figure). MOF-A-GO exhibits a strong fluorescence enhancement upon gel formation. In addition, MOF-A-GO selectively recognizes trinitrotoluene.

Highly efficient blue organic light-emitting diodes based on 2-(diphenylamino)fluoren-7-ylvinylarene derivatives that bear a tert-butyl group.

Blue fluorescent materials with a 2-(diphenylamino)fluoren-7-ylvinylarene emitting unit and tert-butyl-based blocking units were synthesized. The photophysical properties of these materials, including UV/Vis absorption, photoluminescent properties, and HOMO-LUMO energy levels, were characterized and rationalized with quantum-mechanical DFT calculations. The electroluminescent properties of these molecules were examined through the fabrication of multilayer devices with a structure of indium-tin oxide, 4,4'-bis{N-[4-(N,N-di-m-tolylamino)phenyl]-N-phenylamino}biphenyl, 4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl, and blue materials doped in 2-methyl-9,10-di(2-naphthyl)anthracene/tris(8-quinolinolato)aluminum/LiF/Al. All devices exhibit highly efficient blue electroluminescence with high external quantum efficiency (3.20-7.72 % at 20 mA cm(-2)). A deep-blue device with Commission Internationale de l'Eclairage (CIE) coordinates of (0.15, 0.11) that uses 7-[2-(3',5'-di-tert-butylbiphenyl-4-yl)vinyl]-9,9-diethyl-2-N-(3,5-di-tert-butylphenyl)-2,4-difluorobenzenamino-9H-fluorene as a dopant in the emitting layer showed a luminous efficiency and external quantum efficiency of 3.95 cd A(-1) and 4.23 % at 20 mA cm(-2), respectively. Furthermore, a highly efficient sky-blue device that uses the dopant 7-{2-[2-(3,5-di-tert-butylphenyl)-9,9'-spirobifluorene-7-yl]vinyl}-9,9-diethyl-2-N,N-diphenylamino-9H-fluorene exhibited a luminous efficiency and high quantum efficiency of 10.3 cd A(-1) and 7.7 % at 20 mA cm(-2), respectively, with CIE coordinates of (0.15, 0.20).