Investigation of the Effect of the Passivation on the Charge Transfer from MAPbI3 to Electron Transport Layer Using a Heterodyne Transient Grating Spectroscopic Technique.

We fabricated MAPbI3 perovskite thin films with ZnO on a glass substrate, in which a passivation layer (Phenethylammonium iodide (PEAI); p-methoxyphenethylammonium iodide (CH3O-PEAI); 2-methoxyethylammonium iodide (MEAI)) was inserted between two layers. In order to understand the effect of the insertion of each passivation material on the transfer efficiency of the photo-generated electrons from MAPbI3 to ZnO, we observed the near-field heterodyne transient grating (NF-HD-TG) responses of each film and investigated the component arising from the recombination of the trapped electrons at the ZnO surface. Based on the accelerated recombination between photo-generated holes remaining in the MAPbI3 layer and surface-trapped electrons in ZnO and the increase in the number of the trapped electrons in ZnO when either CH3O-PEAI or PEAI was applied, we successfully revealed that the charge transfer efficiency was enhanced by the insertion of the passivation materials including a benzene ring stabilizing the defect states. Particularly, it was demonstrated that CH3O-PEAI showed the highest increase in the charge transfer efficiency, which could be attributed to the high electron density in the benzene ring, resulting from the existence of the electron donating group, CH3O, and its role in the effective transition from 3D to 2D perovskite phases.

Simple Functionalization of a Donor Monomer to Enhance Charge Transfer in Porous Polymer Networks for Photocatalytic Hydrogen Evolution.

Porous polymer networks (PPNs) are promising candidates as photocatalysts for hydrogen production. Constructing a donor-acceptor structure is known to be an effective approach for improving photocatalytic activity. However, the process of how a functional group of a monomer can ensure photoexcited charges transfer and improve the hydrogen evolution rate (HER) has not yet been studied on the molecular level. Herein, we design and synthesize two kinds of triazatruxene (TAT)-based PPNs: TATR-PPN with a hexyl (R) group and TAT-PPN without the hexyl group, to understand the relationship between the presence of the functional group and charge transfer. The hexyl group on the TAT unit was found to ensure the transfer of photoexcited electrons from a donor unit to an acceptor unit and endowed the TATR-PPN with stable hydrogen production.

A new strategy for monitoring the charge transfer from perovskite thin films to electron transport layers using a heterodyne transient grating technique.

We fabricated CH3NH3PbI3 (MAPbI3) thin films with and without a ZnO layer and measured the heterodyne transient grating (HD-TG) responses of each film to investigate the charge injection dynamics from MAPbI3 to ZnO, based on the component arising from the recombination of the surface trapped electrons in the ZnO layer with the remaining holes in MAPbI3. In addition, we observed the HD-TG response of the MAPbI3 thin film coated with the ZnO layer in which phenethyl ammonium iodide (PEAI) was inserted between two layers as a passivation layer and confirmed that the charge transfer was enhanced when PEAI existed, based on the increase in the amplitude of the component arising from the recombination and its acceleration.

Development of charge carrier-selective heterodyne transient grating spectroscopic technique and its application in the distinction of surface trap states in hematite.

We developed a new spectroscopic technique, which is named the charge carrier-selective heterodyne transient grating (CS-HD-TG) method, for the distinction of surface trap states existing in photocatalysts and photovoltaic materials by employing a burn laser inducing depletion of the number of surface trapped charge carriers. In addition, as a case study, we measured the heterodyne transient grating responses of hematite under bias conditions with and without the burn laser and revealed that two distinct trap states co-exist at the surface of the hematite film and only one of them could act as the reaction intermediate for the oxygen evolution reaction (OER), which is consistent with former studies.

The extent of harmful volatile organic compounds released when smoking after breaking the flavor capsules of heat-not-burn (HNB) cigarette products.

A number of flavored capsule heat-not-burn (FC-HNB) tobacco products such as IQOS, Lil, and Glo have been introduced as a new generation of cigarettes. As they can release various types of volatile organic compounds (VOCs), it is important to assess the harmfulness associated with their use. Thus, the composition of VOCs in HNB cigarette vapor was evaluated to investigate the interactive roles of key variables controlling the relationships between VOC composition and capsule breaking, particularly the compositional changes induced by capsule breaking and release of flavor from FC-HNB cigarettes relative to regular products. As the capsules of FC-HNB cigarettes were broken, the total VOC concentrations increased by as high as eight times from 60.3 ± 0.48 to 488 ± 21.8 µg cig-1. The key VOC components released after breaking the flavored capsules were identified as ethyl butyrate (157 ± 13.6 µg cig-1; Lil), isoamyl acetate (76.9 ± 1.98 µg cig-1; Lil), and limonene (52.3 ± 3.29 µg cig-1; Glo). If the primary health risks of FC-HNB cigarette vapor are assessed using National Institute for Occupational Safety & Health (NIOSH) guidelines, 2,3-butanedinone exceeds the maximum daily intake limit (i.e., 0.05 mg day-1). Our study is expected to offer valuable insights into the harmful effects of direct and indirect exposure to various VOCs in FC-HNB products.

Cobalt-Porphyrin-Based Covalent Organic Frameworks with Donor-Acceptor Units as Photocatalysts for Carbon Dioxide Reduction.

Covalent organic frameworks (COFs) have emerged as a promising platform for photocatalysts. Their crystalline porous nature allows comprehensive mechanistic studies of photocatalysis, which have revealed that their general photophysical parameters, such as light absorption ability, electronic band structure, and charge separation efficiency, can be conveniently tailored by structural modifications. However, further understanding of the relationship between structure-property-activity is required from the viewpoint of charge-carrier transport, because the charge-carrier property is closely related to alleviation of the excitonic effect. In the present study, COFs composed of a fixed cobalt (Co) porphyrin (Por) centered tetraamine as an acceptor unit with differently conjugated di-carbaldehyde based donor units, such as benzodithiophene (BDT), thienothiophene (TT), or phenyl (TA), were synthesized to form Co-Por-BDT, Co-Por-TT, or Co-Por-TA, respectively. Their photocatalytic activity for reducing carbon dioxide into carbon monoxide was in the order of Co-Por-BDT>Co-Por-TT>Co-Por-TA. The results indicated that the excitonic effect, associated with their charge-carrier densities and π-conjugation lengths, was a significant factor in photocatalysis performance.

Hexaazatriphenylene-Based Two-Dimensional Conductive Covalent Organic Framework with Anisotropic Charge Transfer.

The development of covalent organic frameworks (COFs) with efficient charge transport is of immense interest for applications in optoelectronic devices. To enhance COF charge transport properties, electroactive building blocks and dopants can be used to induce extended conduction channels. However, understanding their intricate interplay remains challenging. We designed and synthesized a tailor-made COF structure with electroactive hexaazatriphenylene (HAT) core units and planar dioxin (D) linkages, denoted as HD-COF. With the support of theoretical calculations, we found that the HAT units in the HD-COF induce strong, eclipsed π-π stacking. The unique stacking of HAT units and the weak in-plane conjugation of dioxin linkages leads to efficient anisotropic charge transport. We fabricated HD-COF films to minimize the grain boundary effect of bulk COFs, which resulted in enhanced conductivity. As a result, the HD-COF films showed an electrical conductivity as high as 1.25 S cm-1 after doping with tris(4-bromophenyl)ammoniumyl hexachloroantimonate.

Clinical Report: Midday Removal and Reinsertion of Soft Contact Lens Cannot Prevent Post-lens Tear-film Hyperosmolarity.

SIGNIFICANCE: Our analysis shows that post-lens tear-film (PoLTF) hyperosmolarity is not preventable with midday removal and reinsertion of soft contact lenses. However, low lens-salt diffusivity can prevent the PoLTF from becoming hyperosmotic. Lens-salt diffusivity should be lowered to minimize PoLTF osmolarity while also avoiding lens adhesion. PURPOSE: Soft contact lenses with high lens-salt diffusivity result in hyperosmotic PoLTFs. If the time it takes for PoLTF osmolarity to reach periodic steady state is multiple hours, simple midday lens removal and reinsertion can prevent the PoLTF from becoming hyperosmotic. We investigate whether midday removal and reinsertion of a soft contact lens can prevent the PoLTF from becoming hyperosmotic. METHODS: Time to periodic steady state for PoLTF osmolarity upon soft-contact-lens wear is determined with a previously developed transient tear-dynamics continuum model. Interblink period, lens-salt diffusivity, and lens thickness was varied to assess their effects on time to periodic steady state for PoLTF osmolarity. Time to periodic steady states were assessed for both normal and dry eyes. RESULTS: Within the physically realistic ranges of lens-salt diffusivity, lens thickness, and interblink period, PoLTF osmolarity reaches the periodic steady state well within the first hour of lens wear for both normal and dry eyes. Time to periodic steady state for PoLTF osmolarity is predominately dictated by the salt transport across the contact lens between the PoLTF and the pre-lens tear film and water transport from the ocular surface to the PoLTF. CONCLUSIONS: Since the time to periodic steady state is less than 1 hour for physically realistic ranges of lens-salt diffusivity, interblink period, and lens thickness, midday lens removal and reinsertion cannot prevent PoLTF hyperosmolarity. Instead, focus should be on using soft contact lenses with low salt diffusivity to prevent PoLTF hyperosmolarity.

Extreme Enhancement of Carbon Hydrogasification via Mechanochemistry.

Carbon hydrogasification is the slowest reaction among all carbon-involved small-molecule transformations. Here, we demonstrate a mechanochemical method that results in both a faster reaction rate and a new synthesis route. The reaction rate was dramatically enhanced by up to 4 orders of magnitude compared to the traditional thermal method. Simultaneously, the reaction exhibited very high selectivity (99.8 % CH4 , versus 80 % under thermal conditions) with a cobalt catalyst. Our study demonstrated that this extreme increase in reaction rate originates from the continuous activation of reactive carbon species via mechanochemistry. The high selectivity is intimately related to the activation at low temperature, at which higher hydrocarbons are difficult to form. This work is expected to advance studies of carbon hydrogasification, and other solid-gas reactions.

A single mutation in the ACTR8 gene associated with lineage-specific expression in primates.

BACKGROUND: Alternative splicing (AS) generates various transcripts from a single gene and thus plays a significant role in transcriptomic diversity and proteomic complexity. Alu elements are primate-specific transposable elements (TEs) and can provide a donor or acceptor site for AS. In a study on TE-mediated AS, we recently identified a novel AluSz6-exonized ACTR8 transcript of the crab-eating monkey (Macaca fascicularis). In the present study, we sought to determine the molecular mechanism of AluSz6 exonization of the ACTR8 gene and investigate its evolutionary and functional consequences in the crab-eating monkey. RESULTS: We performed RT-PCR and genomic PCR to analyze AluSz6 exonization in the ACTR8 gene and the expression of the AluSz6-exonized transcript in nine primate samples, including prosimians, New world monkeys, Old world monkeys, and hominoids. AluSz6 integration was estimated to have occurred before the divergence of simians and prosimians. The Alu-exonized transcript obtained by AS was lineage-specific and expressed only in Old world monkeys and apes, and humans. This lineage-specific expression was caused by a single G duplication in AluSz6, which provides a new canonical 5' splicing site. We further identified other alternative transcripts that were unaffected by the AluSz6 insertion. Finally, we observed that the alternative transcripts were transcribed into new isoforms with C-terminus deletion, and in silico analysis showed that these isoforms do not have a destructive function. CONCLUSIONS: The single G duplication in the TE sequence is the source of TE exonization and AS, and this mutation may suffer a different fate of ACTR8 gene expression during primate evolution.

Mitochondrial Cl--Selective Fluorescent Probe for Biological Applications.

Herein we describe the development of the first mitochondrial Cl--selective fluorescent probe, Mito-MQAE, and its applications in biological systems. Fluorescence of Mito-MQAE is insensitive to pH over the physiological pH range and is quenched by Cl- with a Stern-Volmer quenching constant of 201 M-1 at pH 7.0. The results of cell studies using Mito-MQAE show that substances with the ability to disrupt mitochondrial membranes cause increases in the mitochondrial Cl- concentration.

SPAM1/HYAL5 double deficiency in male mice leads to severe male subfertility caused by a cumulus-oocyte complex penetration defect.

The glycosylphosphatidylinositol-anchored sperm hyaluronidases (Hyals), sperm adhesion molecule 1 (SPAM1) and HYAL5, have long been believed to assist in sperm penetration through the cumulus-oocyte complex (COC), but their role in mammalian fertilization remains unclear. Previously, we have shown that mouse sperm devoid of either Spam1 or Hyal5 are still capable of penetrating the COC and that the loss of either Spam1 or Hyal5 alone does not cause male infertility in mice. In the present study, we found that Spam1/Hyal5 double knockout (dKO) mice produced significantly fewer offspring compared with wild-type (WT) mice, and this was due to defective COC dispersal. A comparative analysis between WT and Spam1/Hyal5 dKO epididymal sperm revealed that the absence of these 2 sperm Hyals resulted in a marked accumulation of sperm on the outside of the COC. This impaired sperm activity is likely due to the deficiency in the sperm Hyals, even though other somatic Hyals are expressed normally in the dKO mice. The fertilization ability of the Spam1/Hyal5 dKO sperm was restored by adding purified human sperm Hyal to the in vitro fertilization medium. Our results suggest that Hyal deficiency in sperm may be a significant risk factor for male sterility.-Park, S., Kim, Y.-H., Jeong, P.-S., Park, C., Lee, J.-W., Kim, J.-S., Wee, G., Song, B.-S., Park, B.-J., Kim, S.-H., Sim, B.-W., Kim, S.-U., Triggs-Raine, B., Baba, T., Lee, S.-R., Kim, E. SPAM1/HYAL5 double deficiency in male mice leads to severe male subfertility caused by a cumulus-oocyte complex penetration defect.

Idiopathic chronic diarrhea associated with dysbiosis in a captive cynomolgus macaque (Macaca fascicularis).

Chronic inflammatory enteric diseases occur commonly in humans and animals, especially in captive bred macaques. However, information about the etiology of idiopathic chronic inflammatory diarrhea in cynomolgus monkeys is limited. In this paper, we reported the unusual case of idiopathic chronic diarrhea in a captive cynomolgus monkey based on microbial, imaging, and microbiome examinations.

Cooperative evolution of two different TEs results in lineage-specific novel transcripts in the BLOC1S2 gene.

BACKGROUND: The BLOC1S2 gene encodes the multifunctional protein BLOS2, a shared subunit of two lysosomal trafficking complexes: i) biogenesis of lysosome-related organelles complex-1 and i) BLOC-1-related complex. In our previous study, we identified an intriguing unreported transcript of the BLOC1S2 gene that has a novel exon derived from two transposable elements (TEs), MIR and AluSp. To investigate the evolutionary footprint and molecular mechanism of action of this transcript, we performed PCR and RT-PCR experiments and sequencing analyses using genomic DNA and RNA samples from humans and various non-human primates. RESULTS: The results showed that the MIR element had integrated into the genome of our common ancestor, specifically in the BLOC1S2 gene region, before the radiation of all primate lineages and that the AluSp element had integrated into the genome of our common ancestor, fortunately in the middle of the MIR sequences, after the divergence of Old World monkeys and New World monkeys. The combined MIR and AluSp sequences provide a 3' splice site (AG) and 5' splice site (GT), respectively, and generate the Old World monkey-specific transcripts. Moreover, branch point sequences for the intron removal process are provided by the MIR and AluSp combination. CONCLUSIONS: We show for the first time that sequential integration into the same location and sequence divergence events of two different TEs generated lineage-specific transcripts through sequence collaboration during primate evolution.

Transient meiotic arrest maintained by DON (6-diazo-5-oxo-l-norleucine) enhances nuclear/cytoplasmic maturation of porcine oocytes.

The developmental competence of in vitro-matured oocytes is still lower than that of the in vivo-matured oocytes due to precocious meiotic resumption and inappropriate cytoplasmic maturation. Although numerous efforts have been attempted to accomplish better in vitro maturation (IVM) condition, only limited progress has been achieved. Thus, a current study was conducted to examine the effects of 6-diazo-5-oxo-l-norleucine (DON, an inhibitor of hyaluronan synthesis) during the first half period of IVM on nuclear/cytoplasmic maturation of porcine oocytes and subsequent embryonic development. Based on the observation of the nucleus pattern, metaphase II (MII) oocyte production rate in 1 µM DON group was significantly higher than other groups at 44 h of IVM. The 1 µM of DON was suggested to be optimal for porcine IVM and was therefore used for further investigation. Meiotic arrest effect of DON was maximal at 6 h of IVM, which was supported by the maintenance of significantly higher intra-oocyte cAMP level. In addition, increased pERK1/2 levels and clear rearrangement of cortical granules in membrane of MII oocytes matured with DON provided the evidence for balanced meiosis progression between nuclear and cytoplasmic maturation. Subsequently, DON significantly improved blastocyst formation rate, total cell numbers, and cellular survival in blastocysts after parthenogenetic activation, in vitro fertilization, and somatic cell nuclear transfer. Altogether, our results showed for the first time that 1 µM DON can be used to increase the yield of developmentally competent MII oocytes by synchronizing nuclear/cytoplasmic maturation, and it subsequently improves embryo developmental competence.

Microarchitectural changes in the mandibles of ovariectomized rats: a systematic review and meta-analysis.

BACKGROUND: This study aimed to examine radiologic microarchitectural changes in the mandibles of ovariectomized (OVX) rats through a systematic review and meta-analysis and to identify factors of the OVX rat model that influence on the bone microstructure. METHODS: Eligible articles were identified by searching electronic databases, including Embase, Medline, Web of Science, and KoreaMed, for articles published from January 1966 to November 2017. Two reviewers independently performed study selection, data extraction, and quality assessment. The pooled standardized mean difference (SMD) with 95% confidence intervals was calculated using a random-effects model. Subgroup analysis and meta-regression were performed to explore the effect of potential sources on the outcomes. The reliability of the results was assessed by sensitivity analysis and publication bias. RESULTS: Of 1160 studies, 16 studies (120 OVX and 120 control rats) were included in the meta-analysis. Compared to the control group, the OVX rats' trabecular bone volume fraction (SMD = - 2.41, P < 0.01, I2 = 81%), trabecular thickness (SMD = - 1.73, P < 0.01, I2 = 73%) and bone mineral density (SMD = - 0.95, P = 0.01, I2 = 71%) displayed the bone loss consistent with osteoporosis. The trabecular separation (SMD = 1.66, P < 0.01, I2 = 51%) has widen in the OVX mandibular bone in comparison to the control group. However, the trabecular number showed no indication to detect the osteoporosis (SMD = - 0.45, P = 0.38, I2 = 76%). The meta-regression indicated that longer post-OVX periods led to greater changes in bone mineral density (ß = - 0.104, P = 0.017). However, the rats' age at OVX was not linked to bone microstructure change. CONCLUSIONS: Using meta-regression and sensitivity analysis techniques, heterogeneity across the micro CT studies of OVX-induced osteoporosis was found. The major factors of heterogeneity were the region of interest and post-OVX period. Our assessment can assist in designing experiments to maximize the usefulness of OVX rat model.

Successful application of human-based methyl capture sequencing for methylome analysis in non-human primate models.

BACKGROUND: The characterization of genomic or epigenomic variation in human and animal models could provide important insight into pathophysiological mechanisms of various diseases, and lead to new developments in disease diagnosis and clinical intervention. The African green monkey (AGM; Chlorocebus aethiops) and cynomolgus monkey (CM; Macaca fascicularis) have long been considered important animal models in biomedical research. However, non-human primate-specific methods applicable to epigenomic analyses in AGM and CM are lacking. The recent development of methyl-capture sequencing (MC-seq) has an unprecedented advantage of cost-effectiveness, and further allows for extending the methylome coverage compared to conventional sequencing approaches. RESULTS: Here, we used a human probe-designed MC-seq method to assay DNA methylation in DNA obtained from 13 CM and three AGM blood samples. To effectively adapt the human probe-designed target region for methylome analysis in non-human primates, we redefined the target regions, focusing on regulatory regions and intragenic regions with consideration of interspecific sequence homology and promoter region variation. Methyl-capture efficiency was controlled by the sequence identity between the captured probes based on the human reference genome and the AGM and CM genome sequences, respectively. Using reasonable guidelines, 56 and 62% of the human-based capture probes could be effectively mapped for DNA methylome profiling in the AGM and CM genome, respectively, according to numeric global statistics. In particular, our method could cover up to 89 and 87% of the regulatory regions of the AGM and CM genome, respectively. CONCLUSIONS: Use of human-based MC-seq methods provides an attractive, cost-effective approach for the methylome profiling of non-human primates at the single-base resolution level.

Human Lacrimal Production Rates from Modified Schirmer-Tear Test.

SIGNIFICANCE: A simple methodology is presented to quantify basal tear production with a modified Schirmer-tear test. PURPOSE: We introduce a simple clinical procedure to measure quantitative basal tear-production flowrates, QL, from a modified Schirmer-tear test (STT). METHODS: Eight healthy subjects aged at least 18 years underwent modified STTs on both eyes for two visits each. Schirmer strips were sheathed with transparent tape before insertion. Topical anesthetic minimized reflex tearing. Wetting lengths were measured every 30 s for 5 min; QL was calculated from the linear slope of wetting length versus time. Determination of QL requires mass-balance equations on the tear prism and Schirmer strip with strip imbibition kinetics obeying Darcy and Young-Laplace laws. RESULTS: Basal tear production rates varied from essentially 0 to about 2 µl/min. With some exceptions, right and left eyes showed similar tear production rates. CONCLUSIONS: By following the modified STT, QL is established with minimal additional effort over a standard Schirmer test. We predict and observe four different subtypes of imbibition kinetics depending on how short or long the time is for first appearance of the wetting front and on how fast or slow is tear production. For slow lacrimal production rates, the standard 5-min wetting length does not correlate with basal tear production.

Iloprost supports early development of in vitro-produced porcine embryos through activation of the phosphatidylinositol 3-kinase/AKT signalling pathway.

Despite evidence of the presence of prostaglandin (PG) I2 in mammalian oviducts, its role in early development of in vitro-produced (IVP) embryos is largely unknown. Thus, in the present study we examined the effects of iloprost, a PGI2 analogue, on the in vitro developmental competence of early porcine embryos and the underlying mechanism(s). To examine the effects of iloprost on the development rate of IVF embryos, iloprost was added to the in vitro culture (IVC) medium and cultured for 6 days. Supplementation of the IVC medium with iloprost significantly improved developmental parameters, such as blastocyst formation rate, the trophectoderm:inner cell mass ratio and cell survival in IVF and parthenogenetically activated (PA) embryos. In addition, post-blastulation development into the expanded blastocyst stage was improved in iloprost-treated groups compared with controls. Interestingly, the phosphatidylinositol 3-kinase (PI3K)/AKT signalling pathway was significantly activated by iloprost supplementation in a concentration-dependent manner (10-1000nM), and the beneficial effects of iloprost on the early development of porcine IVF and PA embryos was completely ablated by treatment with 2.5µM wortmannin, a PI3K/AKT signalling inhibitor. Importantly, expression of the PI3K/AKT signalling pathway was significantly reduced in somatic cell nuclear transfer (SCNT) compared with IVF embryos, and iloprost supported the early development of SCNT embryos, as was the case for IVF and PA embryos, suggesting a consistent effect of iloprost on the IVC of IVP porcine embryos. Together, these results indicate that iloprost can be a useful IVC supplement for production of IVP early porcine embryos with high developmental competence.

Acute and subchronic (28 days) oral toxicity studies of Codonopsis lanceolata extract in Sprague-Dawley rats.

Codonopsis lanceolata is a perennial plant that has been used as a food and in traditional medicine for the treatment of cough, bronchitis, and inflammation in East Asia including Korea, Japan, and China. However, information regarding its toxicity is limited. Therefore, we performed a safety evaluation of aqueous C. lanceolata root extract (CLE) in Sprague-Dawley rats. Assessment of acute toxicity revealed that CLE did not influence mortality, clinical appearance, body weight gain, or necropsy findings at a dose of 5000 mg/kg body weight. In the subchronic oral toxicity, data revealed that several significant alteration in food consumption, water consumption, protein excretion, WBCs levels, TGs, BUN levels, and the absolute and relative weights in the liver, spleen and lungs. However, these changes were transient and were not considered treatment related because they showed no apparent dose dependent. These results suggest that CLE (1250, 2500, and 5000 mg/kg body weight/day) administered orally does not cause acute or subchronic toxicity to male or female rats. The 50% lethal dose (LD50) of CLE was determined to be greater than 5000 mg/kg.