The unprecedented strong paratropic ring current of a bis-PdII complex of 5,10,23-trimesityl [28]heptaphyrin(1.1.0.0.1.0.0).

Acid-catalyzed Friedel-Crafts-type cyclization of tetrapyrrolic BF2 complex 1 and α,α'-dibromotripyrrin 2 gave 5,10,23-trimesityl [28]heptaphyrin(1.1.0.0.1.0.0) BF2 complex 3BF2 as a stable and moderate antiaromatic macrocycle. Demetalation of 3BF2 with methanesulfonic acid followed by treatment with HCl gave free-base salt 3HCl that holds a chloride anion at the core. This salt displays a planar structure with an inverted pyrrole and a stronger paratropic ring current. Metalation of neutral free-base 3 with PdCl2 gave bis-PdII complex 3Pd2 as a stable antiaromatic molecule. The 1H NMR spectrum of 3Pd2 displays signals due to pyrrolic ß-protons in the range of -1.06 ∼ -1.90 ppm, indicating the unprecedented strong paratropic ring current.

Management of Glaucoma-Related Dry Eye Disease with Intense Pulsed Light: A Randomized Control Study.

Purpose: The objective of this study was to assess the effectiveness of intense pulsed light (IPL) therapy in individuals diagnosed with glaucoma and dry eye disease (DED). Methods: This randomized control study recruited 22 individuals diagnosed with glaucoma, ranging in age from 33 to 82 years. These participants were undergoing treatment with hypotensive eyedrops and had clinical indications and subjective complaints associated with dry eye. Each patient underwent three sessions of IPL therapy in one eye, while the contralateral eye served as the control eye (CT). The following parameters were assessed at three time points: baseline, week-2, and week-4. These parameters include non-invasive breakup time (NITBUT), tear meniscus height (TMH), conjunctivocorneal epithelial staining score (CS), tear film lipid layer (TFLL), meibomian gland expressibility score (MGEx), Schirmer I test, ocular bulbar redness score (OBRS), and ocular surface disease index (OSDI). Intraocular pressure (IOP), best-corrected visual acuity (BCVA), and corneal endothelial cell count (ECC) were assessed for safety. The clinical trial was registered on 25/12/2023 at ClinicalTrials.gov website (NCT06158984). Results: Comparing baseline and 4-week measurements revealed that the IPL group found significant improvements in NITBUT (IPL: 8.74±2.60 sec. vs CT: 5.76±1.75 sec. p<0.01), TMH (IPL: 0.23±0.05mm vs CT: 0.19±0.06mm, p=0.011), C.S. (IPL: 1.14±0.56 vs CT: 1.95±1.17, p=0.005), TFLL (IPL: 2.91±2.91 vs CT:3.36±0.58, p=0.047), MGEx score (IPL: 1.14±0.35 vs CT: 1.45±0.51, p=0.020) and OSDI scores (IPL: 31.77±15.59 vs 50.59±21.55, p=0.002) significantly improved. Conversely, other parameters showed no significant improvements (p>0.05). Conclusion: The progression of ocular surface disease in individuals using topical anti-glaucoma medication may worsen if the condition is not addressed. Nevertheless, IPL therapy has the potential to result in significant improvements in both objective and subjective measures of dry eye. Best-corrected visual acuity, endothelial cell count, and intraocular pressure were determined to be within the permitted limits. No adverse events were reported during the course of the study.

The results show that people who use topical medicines to treat glaucoma may get worse eye surface disease if they do not treat the problem. IPL treatment, on the other hand, can make a big difference in both objective and subjective dry eye tests. The vision, endothelial cell count, and the pressure inside the eye were all found to be within normal limits after the IPL treatment. Even though the people in our study had glaucoma and had been taking glaucoma medicine for it for a year and the fact that the symptoms last for a long time may also change the results. Also, DED caused by glaucoma medication is complicated, with a lot of different symptoms and signs, even in the same stage. Also, subjective complaints may not match up with clinical signs. The type, amount, and length of anti-glaucoma drugs may have affected the results.

Longitudinal on-treatment circulating tumor DNA as a biomarker for real-time dynamic risk monitoring in cancer patients: The EP-SEASON study.

Recurrence risks of cancer patient can change during treatment as a result of treatment-related tumor evolution. However, biomarkers that can monitor these changes are lacking. Here, we investigated whether tracking circulating tumor DNA (ctDNA) dynamics through liquid biopsy can inform real-time recurrence risk. Nasopharyngeal carcinoma (NPC) provides an ideal model where cell-free Epstein-Barr virus (EBV) DNA (cfEBV DNA), a ctDNA, can be sensitively detected. We conducted the EP-SEASON study (NCT03855020) and prospectively recruited 1,000 NPC patients undergoing per-protocol cfEBV DNA assessments at 11 time points and receiving sequential chemo-radiotherapy. Longitudinal cfEBV DNA displayed distinct patterns during neoadjuvant chemotherapy and radiotherapy. Despite the prognostic significance of cfEBV DNA at each time point, real-time recurrence risks changed in sync with cfEBV DNA dynamics. Furthermore, we identified phenotypes of whole-course ctDNA changing dynamics associated with different survival outcomes. In conclusion, tracking longitudinal on-treatment ctDNA can forecast real-time recurrence risk, facilitating risk-adapted, individualized patient management.

Targeting RBM39 through indisulam induced mis-splicing of mRNA to exert anti-cancer effects in T-cell acute lymphoblastic leukemia.

BACKGROUND: Despite the use of targeted therapeutic approaches, T-cell acute lymphoblastic leukemia (T-ALL) is still associated with a high incidence of complications and a poor prognosis. Indisulam (also known as E7070), a newly identified molecular glue compound, has demonstrated increased therapeutic efficacy in several types of cancer through the rapid degradation of RBM39. This study aimed to evaluate the therapeutic potential of indisulam in T-ALL, elucidate its underlying mechanisms and explore the role of the RBM39 gene. METHODS: We verified the anticancer effects of indisulam in both in vivo and in vitro models. Additionally, the construction of RBM39-knockdown cell lines using shRNA confirmed that the malignant phenotype of T-ALL cells was dependent on RBM39. Through RNA sequencing, we identified indisulam-induced splicing anomalies, and proteomic analysis helped pinpoint protein changes caused by the drug. Comprehensive cross-analysis of these findings facilitated the identification of downstream effectors and subsequent validation of their functional roles. RESULTS: Indisulam has significant antineoplastic effects on T-ALL. It attenuates cell proliferation, promotes apoptosis and interferes with cell cycle progression in vitro while facilitating tumor remission in T-ALL in vivo models. This investigation provides evidence that the downregulation of RBM39 results in the restricted proliferation of T-ALL cells both in vitro and in vivo, suggesting that RBM39 is a potential target for T-ALL treatment. Indisulam's efficacy is attributed to its ability to induce RBM39 degradation, causing widespread aberrant splicing and abnormal translation of the critical downstream effector protein, THOC1, ultimately leading to protein depletion. Moreover, the presence of DCAF15 is regarded as critical for the effectiveness of indisulam, and its absence negates the ability of indisulam to induce the desired functional alterations. CONCLUSION: Our study revealed that indisulam, which targets RBM39 to induce tumor cell apoptosis, is an effective drug for treating T-ALL. Targeting RBM39 through indisulam leads to mis-splicing of pre-mRNAs, resulting in the loss of key effectors such as THOC1.

ACSL3 regulates breast cancer progression via lipid metabolism reprogramming and the YES1/YAP axis.

OBJECTIVE: Mitochondrial fatty acid oxidation is a metabolic pathway whose dysregulation is recognized as a critical factor in various cancers, because it sustains cancer cell survival, proliferation, and metastasis. The acyl-CoA synthetase long-chain (ACSL) family is known to activate long-chain fatty acids, yet the specific role of ACSL3 in breast cancer has not been determined. METHODS: We assessed the prognostic value of ACSL3 in breast cancer by using data from tumor samples. Gain-of-function and loss-of-function assays were also conducted to determine the roles and downstream regulatory mechanisms of ACSL3 in vitro and in vivo. RESULTS: ACSL3 expression was notably downregulated in breast cancer tissues compared with normal tissues, and this phenotype correlated with improved survival outcomes. Functional experiments revealed that ACSL3 knockdown in breast cancer cells promoted cell proliferation, migration, and epithelial-mesenchymal transition. Mechanistically, ACSL3 was found to inhibit ß-oxidation and the formation of associated byproducts, thereby suppressing malignant behavior in breast cancer. Importantly, ACSL3 was found to interact with YES proto-oncogene 1, a member of the Src family of tyrosine kinases, and to suppress its activation through phosphorylation at Tyr419. The decrease in activated YES1 consequently inhibited YAP1 nuclear colocalization and transcriptional complex formation, and the expression of its downstream genes in breast cancer cell nuclei. CONCLUSIONS: ACSL3 suppresses breast cancer progression by impeding lipid metabolism reprogramming, and inhibiting malignant behaviors through phospho-YES1 mediated inhibition of YAP1 and its downstream pathways. These findings suggest that ACSL3 may serve as a potential biomarker and target for comprehensive therapeutic strategies for breast cancer.

Socioeconomic Status Plays a Moderating Role in the Association Between Multimorbidity and Health-Related Quality of Life Among Cancer Patients.

This study aimed to explore the moderating role of socioeconomic status (SES) in the association between multimorbidity and health-related quality of life (HRQOL) among cancer patients in Anhui China. A total of 560 cancer patients were recruited for the cross-section study. Socio-demographic and clinical characteristics were analyzed using descriptive statistics. Tobit regression analysis was employed to investigate the relationship between multimorbidity and HRQOL as well as to assess the moderating effect of SES. The research findings indicated that 76.61% of cancer patients experienced multimorbidity, with psychological multimorbidity being the most prevalent (45.54%), followed by physical-psychological multimorbidity (20.89%). Moreover, physical-psychological multimorbidity had the most substantial adverse effect on HRQOL (P < .001). The presence of multimorbidity was correlated with a significant decline in HRQOL, with a 17.5% (P < .001) decrease in HRQOL for each additional multimorbidity. Additionally, SES played a significant role in moderating the impact of multimorbidity on HRQOL in cancer patients. (Marginal effect = -0.022, P < .01). The high SES group exhibited a higher overall HRQOL than the low SES group (Marginal effect = 0.068, P < .001). And with the increase of multimorbidity, HRQOL in the higher SES showed a more pronounced downward trend, compared with the lower SES (ß = -.270 vs ß = -.201, P < .001). Our findings underscore the importance of preventing and managing multimorbidity in cancer patients, particularly those with low SES. Furthermore, it is essential to consider the impact of the rapid decline in HRQOL as the number of multimorbidity increases in individuals with higher SES. It is imperative to explore interdisciplinary and continuous collaborative management models.

Cr (VI)-induced ribosomal DNA copy number variation is associated with semen quality impairment: Evidence from human to animal study.

OBJECTIVES: This study aimed to analyze the possible role of rDNA copy number variation in the association between hexavalent chromium [Cr (VI)] exposure and semen quality in semen donors and further confirm this association in mice. METHODS: In this cross-sectional study, whole blood and semen samples were collected from 155 semen donors in the Zhejiang Human Sperm Bank from January 1st to April 31st, 2021. Adult C57BL/6 J male mice were treated with different doses of Cr (VI) (0, 10, or 15 mg/kg b.w./day). Semen quality, including semen volume, total spermatozoa count, sperm concentration, progressive motility, and total motility, were analyzed according to the WHO laboratory manual. Cr concentration was detected using inductively coupled plasma mass spectrometry. The rDNA copy number was measured using qPCR. RESULTS: In semen donors, whole blood Cr concentration was negatively associated with semen concentration and total sperm counts. Semen 5 S and 45 S rDNA copy numbers were negatively associated with whole blood Cr concentration and whole blood 5.8 S rDNA copy number was negatively associated with semen Cr concentration. In mice, Cr (VI) damaged testicular tissue, decreased semen quality, and caused rDNA copy number variation. Semen quality was related to the rDNA copy number in whole blood, testicular tissue, and semen samples in mice. CONCLUSION: Cr (VI) was associated with decreased semen quality in semen donors and mice. Our findings suggest an in-depth analysis of the role of the rDNA copy number variation in the Cr (VI)-induced impairment of semen quality.

Physiology, Biochemistry, and Transcriptomics Jointly Reveal the Phytotoxicity Mechanism of Acetochlor on Pisum sativum L.

Acetochlor, as a commonly used pre-emergent herbicide, can be toxic to crops and affect production if used improperly. However, the toxic mechanism of acetochlor on plants is not fully understood. The present study used a combination of transcriptomic analysis and physiological measurements to investigate the effects of short-term (15-day) exposure to different concentrations of acetochlor (1, 10, 20 mg/kg) on the morphology, physiology, and transcriptional levels of pea seedlings, aiming to elucidate the toxic response and resistance mechanisms in pea seedlings under herbicide stress. The results showed that the toxicity of acetochlor to pea seedlings was dose-dependent, manifested as dwarfing and stem base browning with increasing concentrations, especially at 10 mg/kg and above. Analysis of the antioxidant system showed that from the 1 mg/kg treatment, malondialdehyde, superoxide dismutase, peroxidase, and glutathione peroxidase in peas increased with increasing concentrations of acetochlor, indicating oxidative damage. Analysis of the glutathione (GSH) metabolism system showed that under 10 mg/kg treatment, the GSH content of pea plants significantly increased, and GSH transferase activity and gene expression were significantly induced, indicating a detoxification response in plants. Transcriptomic analysis showed that after acetochlor treatment, differentially expressed genes in peas were significantly enriched in the phenylpropane metabolic pathway, and the levels of key metabolites (flavonoids and lignin) were increased. In addition, we found that acetochlor-induced dwarfing of pea seedlings may be related to gibberellin signal transduction. Environ Toxicol Chem 2024;00:1-15. © 2024 SETAC.

Age at natural menopause and associated factors with early and late menopause among Chinese women in Zhejiang province: A cross-sectional study.

OBJECTIVES: Menopause is a significant life transition for women, impacting their physical and psychological health. The age at natural menopause (ANM) and its associated factors have differed by race and region. This study aimed to investigate ANM and associated factors of early and late menopause among Chinese women in Zhejiang province. METHODS: A cross-sectional study was conducted using a multi-stage stratified cluster sampling method to recruit 8,006 women aged 40-69 years who had resided in Zhejiang province for over 6 months between July 2019 and December 2021. Self-reported ANM and sociodemographics, lifestyle behaviors, reproductive history, and health-related factors were collected using questionnaires in face-to-face surveys. ANM were categorized into three groups: early menopause (<45 years), normal menopause (45-54 years), and late menopause (≥55 years). Kaplan-Meier survival analysis was utilized to calculate the median ANM. Multivariable multinomial logistic regression was employed to explore the associated factors of early menopause and late menopause. RESULTS: A total of 6,047 women aged 40-69 years were included for survival analysis, with 3,176 of them for the regression analysis. The overall median ANM was 51 years (Inter-quartile range [IQR]: 51-52). Women who were smokers (odds ratio [OR]:4.54, 95% confidence interval [CI]:1.6-12.84), had irregular menstrual cycles (OR:1.78, 95% CI:1.12-2.83) and hypertension (OR:1.55, 95% CI:1.09-2.21) had a higher odds ratio of early menopause, while central obesity (OR:1.33, 95% CI:1.03-1.73) and hyperlipidemia (OR:1.51, 95% CI:1.04-2.18) were factors associated with late menopause. CONCLUSIONS: This study revealed the associations between ANM and various factors among Chinese women. These factors included socio-demographic factors such as age; life behavior factors like current or prior smoking status; reproductive history factors such as irregular menstrual cycles, miscarriages, and breastfeeding; and health-related factors like central adiposity, hypertension, and hyperlipidemia. These findings provided a basis for understanding factors associated with ANM.

Study of tree shrew biology and models: A booming and prosperous field for biomedical research.

The tree shrew ( Tupaia belangeri) has long been proposed as a suitable alternative to non-human primates (NHPs) in biomedical and laboratory research due to its close evolutionary relationship with primates. In recent years, significant advances have facilitated tree shrew studies, including the determination of the tree shrew genome, genetic manipulation using spermatogonial stem cells, viral vector-mediated gene delivery, and mapping of the tree shrew brain atlas. However, the limited availability of tree shrews globally remains a substantial challenge in the field. Additionally, determining the key questions best answered using tree shrews constitutes another difficulty. Tree shrew models have historically been used to study hepatitis B virus (HBV) and hepatitis C virus (HCV) infection, myopia, and psychosocial stress-induced depression, with more recent studies focusing on developing animal models for infectious and neurodegenerative diseases. Despite these efforts, the impact of tree shrew models has not yet matched that of rodent or NHP models in biomedical research. This review summarizes the prominent advancements in tree shrew research and reflects on the key biological questions addressed using this model. We emphasize that intensive dedication and robust international collaboration are essential for achieving breakthroughs in tree shrew studies. The use of tree shrews as a unique resource is expected to gain considerable attention with the application of advanced techniques and the development of viable animal models, meeting the increasing demands of life science and biomedical research.

Nanosheet BiOBr Modified Rock Wool Composites for High Efficient Oil/Water Separation and Simultaneous Dye Degradation by Activating Peroxymonosulfate.

The development of superlyophobic materials in liquid systems, enabling synchronous oil/water separation and dye removal from water, is highly desirable. In this study, we employed a novel superwetting array-like BiOBr nanosheets anchored on waste rock wool (RW) fibers through a simple neutralization alcoholysis method. The resulting BiOBr/RW fibers exhibited superoleophilic and superhydrophilic properties in air but demonstrated underwater superoleophobic and underoil superhydrophobic characteristics. Utilizing its dual superlyophobicity, the fiber layer demonstrated high separation efficiencies and flux velocity for oil/water mixtures by prewetting under a gravity-driven mechanism. Additionally, the novel BiOBr/RW fibers also exhibited excellent dual superlyophobicity and effective separation for immiscible oil/oil systems. Furthermore, the BiOBr/RW fibers could serve as a filter to continuously separate oil/water mixtures with high flux velocity and removal rates (>93.9%) for water-soluble dye rhodamine B (RhB) simultaneously by directly activating peroxymonosulfate (PMS) in cyclic experiments. More importantly, the mechanism of simultaneous oil/water separation and RhB degradation was proposed based on the reactive oxygen species (ROS) quenching experiments and electron paramagnetic resonance (EPR) analysis. Considering the simple modified process and the waste RW as raw material, this work may open up innovative, economical, and environmentally friendly avenues for the effective treatment of wastewater contaminated with oil and water-soluble pollutants.

ARID1A safeguards the canalization of the cell fate decision during osteoclastogenesis.

Chromatin remodeler ARID1A regulates gene transcription by modulating nucleosome positioning and chromatin accessibility. While ARID1A-mediated stage and lineage-restricted gene regulation during cell fate canalization remains unresolved. Using osteoclastogenesis as a model, we show that ARID1A transcriptionally safeguards the osteoclast (OC) fate canalization during proliferation-differentiation switching at single-cell resolution. Notably, ARID1A is indispensable for the transcriptional apparatus condensates formation with coactivator BRD4/lineage-specifying transcription factor (TF) PU.1 at Nfatc1 super-enhancer during safeguarding the OC fate canalization. Besides, the antagonist function between ARID1A-cBAF and BRD9-ncBAF complex during osteoclastogenesis has been validated with in vitro assay and compound mutant mouse model. Furthermore, the antagonistic function of ARID1A-"accelerator" and BRD9-"brake" both depend on coactivator BRD4-"clutch" during osteoclastogenesis. Overall, these results uncover sophisticated cooperation between chromatin remodeler ARID1A, coactivator, and lineage-specifying TF at super-enhancer of lineage master TF in a condensate manner, and antagonist between distinct BAF complexes in the proper and balanced cell fate canalization.

Retinomorphic X-ray detection using perovskite with hydrion-conductive organic cations.

X-ray detection is crucial across various sectors, but traditional techniques face challenges such as inefficient data transmission, redundant sensing, high power consumption, and complexity. The innovative idea of a retinomorphic X-ray detector shows great potential. However, its implementation has been hindered by the absence of active layers capable of both detecting X-rays and serving as memory storage. In response to this critical gap, our study integrates hybrid perovskite with hydrion-conductive organic cations to develop a groundbreaking retinomorphic X-ray detector. This novel device stands at the nexus of technological innovation, utilizing X-ray detection, memory, and preprocessing capabilities within a single hardware platform. The core mechanism underlying this innovation lies in the transport of electrons and holes within the metal halide octahedral frameworks, enabling precise X-ray detection. Concurrently, the hydrion movement through organic cations endows the device with short-term resistive memory, facilitating rapid data processing and retrieval. Notably, our retinomorphic X-ray detector boasts an array of formidable features, including reconfigurable short-term memory, a linear response curve, and an extended retention time. In practical terms, this translates into the efficient capture of motion projections with minimal redundant data, achieving a compression ratio of 18.06% and an impressive recognition accuracy of up to 98.6%. In essence, our prototype represents a paradigm shift in X-ray detection technology. With its transformative capabilities, this retinomorphic hardware is poised to revolutionize the existing X-ray detection landscape.

Influences of thioalcohols on the release of aromas in sesame-flavor baijiu.

This study investigated the interactions between 2-furylmethanethiol, benzenemethanethiol, and 18 skeletal aroma-active compounds as well as four aroma notes in sesame-flavor baijiu based on the Feller Additive Model, the Odor Activity Value (OAV) Approach, and the Sigma-Tau (σ-τ) plots. In addition, a predictive model for the interactions between 2-furylmethanethiol and esters was developed, and the determinants of the interaction results in complex systems were explored. The results reveal that both thioalcohols interacted with the skeletal aroma-active compounds in a similar trend, where 2-furylmethanethiol tends to enhance the release of fruit and acid aroma. Moreover, the intensity of the thiols and their intensity ratio to the notes were the determinants of the interaction results in the multivariate blended system, with the lower the concentration of the thiols, the closer the ratio was to 1, and the more likely that additive interactions would take place. Predictive modeling showed that 2-furylmethanethiols were more likely to have additive or synergistic effects with esters when the olfactory thresholds of the esters were between 75.86 and 199.53 µg/L. Conversely, masking effects were more likely.

Unique Plant Resources and Distribution Patterns in the Valley Forest of the Irtysh River Basin.

The river valley forests of the Irtysh River Basin are a germplasm bank of Salicaceae species and rare plant resources in China, and the distribution varies with the river and is highly distinctive. However, there is a dearth of systematic research on the characteristics of plant resources. In this study, a comprehensive investigation was conducted in the trunk stream and six tributaries with valley forest distribution in the Irtysh River Basin, and 244 quadrats were set up. The analysis focused on the composition of the flora and resource characteristics. The results reveal the following: (1) The valley forests of the Irtysh River Basin contain 256 species of plants belonging to 57 families and 178 genera, among which 19 species of trees, 23 species of shrubs, and 214 species of herbs were investigated. (2) Among the identified species, 226 (88.67%) were recognized as resource plants, with medicinal plants being the most abundant (176 species, 68.75% of the total). (3) The distribution patterns of trees, shrubs, and herbs of each resource type vary across rivers. Elevation drop, river length, and river distance all significantly affect the number of specie. This study elucidated the current status and distributional characteristics of plant resources in the valley forests of the Irtysh River Basin, which is essential for both biodiversity conservation and sustainable resource utilization.

Agreement and repeatability of scotopic pupil size measurement with the 2WIN-S portable refractor in Chinese adults.

To assess the agreement and repeatability of scotopic pupil size measurement using 2WIN-S (Adaptica, Padova, Italy) portable refractor in Chinese adults. This prospective non-randomized open-label controlled study assessed the scotopic pupil size of 100 right eyes using OPD-Scan III (Optical path difference) (Nidek Technologies, Gamagori, Japan) and 2WIN-S. OPD-Scan III and 2WIN-S measure pupil size using infrared light and detector, while 2WIN-S measures bilateral eyes simultaneously, OPD-Scan III measures unilateral eyes individually. Participants were first measured once using OPD-Scan III and two consecutive measurements were performed using 2WIN-S after 15 min of rest interval. The primary outcome was to evaluate the agreement between 2WIN-S and OPD-Scan III, and the secondary outcome was to evaluate the repeatability of 2WIN-S. Scotopic pupil size of 100 right eyes of 100 adults (28 male and 72 female) aged 18-53 years (mean 36 ± 12 years) was assessed using OPD-Scan III and 2WIN-S, respectively. The mean scotopic pupil size of OPD-Scan III and 2WIN-S was recorded to be 6.24 ± 0.88 mm and 6.27 ± 0.81 mm, respectively. For the mean scotopic pupil size of OPD-Scan III and 2WIN-S the difference was - 0.03 mm (95%CI - 0.10 to 0.04 mm), p = 0.445, the 95% limits of agreement (LOA) was - 0.71 to 0.66 mm. ICC between the two devices was 0.92 (95% CI 0.88-0.94) (ICC > 0.9 indicates excellent consistency). Coefficients of repeatability (CoR) of 2WIN-S was 0.37, which has a high repeatability. For the mean scotopic pupil size of 2WIN-S of the repeated measurements, the difference was -0.04 mm (95%CI - 0.08 to 0.01 mm), p = 0.019, the 95% limits of agreement (LOA) was - 0.41 to 0.32 mm, with a narrow LOA. However, the majority of the variations were less than ± 0.50 mm (98% of scotopic pupil size measurements were below this threshold), within the clinically acceptable range (± 0.50 mm). Our study showed excellent agreement between 2WIN-S and OPD-Scan III (ICC > 0.9) and a good repeatability of 2WIN-S (CoR = 0.37). This study suggests a novel technique for measuring pupillary responses in low light conditions, which can be considered an alternative to OPD-Scan III in clinical settings.

Synthesis of NiII porphyrin-NiII 5,15-diazaporphyrin hybrid tapes.

NiII porphyrin (P) and NiII 5,15-diazaporphyrin (DAP) hybrid tapes were synthesized by Suzuki-Miyaura cross-coupling reactions of meso- or ß-borylated P with ß-brominated DAP followed by intramolecular oxidative fusion reactions. Meso-ß doubly linked hybrid tapes were synthesized by oxidation of singly linked precursors with DDQ-FeCl3. Synthesis of triply linked hybrid tapes was achieved by oxidation with DDQ-FeCl3-AgOTf with suppression of peripheral ß-chlorination. In these tapes, DAP segments were present as a 20π-electronic unit, but their local antiaromatic contribution was trivial. Remarkably, these hybrid tapes were stable and exhibited extremely enhanced absorption bands in the NIR region and multiple reversible redox waves. A pentameric hybrid tape showed a remarkably sharp and red-shifted band at 1168 nm with ε = 5.75 × 105 M-1 cm-1. Singly linked P-DAP dyads were oxidized with DDQ-FeCl3 to give stable radicals, which were oxidized further to afford dimeric hybrid tapes possessing a nitrogen atom at the peripheral-side meso-position.

5,18-Dimesitylorangarin: a Stable Antiaromatic [20]Pentaphyrin(1.0.1.0.0) Displaying Remarkable Oxidative Self-Coupling Reactions.

5,18-Dimesitylorangarin and its BF2 complex were synthesized by double SNAr reaction of 3,5-dibromo-BODIPY with a-(pyro-2-ly)dipyrrin as the first examples of meso-aryl-substituted orangarin. These orangarins, delineated as [20]pentaphyrin(1.0.1.0.0), are strongly antiaromatic but rather stable. The free base orangarin was coupled by oxidation with MnO2 to give a 11,11'-linked dimer, a cyclooctatetraene(COT)-centered trimer, and a spiro-trimer. Fused COT-centered 3H-orangarin dimer was oxidized to the corresponding 2H-orangarin dimer, which was further coupled to give a triply COT centered 2H-orangarin tetramer. 3H-Orangarin oligomers are all antiaromatic as evinced by extremely low-field-shifted 1H NMR signals of the inner NH and ill-defined absorption spectra with broad tails. In contrast, COT-centered 2H-orangarin dimer and tetramer show moderately low-field-shifted NH signals and intense NIR absorbance over 900 nm, suggesting the effective p-conjugation through the COT bridge and almost non-antiaromatic character. These orangarin oligomers exhibit many reversible redox potentials owing to the intramolecular electronic interactions. Regardless of the different aromatic characters, all the orangarin monomers and oligomers exhibit very rapid excited-state decays.

m-Pyripentaphyrins(1.0.0.0.0): BIII Complexes and ß-ß Directly Linked Dimers.

m-Pyripentaphyrins(1.0.0.0.0) were synthesized by Suzuki-Miyaura coupling of 3,5-bis(5-borylpyrrol-2-yl)-BODIPY with 2,6-dibromopyridine. Upon treatment with PhBCl2, pyripentaphyrin 1 provided mono- and bis-BIII complexes sequentially. The Mono-BIII complex shows a distorted tetrahedral coordinated BIII with a σ-phenyl ligand on the BIII and the bis-BIII complex shows an additional distorted tetrahedral coordinated BIII with a B-H bond. Bromination of the pyripentaphyrins with N-bromosuccinimide (NBS) resulted in regioselective formation of 8-bromopyripentaphyrins, which were dimerized to 8,8'-linked dimers by reductive coupling with Ni(cod)2. While all these pyripentaphyrins are nonaromatic, they exhibit characteristic broad absorption bands at long wavelength near the NIR region, indicating the presence of effective macrocyclic conjugation.