A Domino Protocol toward High-performance Unsymmetrical Dibenzo[d,d']thieno[2,3-b;4,5-b']dithiophenes Semiconductors.

Unsymmetric organic semiconductors have many advantages such as good solubility, rich intermolecular interactions for potential various optoelectronic applications. However, their synthesis is more challenging due to intricate structures thus normally suffering tedious synthesis. Herein, we report a trisulfur radical anion (S3⋅-) triggered domino thienannulation strategy for the synthesis of dibenzo[d,d']thieno[2,3-b;4,5-b']dithiophenes (DBTDTs) using readily available 1-halo-2-ethynylbenzenes as starting materials. This domino protocol features no metal catalyst and the formation of six C-S and one C-C bonds in a one-pot reaction. Mechanistic study revealed a unique domino radical anion pathway. Single crystal structure analysis of unsymmetric DBTDT shows that its unique unsymmetric structure endows rich and multiple weak S⋅⋅⋅S interactions between molecules, which enables the large intermolecular transfer integrals of 86 meV and efficient charge transport performance with a carrier mobility of 1.52 cm2 V-1 s-1. This study provides a facile and highly efficient synthetic strategy for more high-performance unsymmetric organic semiconductors.

Balancing public health and privacy rights: a mixed-methods study on disclosure obligations of people living with HIV to their partners in China.

BACKGROUND: In 2021, a Chinese court, based on the newly enacted Civil Code, first revoked a marriage license due to the spouse's failure to disclose their HIV infection before the marriage. This landmark case ignited a fresh debate on whether people living with HIV (PLHIV) have a legal duty to inform their spouses and sexual partners. Advances in medicine have partially isolated HIV transmission from sexual contact, extending the legal basis for the obligation to disclose beyond disease prevention. This study investigates some possibly unforeseen challenges for PLHIV in China to fulfill this duty, and the outcomes of their decisions in light of the government's goal to promote health. METHODS: This study aims to provide a detailed examination of the legal provisions and practices concerning partner notification among PLHIV in China. A mixed-methods research approach was employed between 2019 and 2020, combining questionnaire surveys, in-depth interviews, and participatory observations. A total of 433 valid responses were obtained through a questionnaire posted on a Chinese online platform for PLHIV. Following the collection and random coding of the questionnaire data, 40 individuals living with HIV were selected for in-depth interviews. Subsequently, a six-month field investigation was conducted in Guan ai jia yuan (Caring Home) in Jinhua City to further explore this issue. RESULTS: A considerable proportion of PLHIV exhibit a high rate of disclosure to their spouses (nearly 80%). In the context of sexual partners, 56% of PLHIV stated that their sexual partners were aware of their HIV infection. Whether married PLHIV disclosing to their spouses or unmarried/divorced PLHIV disclosing to sexual partners, however, a substantial majority expressed apprehension about the potential disruption to their relationships that the disclosure might cause. The sole exception was observed among married PLHIV in extramarital relationships who demonstrated a slightly diminished level of concern in this context. Reasons for non-disclosure predominantly included undetectable viral load and the adoption of protective measures. DISCUSSION: This study reveals that a prevailing "HIV stigma" hinders PLHIV from voluntarily fulfilling the disclosure duties bestowed by Article 38 of the Regulations on the Prevention and Control of HIV/AIDS, and the unclear legal provisions of the new Civil Code play a significant role in this regard. Addressing this issue necessitates not only increasing societal tolerance toward PLHIV and reducing instances of social exclusion but also shifting the legal basis of disclosure duties from disease prevention to rights and obligations within the legal relationships of the parties involved. When it comes to the recipients of disclosure, for instance, it is crucial to differentiate between spouses and sexual partners. As for PLHIV failing to fulfill their disclosure duties, apart from interventions involving indirect notifications, the addition of further legal responsibilities may not be advisable. Intentional transmission actions, on the other hand, should still be subject to severe penalties. CLINICAL TRIAL NUMBER: Not applicable.

High Mobility Emissive Excimer Organic Semiconductor Towards Color-Tunable Light-Emitting Transistors.

Organic light-emitting transistors (OLETs) are highly integrated and minimized optoelectronic devices with significant potential superiority in smart displays and optical communications. To realize these various applications, it is urgently needed for color-tunable emission in OLETs, but remains a great challenge as a result of the difficulty for designing organic semiconductors simultaneously integrating high carrier mobility, strong solid-state emission, and the ability for potential tunable colors. Herein, a high mobility emissive excimer organic semiconductor, 2,7-di(2-anthryl)-9H-fluorene (2,7-DAF) was reasonably designed by introducing a rotatable carbon-carbon single bond connecting two anthracene groups at the 2,7-sites of fluorene, and the small torsion angles simultaneously guarantee effective conjugation and suppress fluorescence quenching. Indeed, the unique stable dimer arrangement and herringbone packing mode of 2,7-DAF single crystal enables its superior integrated optoelectronic properties with high carrier mobility of 2.16 cm2 ⋅ V-1 ⋅ s-1 , and strong excimer emission with absolute photoluminescence quantum yield (PLQY) of 47.4 %. Furthermore, the voltage-dependent electrically induced color-tunable emission from orange to blue was also demonstrated for an individual 2,7-DAF single crystal based OLETs for the first time. This work opens the door for a new class of high mobility emissive excimer organic semiconductors, and provides a good platform for the study of color-tunable OLETs.

Advances in heterocycle synthesis through photochemical carbene transfer reactions.

Heterocyclic skeletons are commonly found in various bioactive molecules and pharmaceutical compounds, making them crucial in areas such as medicinal chemistry, materials science, and the realm of natural product synthesis. In recent years, the rapid advancements of visible light methodologies in organic synthesis have shown promising potential for the development of light-induced carbene transfer reactions. This is particularly significant as most organic molecules do not absorb visible light. Free carbene, known for its high activity, is frequently utilized for insertion reactions or cyclopropanation reactions. This review focuses on the photochemical strategy for the construction of heterocyclic skeletons, specifically highlighting the methods that employ visible light-promoted carbene transfer reactions.

Association of tirofiban with improvement of functional outcomes of direct thrombectomy for acute anterior circulation occlusion: a retrospective, nonrandomized, multicenter, real-world study.

OBJECTIVE: Although tirofiban and endovascular thrombectomy have been widely used in the treatment of acute ischemic stroke (AIS) patients, the effectiveness of their combined application remains a subject of debate. This study aimed to assess the efficacy and safety of tirofiban in direct thrombectomy for AIS with anterior circulation vessel occlusion. METHODS: A total of 204 patients undergoing direct thrombectomy between January 2020 and December 2021 for AIS with anterior circulation vessel occlusion from four hospitals were included in this study. Patients at high risk of reocclusion with severe atherosclerosis, those who achieved successful recanalization for ≥ 3 stent retriever passes, or those who underwent emergency stenting or balloon angioplasty for severe residual stenosis were treated with tirofiban. Following a low-dose intra-arterial bolus (0.25-1 mg) immediately after endovascular treatment, tirofiban was administered continuously through intravenous infusion (0.1 µg/kg/min) for 12-24 hours. The primary efficacy outcome was evaluated using the 90-day modified Rankin Scale score. The safety outcome was assessed using symptomatic intracerebral hemorrhage (sICH) and mortality rates. RESULTS: The tirofiban group and nontirofiban group each included 102 patients. The favorable outcome rate in the tirofiban group was significantly higher than that in the nontirofiban group (53.9% vs 35.3%, p = 0.007). However, the sICH and 90-day mortality rates were lower in the tirofiban group, despite a lack of statistical significance (sICH: 15.7% vs 16.7%, p = 0.849; 90-day mortality: 16.67% vs 24.51%, p = 0.166). Finally, it was found that older patients (> 72 years), male patients, patients with admission National Institutes of Health Stroke Scale scores > 14, patients with a time from onset to reperfusion > 327 minutes, and patients with a medical history of diabetes tend to benefit from tirofiban treatment. CONCLUSIONS: This study suggests that tirofiban combined with direct thrombectomy improves functional outcomes of AIS and reduces the 90-day mortality rate. Therefore, it could be considered as a suitable treatment option for AIS patients with anterior circulation vessel occlusion.

A Presurgical Unfavorable Prediction Scale of Endovascular Treatment for Acute Ischemic Stroke.

Objective: To develop a prognostic prediction model of endovascular treatment (EVT) for acute ischemic stroke (AIS) induced by large-vessel occlusion (LVO), this study applied machine learning classification model light gradient boosting machine (LightGBM) to construct a unique prediction model. Methods: A total of 973 patients were enrolled, primary outcome was assessed with modified Rankin scale (mRS) at 90 days, and favorable outcome was defined using mRS 0-2 scores. Besides, LightGBM algorithm and logistic regression (LR) were used to construct a prediction model. Then, a prediction scale was further established and verified by both internal data and other external data. Results: A total of 20 presurgical variables were analyzed using LR and LightGBM. The results of LightGBM algorithm indicated that the accuracy and precision of the prediction model were 73.77 and 73.16%, respectively. The area under the curve (AUC) was 0.824. Furthermore, the top 5 variables suggesting unfavorable outcomes were namely admitting blood glucose levels, age, onset to EVT time, onset to hospital time, and National Institutes of Health Stroke Scale (NIHSS) scores (importance = 130.9, 102.6, 96.5, 89.5 and 84.4, respectively). According to AUC, we established the key cutoff points and constructed prediction scale based on their respective weightings. Then, the established prediction scale was verified in raw and external data and the sensitivity was 80.4 and 83.5%, respectively. Finally, scores >3 demonstrated better accuracy in predicting unfavorable outcomes. Conclusion: Presurgical prediction scale is feasible and accurate in identifying unfavorable outcomes of AIS after EVT.

Integrating Unexpected High Charge-Carrier Mobility and Low-Threshold Lasing Action in an Organic Semiconductor.

Integrating high charge-carrier mobility and low-threshold lasing action in an organic semiconductor is crucial for the realization of an electrically pumped laser, but remains a great challenge. Herein, we present an organic semiconductor, named as 2,7-di(2-naphthyl)-9H-fluorene (LD-2), which shows an unexpected high charge-carrier mobility of 2.7 cm2  V-1 s-1 and low-threshold lasing characteristic of 9.43 µJ cm-2 and 9.93 µJ cm-2 and high-quality factor (Q) of 2131 and 1684 at emission peaks of 420 and 443 nm, respectively. Detailed theoretical calculations and photophysical data analysis demonstrate that a large intermolecular transfer integral of 10.36-45.16 meV together with a fast radiative transition rate of 8.0×108  s-1 are responsible for the achievement of the superior integrated optoelectronic properties in the LD-2 crystal. These optoelectronic performances of LD-2 are among the highest reported low-threshold lasing organic semiconductors with efficient charge transport, suggesting its promise for research of electrically pumped organic lasers (EPOLs).

The RNA Directed DNA Methylation (RdDM) Pathway Regulates Anthocyanin Biosynthesis in Crabapple (Malus cv. spp.) Leaves by Methylating the McCOP1 Promoter.

The synthesis of anthocyanin pigments in plants is known to be regulated by multiple mechanisms, including epigenetic regulation; however, the contribution of the RNA-directed DNA methylation (RdDM) pathway is not well understood. Here, we used bisulfite sequencing and Real Time (RT)-quantitative (q) PCR to analyze the methylation level of the promoter of constitutively photomorphogenic 1 (McCOP1) from Malus cv. spp, a gene involved in regulating anthocyanin biosynthesis. The CHH methylation level of the McCOP1 promoter was negatively correlated with McCOP1 RNA expression, and inhibiting DNA methylation caused decreased methylation of the McCOP1 promoter and asymmetric cytosine CHH methylation. We observed that the McCOP1 promoter was a direct target of the RdDM pathway argonaute RISC component 4 (McAGO4) protein, which bound to a McCOP1 promoter GGTTCGG site. Bimolecular fluorescence complementation (BIFC) analysis showed that RNA-directed DNA methylation (McRDM1) interacted with McAGO4 and another RdDM protein, domains rearranged methyltransferase 2 (McDRM2), to regulate the CHH methylation of the McCOP1 promoter. Detection of CHH methylation and COP1 gene expression in the Arabidopsis thalianaatago4, atdrm2 and atrdm1 mutants showed that RDM1 is the effector of the RdDM pathway. This was confirmed by silencing McRDM1 in crabapple leaves or apple fruit, which resulted in a decrease in McCOP1 CHH methylation and an increase in McCOP1 transcript levels, as well as in anthocyanin accumulation. In conclusion, these results show that the RdDM pathway is involved in regulating anthocyanin accumulation through CHH methylation of the McCOP1 promoter.

Universal and versatile morphology engineering via hot fluorous solvent soaking for organic bulk heterojunction.

After explosive growth of efficiency in organic solar cells (OSCs), achieving ideal morphology of bulk heterojunction remains crucial and challenging for advancing OSCs into consumer market. Herein, by utilizing the amphiphobic nature and temperature-dependent miscibility of fluorous solvent, hot fluorous solvent soaking method is developed to optimize the morphology with various donor/acceptor combinations including polymer/small-molecule, all-polymer and all-small-molecule systems. By immersing blend film into hot fluorous solvent which is utilized as liquid medium with better thermal conductivity, the molecular reorganization is accelerated. Furthermore, fluorous solvent can be miscible with the residue of chloroform and chloronaphthalene above upper critical solution temperature. This mixed solvent diffuses around inside the active layer and selectively promotes molecular reorganization, leading to optimized morphology. Compared to widely-used thermal annealing, this approach processed under mild conditions achieves superior photovoltaic performance, indicating the practicality and universality for morphological optimization in OSCs as well as other optoelectronic devices.

A perylene diimide-containing acceptor enables high fill factor in organic solar cells.

A new non-fullerene acceptor PDFC is prepared by introducing perylene diimide into the core of an A-DA'D-A architecture. Due to the large conjugation and electron-deficient ability of perylene diimide, PDFC shows strong absorption, suitable energy levels and favorable face-on packing. The optimal device realizes a PCE of 12.56% with one of the highest fill factors (81.3%). A PCE of 9.66% is obtained in a 570 nm thick-film device based on PDFC.

Fe-Catalyzed decarbonylative cascade reaction of N-aryl cinnamamides with aliphatic aldehydes to construct 3,4-dihydroquinolin-2(1H)-ones.

A practical Fe-catalyzed decarbonylative cascade reaction of N-aryl cinnamamides with aliphatic aldehydes to provide C3 alkylated 3,4-dihydroquinolin-2(1H)-ones is developed. Aliphatic aldehydes were oxidatively decarbonylated into 1°, 2° and 3° alkyl radicals conveniently, allowing for the subsequent cascade construction of C(sp3)-C(sp3) and C(sp3)-C(sp2) bonds via radical addition and HAS-type cyclization. The importance of the amide linkage and the selectivity of the 6-endo-trig over 5-exo-trig cyclization pathway were elucidated by experimental results and DFT calculations.

[A pedigree study of a patient with primary pigmented nodular adrenocortical disease and familial gene mutation].

OBJECTIVE: To clarify the clinical features and genetic background of a kindred of primary pigmented nodular adrenocortical disease (PPNAD). METHODS: Detailed clinical characteristics and laboratory test results from a ten-year old girl diagnosed as PPNAD were collected. Seven members of her family were screened for Cushing syndrome and Carney complex, and their blood DNA was extracted and sequenced for PRKAR1A, PDE11A, PDE8B and CTNNB1 mutations with ABI3730. RESULTS: The girl presented with symptoms and signs of hypercortisolism, while no features of Carney complex were observed. Hypercortisolemia, suppressed corticotrophin and high urinary free cortisol level were revealed. Cortisol level could not be suppressed both in high and low dose dexamethasone suppression test. The diagnosis of adrenocorticotrophic hormone (ACTH)-independent Cushing syndrome was established. Image and pathology of adrenal glands were in accordance with PPNAD. Other family members showed no evidence of Cushing syndrome or Carney complex. DNA sequencing showed that the patient harbored a missense mutation, C18G. Her father and younger sister were proved to be carriers of this mutation. CONCLUSION: A Chinese PPNAD family was identified clinically and genetically, and a novel missense mutation of PRKAR1A was found.