Regioselective N-Trideuteromethylation of Tautomeric Polyaza Heterocycles.

Methods for regioselective N-trideuteromethylation of tautomeric polyaza heterocycles are highly sought-after. Disclosed herein is an N-trideuterated methylation reaction of imidazoles and pyrazoles with high regioselectivity and deuterium purity using easily available CF3SO3CD3 as the -CD3 source. This method enables the easy synthesis of important deuterium-labeled azoles, including dimetridazole-d3, ipronidazole-d3, hydroxy dimetridazole-d3, and ronidazole-d3.

Constructing eRNA-mediated gene regulatory networks to explore the genetic basis of muscle and fat-relevant traits in pigs.

BACKGROUND: Enhancer RNAs (eRNAs) play a crucial role in transcriptional regulation. While significant progress has been made in understanding epigenetic regulation mediated by eRNAs, research on the construction of eRNA-mediated gene regulatory networks (eGRN) and the identification of critical network components that influence complex traits is lacking. RESULTS: Here, employing the pig as a model, we conducted a comprehensive study using H3K27ac histone ChIP-seq and RNA-seq data to construct eRNA expression profiles from multiple tissues of two distinct pig breeds, namely Enshi Black (ES) and Duroc. In addition to revealing the regulatory landscape of eRNAs at the tissue level, we developed an innovative network construction and refinement method by integrating RNA-seq, ChIP-seq, genome-wide association study (GWAS) signals and enhancer-modulating effects of single nucleotide polymorphisms (SNPs) measured by self-transcribing active regulatory region sequencing (STARR-seq) experiments. Using this approach, we unraveled eGRN that significantly influence the growth and development of muscle and fat tissues, and identified several novel genes that affect adipocyte differentiation in a cell line model. CONCLUSIONS: Our work not only provides novel insights into the genetic basis of economic pig traits, but also offers a generalizable approach to elucidate the eRNA-mediated transcriptional regulation underlying a wide spectrum of complex traits for diverse organisms.

Application of Composite Tissue Flap Pedicled With Superficial Temporal Artery and its Branches in the Repair of Various Maxillofacial Defects.

OBJECTIVE: To discuss and study the application of composite tissue flaps pedicled with the superficial temporal artery (STA) and its branches in the repair of various defects, analyze the advantages and disadvantages of such composite tissue flaps, and provide a reference for the personalized design of various maxillofacial defect repairs. MATERIALS AND METHODS: In recent years, 12 cases of various maxillofacial defects were repaired with composite tissue flaps pedicled with the STA and its branches. The application strategies of this type of tissue flaps were summarized by summarizing experience and reviewing literature. RESULTS: According to the different defect characteristics of patients and the requirements of patients for surgery, different tissue flaps have been designed, and good results have been obtained. Except for 2 patients who developed dark purple skin flap within 48 hours after operation, the remaining patients were followed up for 6 to 24 months without serious complications. CONCLUSION: The composite tissue flap pedicled with the STA and its branches is a kind of functional tissue flap for facial defect repair. Individualized repair schemes can be designed according to different defect types of patients.

Application of Surgery-First Approach in Treating Skeletal Dentofacial Asymmetry with Orthognathic Surgery.

BACKGROUND: Skeletal dentofacial asymmetry decreases patient's attractiveness by deteriorating symmetry of facial appearance which is of great significance to individuals. Surgery-first orthognathic approach manifests its advantages of shortening treatment time and improving patient's quality of life. However, current literature on surgery-first approach mainly focuses on treating prognathism, overlooking its efficacy in improving facial symmetry of skeletal dentofacial asymmetry patients. This study aimed to assess SFA's efficacy in improving facial appearance by analyzing morphological features of asymmetric bone and facial soft tissue in a three-dimensional manner. METHODS: Thirty-four patients who received orthognathic surgery in a surgery-first fashion were included. Based on three-dimensional CT reconstruction, bilateral preoperative morphological features and postoperative symmetry of hard tissue were compared respectively. Efficacy of facial soft tissue symmetry restoration was evaluated using root mean square deviation (RMSD). RESULTS: Asymmetric features mainly located in menton, mandibular body length, angulation between ramus and midsagittal plane (MSP), distance between gonion and MSP and so on, which were significantly restored after the whole treatment. RMSD of facial soft tissue surface were significantly declined after the treatment and prognathism was corrected simultaneously if existed. CONCLUSIONS: Surgery-first orthognathic approach is proved to be capable of treating skeletal dentofacial asymmetry effectively and efficiently.

Application and Accuracy of Craniomaxillofacial Plastic Surgery Robot in Congenital Craniosynostosis Surgery.

OBJECTIVE: The objective of this study was to observe the accuracy and security of the craniomaxillofacial plastic surgery robot in congenital craniosynostosis surgery and to enhance and improve its performance. MATERIALS AND METHODS: We performed model surgical experiments on computed tomography data of 5 children with congenital craniosynostosis who were diagnosed and treated in our hospital, and model surgical experiments and animal experiments on the skulls of 3 Bama minipigs. RESULTS: There was no statistically significant difference shown either in model experiments or animal experiments in comparing the actual operation with the surgical simulation and inside the groups ( P >0.05). CONCLUSIONS: The craniomaxillofacial plastic surgery robot has achieved good security and accuracy in model surgery and animal experiments. Further studies are needed to be conducted to confirm its security and accuracy and to continuously improve and refine the robot's performance.

Comprehensive Serial Treatment of Treacher Collins Syndrome.

OBJECTIVE: To discuss and summarize the comprehensive serial surgical treatment of Treacher Collins syndrome. MATERIALS AND METHODS: From September 2012 to January 2020, 12 patients with Treacher Collins syndrome were treated by autologous fat graft, mandibular distraction osteogenesis, orbitozygomatic reconstruction with calvarial external lamina, orthognathic surgery combined with postoperative orthodontics, transplantation of upper eyelid orbicularis myocutaneous flap, lateral canthal ligament reduction, and other methods. The authors evaluated the postoperative improvement, summarized experiences, and reviewed literatures about the comprehensive serial treatment of Treacher Collins syndrome. RESULTS: All patients showed significant improvement in appearance and function, and no complications were found during the follow-up period of 5 months to 3 years. CONCLUSIONS: The deformities of Treacher Collins syndrome involves multiple craniofacial region, and only by formulating comprehensive serial treatment strategies according to the malformation characteristics of different patients can the best effect be achieved.

A Novel and Simplified Parameter for Mandible Angle Asymmetry Evaluation in Chinese Females.

AIM: To develop a novel and simplified parameter for mandible angle asymmetry (MAA) evaluation for facial countering surgeries in Chinese females. MATERIALS AND METHODS: A total of 250 craniofacial computer tomography of healthy Chinese individuals were collected in this retrospective study. Mimics 21.0 was applied for 3-dimensional anthropometry. The Frankfort and Green planes were set as referenced vertical and horizontal planes for measuring the distances to gonions. The differences in both orientations were analyzed to verify the symmetry. Mandible angle asymmetry (∠Go-N-ANS, MAA) which comprehensively represented horizontal and vertical placements was defined qas the novel parameter for asymmetric evaluation and quantitative analysis was conducted to generate referenced materials. RESULTS: Mandible angle asymmetry was divided into horizontal and vertical asymmetry. No significant differences were found in either horizontal or vertical orientations. The horizontal difference was 3.09±2.52 mm, the reference range was (0.28, 7.54) mm, whereas the±ertical difference was 2.59±2.48 mm, the reference range was (0.12, 6.34) mm. The difference of MAA was 1.74±1.30 degrees, and the reference range was (0.10,4.32）degrees. CONCLUSION: This study provided a novel parameter for asymmetric evaluation in the mandible angle region through quantitative 3-dimensional anthropometry, arousing plastic surgeons' attention to both aesthetics and symmetry in facial contouring surgery.

DeepSATA: A Deep Learning-Based Sequence Analyzer Incorporating the Transcription Factor Binding Affinity to Dissect the Effects of Non-Coding Genetic Variants.

Utilizing large-scale epigenomics data, deep learning tools can predict the regulatory activity of genomic sequences, annotate non-coding genetic variants, and uncover mechanisms behind complex traits. However, these tools primarily rely on human or mouse data for training, limiting their performance when applied to other species. Furthermore, the limited exploration of many species, particularly in the case of livestock, has led to a scarcity of comprehensive and high-quality epigenetic data, posing challenges in developing reliable deep learning models for decoding their non-coding genomes. The cross-species prediction of the regulatory genome can be achieved by leveraging publicly available data from extensively studied organisms and making use of the conserved DNA binding preferences of transcription factors within the same tissue. In this study, we introduced DeepSATA, a novel deep learning-based sequence analyzer that incorporates the transcription factor binding affinity for the cross-species prediction of chromatin accessibility. By applying DeepSATA to analyze the genomes of pigs, chickens, cattle, humans, and mice, we demonstrated its ability to improve the prediction accuracy of chromatin accessibility and achieve reliable cross-species predictions in animals. Additionally, we showcased its effectiveness in analyzing pig genetic variants associated with economic traits and in increasing the accuracy of genomic predictions. Overall, our study presents a valuable tool to explore the epigenomic landscape of various species and pinpoint regulatory deoxyribonucleic acid (DNA) variants associated with complex traits.

Treatment of Asymmetric Crying Face by Fascia lata Grafting.

OBJECTIVE: To evaluate and discuss the plastic surgery treatment of asymmetric crying face. METHODS: From 2019 to 2022, 60 patients with asymmetric crying face were treated by fascia lata grafting. We evaluated the postoperative improvement, summarized experiences and reviewed literatures about the treatment of asymmetric crying face. RESULTS: 59 patients showed varying degrees of improvement in the movement of the affected corner of mouth, and no complications were found during the follow-up period of 6 months to 24 months. CONCLUSIONS: The cause of asymmetric crying face is still uncertain. Fascia lata grafting has shown a certain effect in the treatment of asymmetric crying face. This study evaluated this method with quite large sample. More researches are needed to explore the most appropriate treatment for asymmetric crying face.

Medium-Ring Strategy Enables Multiple Resonance Emitters with Twisted Geometry and Fast Spin-Flip to Suppress Efficiency Roll-Off.

Suppressing aggregation-caused quenching (ACQ) effect and reducing device efficiency roll-off are both crucial yet challenging for multi-resonance (MR) emitters. Herein, we put forward a medium-ring strategy to design efficient MR emitters that feature heptagonal tribenzo[b,d,f]azepine (TBA) donors. The highly twisted conformation enlarges the intermolecular distances between the MR-emitting cores, and thus suppresses ACQ effect. Meanwhile, the introduction of heptagonal donors enhances spin-orbital coupling, so as to accelerate reverse intersystem crossing (RISC) process. This medium-ring strategy gives rise to the first example of blue MR emitter that simultaneously possesses radiative decay rate as fast as 108  s-1 and RISC rate as fast as 106  s-1 . Accordingly, DTBA-B2N3 enables to assemble high-performance blue organic light-emitting diodes (OLEDs) with maximum external quantum efficiency (EQEmax ) of 30.9 % and alleviated efficiency roll-off (EQE1000 : 20.5 %).

Accuracy and Security Analysis of a Cranio-Maxillofacial Plastic Surgery Robot Equipped with Piezosurgery in Genioplasty.

ABSTRACT: This study aims to verify that the craniofacial plastic surgery robot with piezosurgery is more accurate and safer than traditional operations in genioplasty. This study chose data from the Digital Plastic Surgery of Plastic Surgery Hospital in the Chinese Academy of Medical Sciences and Peking Union Medical College. The CT data of the patient's skull were reconstructed in the software, and the authors designed the measurement index. The surgical plan was designed as an ideal scheme (control group). Patients underwent traditional surgery according to the preoperative surgery plan (clinical group). Guided by surgical navigation, the osteotomy was operated on patients' same size plaster model using the surgery robot equipped with a piezosurgery (robot group). At last, the accuracy was calculated by CT data. There was no significant difference between the robotic group and control groups in the postoperative measurement index (P < 0.05). There was no significant difference between the robotic group and the control group (P > 0.05) in the line of osteotomy, but there was a significant difference between the clinical group and the control group in the line of the osteotomy.

Modified Intramolecular-Lock Strategy Enables Efficient Thermally Activated Delayed Fluorescence Emitters for Non-Doped OLEDs.

The development of intramolecular-lock strategy is an appealing task for designing efficient thermally activated delayed fluorescence (TADF) molecules, but only limited examples have been reported so far. Herein we present a "medium ring"-lock strategy to develop TADF emitters for improving the efficiency of organic light-emitting diodes (OLEDs). The installation of an electron-deficient heptagonal diimide lock onto a highly rotatable biphenyl-based emitter not only enhances electron-withdrawing ability of acceptor that decreases singlet-triplet energy gap (ΔEST ), but also endows the skeleton with modest rigidity and flexibility that increases photoluminescence quantum yield (PLQY) in neat film. In particular, the integration of the diimide lock also leads to an increase in horizontal orientation factor (Θ// ) from 69 % to 83 %. Consequently, this modified intramolecular-lock strategy enables an efficient TADF emitter to assemble high-performance non-doped OLEDs with a high external quantum efficiency of 26.2 % and a power efficiency of 76.6 lm W-1 .

Structurally Nontraditional Benzo[c]cinnoline-Based Electron-Transporting Materials with 3D Molecular Interaction Architecture.

The academically widely used electron-transporting materials (ETMs) typically suffer from low glass transition temperatures (Tg ) that could lead to poor device stability. Considering practical applications, we herein put forward a "3D molecular interaction architecture" strategy to design high-performance ETMs. As a proof-of-concept, a type of structurally nontraditional ETMs with the benzo[c]cinnoline (BZC) skeleton have been proposed and synthesized by the C-H/C-H homo-coupling of N-acylaniline as the key step. 2,9-diphenylbenzo[c]cinnoline (DPBZC) exhibits strong intermolecular interactions that feature a 3D architecture, which boosts Tg to exceedingly high 218 °C with a fast electron mobility (µe ) of 6.4×10-4  cm2 V-1 s-1 . DPBZC-based fluorescent organic light-emitting diodes show outstanding electroluminescent performances with an external quantum efficiency of 20.1 % and a power efficiency as high as 70.6 lm W-1 , which are superior to those of the devices with the commonly used ETMs.

Space-Confined Donor-Acceptor Strategy Enables Fast Spin-Flip of Multiple Resonance Emitters for Suppressing Efficiency Roll-Off.

Multi-resonance boron-nitrogen-containing thermally activated delayed fluorescence (MR-TADF) emitters have experienced great success in assembling narrowband organic light-emitting diodes (OLEDs). However, the slow reverse intersystem crossing rate (kRISC ) of MR-emitters (103 -105  s-1 ) that will lead to severe device efficiency roll-off has received extensive attention and remains a challenging issue. Herein, we put forward a "space-confined donor-acceptor (SCDA)" strategy to accelerate RISC process. The introduction of SCDA units onto the MR-skeleton induces intermediate triplet states, which leads to a multichannel RISC process and thus increases kRISC . As illustrated examples, efficient MR-emitters have been developed with a sub-microsecond delayed lifetime and a high kRISC of 2.13×106  s-1 , which enables to assemble high-performance OLEDs with a maximum external quantum efficiency (EQEmax ) as high as 32.5 % and an alleviated efficiency roll-off (EQE1000 : 22.9 %).

One-Half Wedge Osteotomy Genioplasty for Correction of Chin Deviation Based on Three-Dimensional Computed Tomography Measurements and Simulation.

ABSTRACT: Conventional operations correcting chin deviations mainly rely on the observation and experience of the surgeons during the operation. We have created a new surgical method, one-half wedge osteotomy genioplasty (1/2WOG), that combines three-dimensional computed tomography measurements and simulation. This study evaluated the clinical effect of chin deviation correction with the 1/2WOG method. A total of 38 patients (15 men and 23 women) who underwent 1/2WOG between October 2019 and October 2014 were evaluated. The chin deviation angle and distance, and partial chin deformity were measured preoperatively using three-dimensional computed tomography data. Precise calculations and osteotomy lines were achieved by preoperative simulation. All patients underwent the same surgery by the same surgical team. The clinical effect of 1/2WOG was evaluated according to the preoperative and postoperative data and patient satisfaction. All 38 patients achieved satisfactory aesthetic results without major complications such as chin nerve injury or bone nonunion. Eight patients occured numbness of the lower lip after surgery; at 6-month follow-up, the numbness was reduced in 2 patients and disappeared in 6 patients. Compared with preoperative data, the chin deviation angle, chin deviation distance, and gonion-menton difference were significantly reduced postoperatively. During the 12-month follow-up, the patient satisfaction rate reached 90%. We conclude that chin deviation can be improved by 1/2WOG. The combination of digital technology measurements and simulation can increase the accuracy of the osteotomy line design, thus reducing surgical trauma and increasing patient satisfaction, which is worthy of clinical promotion.

Efficient metal-free aminoiodination of alkenes with N-fluorobenzenesulfonimide under mild conditions.

A novel efficient metal-free aminoiodination of alkenes with N-fluorobenzenesulfonimide (NFSI) through an iodonium intermediate under mild conditions with good regioselectivity and stereoselectivity is reported. Unlike transition-metal catalysed aminative bisfunctionalization with NFSI in which the oxidative addition of NFSI to transition-metals affords an electrophilic amino radical, the oxidation of anionic iodide by NFSI in situ generates an electrophilic iodine cation and an amino nucleophile to fulfil this efficient reaction. 2,2,6,6-Tetramethyl-piperidine-1-oxyl (TEMPO) could considerably promote this iodoamination at room temperature. A preliminary trial suggests that bromoamination could also be achieved under similar conditions.

Lymph node ratio (LNR) as a complementary staging system to TNM staging in salivary gland cancer.

PURPOSE: The role of lymph node ratio (LNR, ratio of metastatic to examined nodes) in the staging of multiple human malignancies has been reported. We aim to evaluate its value in salivary gland cancer (SGC). METHODS: Records of SGC patients from Surveillance, Epidemiology, and End Results database (SEER, training set, N = 4262) and Fudan University Shanghai Cancer Center (FUSCC, validating set, N = 154) were analyzed for the prognostic value of LNR. Kaplan-Meier survival estimates, the Log-rank χ2 test and Cox proportional hazards model were used for univariate and multivariate analysis. Optimal LNR cutoff points were identified by X-tile. RESULTS: Optimal LNR cutoff points classified patients into four risk groups, R0, R1 (≤ 0.17), R2 (0.17-0.56) and R3 (> 0.56), corresponding to 5-year cause-specific survival in SEER patients of 88.6%, 57.2%, 53.1% and 39.7%, disease-free survival in FUSCC patients of 69.2%, 63.3%, 34.6% and 0%, and disease-specific survival in FUSCC patients of 92.3%, 90.0%, 71.4% and 0%, respectively. Compared with TNM staging, TNM + R staging showed smaller AIC values and higher C-index values in the Cox regression model in both patient sets. CONCLUSIONS: LNR classification should be considered as a complementary system to TNM staging and LNR classification based clinical trials deserve further research.

Central Lymph Node Status has Significant Prognostic Value in the Clinically Node-Negative Tall-Cell Variant of Papillary Thyroid Cancer Regardless of T-Staging and Radioactive Iodine Administration: First Evidence From a Population-Based Study.

BACKGROUND: The prognostic value of central lymph node (CLN) status in papillary thyroid cancer (PTC) remains controversial. This study aimed to provide the first evidence on this issue for the aggressive tall-cell variant (TCV) subtype. METHODS: The study identified TCV patients from the Surveillance, Epidemiology, and End Results database. The Kaplan-Meier method, log-rank test, and multivariate Cox regression models were used for analysis. RESULTS: Of the 744 patients included, 404 were recorded as N0, which were pathologically or only clinically confirmed. Overall survival (OS) and cancer-specific survival (CSS) did not differ significantly between the N0 and pN1a patients (p > 0.05). To investigate the reason, the N0 patients were subdivided according to the number of examined lymph nodes (ELN). The patients with a N0 diagnosis confirmed by two or more ELNs (N0-e2+) showed significantly better outcomes than the pN1a patients and their N0 counterparts without ELN (N0-e0) (p < 0.05), whereas the N0-e0 and pN1a groups demonstrated comparable outcomes in both the log-rank and multivariate analyses (p > 0.05). Moreover, the subgroup analyses showed that even among the patients with early T-staging (T1-T2) or receipt of radioactive iodine (RAI) therapy, the N0-e0 patients still demonstrated compromised OS compared with the N0-e2+ group (p < 0.05). CONCLUSION: The cN0 patients without ELN (N0-e0) had outcomes similar to those of the pN1a patients, but showed a poorer OS than the N0-e2+ group regardless of T-staging and RAI administration, suggesting that occult CLN metastases might act as a negative prognosticator in cN0 TCV. Therefore, prophylactic central neck dissection might be considered for biopsy-proven cN0 TCV patients. Prospective studies are expected to further validate our conclusions.

NFSI-participated intermolecular aminoazidation of alkene through iron catalysis.

An iron-catalysed intermolecular vicinal aminoazidation of alkenes, using N-fluorobenzenesulfonimide (NFSI) and trimethylsilyl azide (TMSN3) as the imidating and azidating reagents, respectively, is described, which could potentially provide a valuable route toward diverse vicinal diamine derivatives of great significance in medicinal chemistry and organic synthesis. Such iron-catalysed aminative bisfunctionalization of alkenes with NFSI has not been reported yet. Comparing to previously employed copper or palladium catalysts, the iron catalyst, FeCl2, was demonstrated to be a good alternative for its comparable efficiency and broad alkene scope. Preliminary mechanistic study suggested that this iron-catalysed reaction is realized through radical processes.

DDQ-promoted direct C5-alkylation of oxazoles with alkylboronic acids via palladium-catalysed C-H bond activation.

A novel and concise C5-alkylation of oxazoles using alkylboronic acids as alkyl donors via Pd(ii)-catalysed C-H bond activation has been achieved in moderate to good yields with satisfactory functional group tolerance. Instead of commonly used BQ as a key promoter, DDQ was discovered to be a better additive that significantly promoted this alkylation. This efficient and advanced method represents the first C(sp2)-C(sp3) cross-coupling reaction at the C5-position of oxazoles, which is particularly attractive due to its potential applications in the late-stage functionalization of oxazole-containing bioactive molecules.