One-Pot Synthesis of Chiral 1-Aryl-2-Aminoethanols via Ir-Catalyzed Asymmetric Hydrogenation.

A straightforward synthesis approach to chiral 1-aryl-2-aminoethanols via the one-pot asymmetric hydrogenation catalyzed by Ir catalyst was developed. This tandem process involves the in situ generation of α-amino ketones via the nucleophilic substitution of α-bromoketones with amines and the Ir-catalyzed asymmetric hydrogenation of ketone intermediates to provide diverse enantiomerically enriched ß-amino alcohols. The excellent yields and enantioselectivities (up to 96 % yield and up to >99 % ee) with a wide substrate scope in this one-pot strategy were obtained.

Iridium-Catalyzed Asymmetric Hydrogenation of Simple Ketones with Tridentate PNN Ligands Bearing Unsymmetrical Vicinal Diamines.

An iridium catalytic system with a ferrocene-based phosphine ligand bearing a modular and tunable unsymmetrical vicinal diamine scaffold was developed for the asymmetric hydrogenation of aryl ketones. This approach provided a powerful tool for the enantioselective synthesis of diverse chiral alcohols with excellent reactivity and enantioselectivity (up to 99% yield, up to 99% ee, and up to 50,000 turnover number). The substituents and chirality of unsymmetrical diamines in ligands played an important role in the satisfactory results.

Study on the correlation between early three-dimensional gait analysis and clinical efficacy after robot-assisted total knee arthroplasty.

PURPOSE: Robot-assisted technology is a forefront of surgical innovation that improves the accuracy of total knee arthroplasty (TKA). But whether the accuracy of surgery can improve the clinical efficacy still needs further research. The purpose of this study is to perform three-dimensional (3D) analysis in the early postoperative period of patients who received robot-assisted total knee arthroplasty (RATKA), and to study the trend of changes in gait parameters after RATKA and the correlation with the early clinical efficacy. METHODS: Patients who received RATKA in the Center of Joint Surgery, the First Hospital Affiliated to Army Military Medical University from October 2020 to January 2021 were included. The imaging parameters, i.e., hip-knee-ankle angle, lateral distal femoral angle, medial proximal tibial angle, posterior condylar angle were measured 3 months post-TKA. The 3D gait analysis and clinical efficacy by Western Ontario Mac Master University Index (WOMAC) score were performed pre-TKA, 3 and 6 months post-TKA. The differences in spatiotemporal parameters of gait, kinetic parameters, and kinematic parameters of the operated limb and the contralateral limb were compared. The correlation between gait parameters and WOMAC scores was analyzed. Paired sample t-test and Wilcoxon rank-sum test were used to analyze the difference between groups, and Spearman correlation coefficient was used to analyze the correlation. RESULTS: There were 31 patients included in this study, and the imaging indexes showed that all of them returned to normal post-TKA. The WOMAC score at 3 months post-TKA was significantly lower than that pre-TKA, and there was no significant difference between at 3 and 6 months. The 3D gait analysis results showed that the double support time of the operated limb reduced at 3 and 6 months (all p < 0.05), the maximum extension and maximum external rotation of the knee joint increased at stance phase, and the maximum flexion angle, the range of motion and the maximum external rotation increased at swing phase. Compared with the preoperative data, there were significant improvements (all p < 0.05). Compared with the contralateral knee joint, the maximum external rotation of the knee joint at swing phase was smaller than that of the contralateral side, and the maximum flexion and extension moment was greater than that of the contralateral knee. The maximum external rotation moment of the joint was greater than that of the contralateral knee joint (p < 0.05). There was a negative correlation between the single support time pre-TKA and the WOMAC score at 3 months (p = 0.017), and the single support time at 3 months was negatively correlated with the WOMAC score at 6 months (p = 0.043). The cadence at 6 months was negatively correlated with the WOMAC score at 6 months (p = 0.031). The maximum knee extension at stance phase at 6 months was negatively correlated with the WOMAC score at 6 month (p = 0.048). The maximum external rotation at stance phase at 6 months was negatively correlated with the WOMAC score at 6 months (p = 0.024). CONCLUSION: The 3D gait analysis of RATKA patients is more sensitive than WOMAC score in evaluating the clinical efficacy. Trend of changes in gait parameters shows that the knee joint support, flexion and extension function, range of motion, external rotation and varus deformity moment of the patient were significantly improved at 3 months after surgery, and continued to 6 months after surgery. Compared with the contralateral knee, the gait parameters of the operated limb still has significant gaps in functionality, such as the external rotation and flexion and extension. The single support time, cadence, knee extension, and knee external rotation of the operated limb have a greater correlation with the postoperative WOMAC score. Postoperative rehabilitation exercises should be emphasized, which is of great value for improving the early efficacy of RATKA.

Synthesis of Phenols from Aryl Ammonium Salts under Mild Conditions.

A general method for the synthesis of phenols from electron-deficient aryl ammonium salts or heteroaryl ammonium salts under mild conditions was developed. Benzaldehyde oxime, acetohydroxamic acid, and hydroxylamine hydrochloride were investigated as hydroxide surrogates respectively. With these hydroxide surrogates, a series of phenols were prepared in yields of 20-98%.

Synthesis of triarylphosphines from arylammonium salts via one-pot transition-metal-free C-P coupling.

A nucleophilic aromatic substitution (SNAr) reaction that allowed transition-metal-free C-P bond construction via C-N bond cleavage was developed. The coupling between aryltrimethylammonium salts and secondary phosphines from the in situ reduction of diarylphosphine oxides led to the formation of diverse triarylphosphines with various functional groups. This one-pot process was not only a pertinent SNAr precedent but also a favorable transition-metal-free alternative for C-P coupling.

A Nuclear Factor Y-B Transcription Factor, GmNFYB17, Regulates Resistance to Drought Stress in Soybean.

Soybean is sensitive to drought stress, and increasing tolerance to drought stresses is an important target for improving the performance of soybean in the field. The genetic mechanisms underlying soybean's drought tolerance remain largely unknown. Via a genome-wide association study (GWAS) combined with linkage analysis, we identified 11 single-nucleotide polymorphisms (SNPs) and 22 quantitative trait locus (QTLs) that are significantly associated with soybean drought tolerance. One of these loci, namely qGI10-1, was co-located by GWAS and linkage mapping. The two intervals of qGI10-1 were differentiated between wild and cultivated soybean. A nuclear factor Y transcription factor, GmNFYB17, was located in one of the differentiated regions of qGI10-1 and thus selected as a candidate gene for further analyses. The analysis of 29 homologous genes of GmNFYB17 in soybean showed that most of the genes from this family were involved in drought stress. The over-expression of GmNFYB17 in soybean enhanced drought resistance and yield accumulation. The transgenic plants grew better than control under limited water conditions and showed a lower degree of leaf damage and MDA content but higher RWC, SOD activity and proline content compared with control. Moreover, the transgenic plants showed a fast-growing root system, especially regarding a higher root-top ratio and more branching roots and lateral roots. The better agronomic traits of yield were also found in GmNFYB17 transgenic plants. Thus, the GmNFYB17 gene was proven to positively regulate drought stress resistance and modulate root growth in soybean. These results provide important insights into the molecular mechanisms underlying drought tolerance in soybean.

Robotic arm-assisted arthroplasty: The latest developments.

Joint arthroplasty is an effective method for treating end-stage joint lesions and damages. Robotic arm-assisted arthroplasty, a rapidly developing technology that combines navigation technology, minimally invasive technology, and precise control technology of the robotic arm, can achieve accurate preoperative planning, optimal selection of implants, minimally invasive surgery, precise osteotomy, and accurate placement of the artificial joint. It has the characteristics of high accuracy and stability, and thus is more and more widely used in the field of joint surgery. In this paper, we systematically reviewed the application and clinical efficacy of robotic arm-assisted technology in hip and knee arthroplasty to provide reference for its future promotion.

Primary amine catalyzed diastereo- and enantioselective Michael reaction of thiazolones and α,ß-unsaturated ketones.

The chiral primary amine catalyzed asymmetric Michael reaction of thiazolones and α,ß-unsaturated ketones was reported. Two different optimal catalytic systems were obtained corresponding to cyclic and linear α,ß-unsaturated ketones. By employing chiral primary amines as the catalysts and amino-acid derivatives as the additives, a variety of Michael adducts containing the scaffold of the thiazole ring were prepared in moderate to good yields and with excellent diastereo- and enantioselectivities (up to 95% yield, all up to >19/1 dr, up to 96% ee). The reaction was scaled up to obtain 1.73 grams of the Michael adduct with the maintenance of yield and stereoselectivity.

Semiactive robotic-arm system versus patient-specific instrumentation in primary total knee arthroplasty: Efficacy and accuracy.

OBJECTIVE: To compare the difference in efficacy and accuracy during total knee arthroplasty (TKA) among robotic-arm system, patient-specific instrumentation (PSI) and conventional TKA (COTKA). METHODS: Retrospective analysis of 90 advanced knee osteoarthritis (OA) patients in our hospital between June 2019 and December 2020 was conducted. Patients were divided into robotic arm-assisted (RA)TKA (group A), PSITKA (group B) and COTKA (group C), 30 cases in each group. The operation time, intraoperative bleeding, and length of hospital stay were counted. Imaging data of hip-knee-ankle angle (HKA), posterior condylar angle (PCA), lateral distal femoral angle (LDFA), medial proximal tibial angle (MPTA), and sagittal tibial component angle (sTCA) were statistically analyzed. The postoperative recovery of the patients was evaluated by Knee Society Score (KSS) and the Western Ontario Mac Master University Index Score (WOMAC). RESULTS: Group A had the least intraoperative bleeding. For operation time, group A was the longest compared with group B and group C (P < 0.05), while group B was longer than group C (P < 0.05). There was no significant difference in HKA, LDFA, and MPTA among the three groups, and the lower limb alignments were all restored to the neutral position. PCA of group A and B were both smaller than that of group C and closer to 0° (P < 0.05), but the difference between group A and B was not statistically significant. The sTCA in group A was significantly better than group B, and group B was significantly better than group C (P < 0.05). There were no significant differences in function scores among the three groups. CONCLUSION: Compared to the PSI and CO, RA is more minimally invasive and more accurate in radiographic results.

3D-printed external fixation guide combined with video-assisted thoracoscopic surgery for the treatment of flail chest: a technical report and case series.

Background: Flail chest is a common and serious traumatic condition in thoracic surgery. The treatment of flail chest often includes open reduction and internal fixation, which is relatively traumatic, complicated, and expensive. As three-dimensional (3D) printing technology is widely used in the clinical field, the application of 3D-printed products to chest trauma will become a new treatment option. To date, the use of 3D-printed external fixation guides for flail chests has not been reported. Thus, we aimed to assess the short-term efficacy of a new technology that treated flail chests with an individualized 3D-printed external fixation guide combined with video-assisted thoracoscopic surgery (VATS). Patients and methods: A retrospective analysis was performed on patients with flail chest treated with this new technique at our center from January 2020 to December 2022. The following parameters were included: operative time, thoracic tube extraction time, intensive care unit time, thoracic volume recovery rate, visual analog scale score 1 month postoperatively, and postoperative complication rate. All patients were followed up for at least 3 months. Results: Five patients (mean age: 45.7 years) were enrolled; they successfully underwent surgery without chest wall deformity and quickly returned to daily life. The average number of rib fractures was 8.4; all patients had lung contusion, hemopneumothorax, and anomalous respiration. The abnormal breathing of all patients was completely corrected on postoperative day 1, and the chest wall was stable. One case experienced mild loosening of the 3D-printed guide postoperatively; however, the overall stability was not affected. The other four cases did not experience such loosening because we replaced the ordinary silk wire with a steel wire. All cases were discharged from the hospital 2 weeks postoperatively and returned to normal life 1 month after the removal of the 3D-printed guide on average. Only one case developed a superficial wound infection postoperatively, and no perioperative death occurred. Conclusions: The 3D-printed external fixation guide combined with video-assisted thoracoscopic surgery is a novel technique in the treatment of flail chest and is safe, effective, feasible, and minimally invasive, with satisfactory clinical efficacy.

Direct electrochemical synthesis of quinones from simple aromatics and heteroaromatics.

We developed an electrochemical strategy for the synthesis of quinones through direct oxidation of widely accessible arenes and heteroarenes under mild conditions. A variety of quinones and hetero quinones were prepared with moderate to good yields, without the involvement of the pre-functionalized substrates. In addition, this atom economic method also exhibits wide functional group tolerance, including C(sp2)-I bond, ester, aldehyde, and OTf groups. This synthetic approach provides a straightforward and atom economic method for the transformation of C(sp2)-H bonds.

[Progress on nitrogen regulation gene expression of plant pathogenic fungi under nitrogen starvation].

It has been confirmed that the occurrence of plant disease is caused by the effector molecules secreted by plant pathogens. The regulation effector gene expression is an important aspect in understanding of the infection process. The nutritional status of cells has been postulated to be a vital role for effector gene expression. Studies have indicated that the induction of the same effecter genes during growth in vitro as those during growth in planta under nitrogen-starved conditions. This showed that the nitrogen poor environment existed in the early time of plant evolution. This paper describes the system in the pathogenesis of several fungal pathogens and nitrogen in the process of gene expression effects from the results of several species by comparing and contrasting the function of nitrogen regulatory genes, as well as by studying plants in vivo and in vitro gene under nitrogen limitation inductive effect in order to reveal the effectiveness of nitrogen in the development process of host plant disease is an important factor.

Rapid Synthesis of α-Chiral Piperidines via a Highly Diastereoselective Continuous Flow Protocol.

A practical continuous flow protocol has been developed using readily accessible N-(tert-butylsulfinyl)-bromoimine and Grignard reagents, providing various functionalized piperidines (34 examples) in superior results (typically >80% yield and with >90:10 dr) within minutes. The high-performance scale-up is smoothly carried out, and efficient synthesis of the drug precursor further showcases its utility. This flow process offers rapid and scalable access to enantioenriched α-substituted piperidines.

Genome-Wide Association Analysis and Gene Mining of Resistance to China Race 1 of Frogeye Leaf Spot in Soybean.

Soybean frogeye leaf spot (FLS) is a worldwide fungal disease. Its higher occurrence frequency and wider distribution range always led to severe yield losses of soybean, therefore, breeding new cultivars with FLS resistance has been an important breeding goal for soybean breeders. In this study, an association panel of 183 representative soybean accessions was used to evaluate their resistance to FLS race 1, and to identify quantitative trait nucleotides (QTNs) and candidate genes based on genome-wide association study (GWAS) and high-throughput single-nucleotide polymorphisms (SNPs). A total of 23,156 high-quality SNPs were developed using the specific locus-amplified fragment sequencing (SLAF-seq) approach. Finally, 13 novel association signals associated with FLS race 1 resistance were identified by the compressed mixed linear model (CMLM). In addition, 119 candidate genes were found within the 200-kb flanking genomic region of these 13 peak SNPs. Based on the gene-based association analysis, haplotype analysis, expression pattern analysis, and virus-induced gene silencing (VIGS) systems, four genes (Glyma.05G121100, Glyma.17G228300, Glyma.19G006900, and Glyma.19G008700) were preliminarily proved to play an important role in the soybean resistance to FLS race 1.

A Newly Designed "SkyWalker" Robot Applied in Total Knee Arthroplasty: A Retrospective Cohort Study for Femoral Rotational Alignment Restoration.

OBJECTIVE: This study explored whether robotic arm-assisted total knee arthroplasty (RATKA) has the advantage of restoring femoral rotational alignment compared to conventional total knee arthroplasty (COTKA). METHODS: Sixty patients (45 women and 15 men) attending our department from May 2019 to December 2020 were selected and divided into two groups, with 30 patients in each group, according to whether they underwent COTKA or RATKA. Femoral rotational alignment results, such as, posterior condylar angle (PCA), patella transverse axis-femoral transepicondylar axis angle (PFA), radiological findings, such as, hip-knee-ankle angle (HKA), lateral distal femoral angle (LDFA), and medial proximal tibial angle (MPTA), and operative data (operation time, intraoperative blood loss, tourniquet time, and length of stay (LOS), and clinical outcomes, such as maximum knee flexion angle (MKFA), Knee Society Score (KSS), and Western Ontario Mac Master University Index Score (WOMAC) were compared within and between the two groups. RESULTS: PCA and PFA in the RATKA group were (0.6 ± 0.3)° and (0.9 ± 0.3)°, respectively, which were smaller than (1.5 ± 2.0)° and (3.1 ± 1.1)° in the COTKA group (P < 0.05), and were closer to 0°; the differences in HKA, LDFA, and MPTA were not statistically significant. With the exception of the LDFA, the HKA, MPTA, PCA, and PFA improved in both groups after surgery (P < 0.05). The blood loss and the LOS of RATKA group were 192.3 ± 23.1 mL and 8.2 ± 1.4 days, which were less than 203.7 ± 29.8 mL and 9.3 ± 1.1 days of the COTKA group, but the operation time showed no statistically significant difference, and the tourniquet time was longer (P < 0.05). The MKFA in the RATKA group was (123.0 ± 3.7)°, which was greater than (116.3 ± 4.6)° in the COTKA group (P < 0.05). In terms of scores, the postoperative results were better than the preoperative results in both groups (P < 0.05). However, there was no statistically significant difference between the groups. CONCLUSION: The accuracy of femoral rotational alignment reconstructed achieved by RATKA is significantly better than that of COTKA and is more conducive to the recovery of knee flexion function after surgery; although RATKA reduces intraoperative blood loss and postoperative LOS, the short-term clinical efficacy comparison has not yet demonstrated the advantages of robotic technology, and a more optimized design is needed to improve the efficiency of RATKA surgery.

Electricity-driven three-component reductive coupling reaction for the synthesis of diarylmethylamine.

A three-component reductive coupling reaction of aldehydes, amines and cyanopyridines under electrochemical conditions has been developed. The in situ generated imine and cyanopyridine simultaneously undergo single-electron reduction at the cathode, and afford diarylmethylamines through radical coupling without the participation of reducing agents. The one-pot electrolysis method can modularly obtain various secondary and tertiary amines and exhibits broad functional group compatibility. Mechanistic experiments verify the pivotal reduction step from imine to α-amino radical and reveal the key role of benzoic acid in reducing the reduction potential of imine and cyanopyridine.

Ritter-type amination of C(sp3)-H bonds enabled by electrochemistry with SO42.

By merging electricity with sulfate, the Ritter-type amination of C(sp3)-H bonds is developed in an undivided cell under room temperature. This method features broad substrate generality (71 examples, up to 93% yields), high functional-group compatibility, facile scalability, excellent site-selectivity and mild conditions. Common alkanes and electron-deficient alkylbenzenes are viable substrates. It also provides a straightforward protocol for incorporating C-deuterated acetylamino group into C(sp3)-H sites. Application in the synthesis or modification of pharmaceuticals or their derivatives and gram-scale synthesis demonstrate the practicability of this method. Mechanistic experiments show that sulfate radical anion, formed by electrolysis of sulfate, served as hydrogen atom transfer agent to provide alkyl radical intermediate. This method paves a convenient and flexible pathway for realizing various synthetically useful transformations of C(sp3)-H bonds mediated by sulfate radical anion generated via electrochemistry.

[Genome-wide analysis of the secreted proteins of phytophthora infestans].

Based on the Phytophthora infestans genome sequence, we used bioinformatics and computer-based prediction algorithms to predict the secreted proteins of P infestans in detail, which would help us to elucidate the molecular mechanism underlying the interaction between the host plants and the P infestans. In this study, the signal peptide prediction algorithms SignalP v3.0 and PSORT, transmembrane helix prediction algorithms TMHMM-2.0 and THUMBUP, GPI-anchoring site prediction algorithm big-PI Predictor, and subcellular protein location distribution algorithm TargetP v1.01 were used to analyze the 22658 protein sequences of P infestans published. Our results suggested that there might be 671 secreted pro- teins, accounting for 3.0% of the total proteins. Among them, the functions of the 45 secreted proteins had been described previously. Their functions involved cellular metabolism and signal transduction etc. In addition, some of the secreted proteins were functionally similar to elicitin, which were likely to be associated with the virulence of P. infestans.

[Effect of robotic-arm assisted total knee arthroplasty on femoral rotation alignment and its short-term effectiveness].

OBJECTIVE: To investigate the improvement of femoral rotation alignment in total knee arthroplasty (TKA) by robotic-arm assisted positioning and osteotomy and its short-term effectiveness. METHODS: Between June 2020 and November 2020, 60 patients (60 knees) with advanced osteoarthritis of the knee, who met the selection criteria, were selected as the study subjects. Patients were randomly divided into two groups according to the random number table method, with 30 patients in each group. Patients were treated with robotic-arm assisted TKA (RATKA) in trial group, and with conventional TKA in control group. There was no significant difference in gender, age, side and course of osteoarthritis, body mass index, and the preoperative hip-knee-ankle angle (HKA), lateral distal femoral angle (LDFA), medial proximal tibial angle (MPTA), posterior condylar angle (PCA), knee society score-knee (KSS-K) and KSS-function (KSS-F) scores between the two groups ( P>0.05). The clinical (KSS-K, KSS-F scores) and imaging (HKA, LDFA, MPTA, PCA) evaluation indexes of the knee joints were compared between the two groups at 3 months after operation. RESULTS: All patients were successfully operated. The incisions in the two groups healed by first intention, with no complications related to the operation. Patients in the two groups were followed up 3-6 months, with an average of 3.9 months. KSS-K and KSS-F scores of the two groups at 3 months after operation were significantly higher than those before operation ( P<0.05), but there was no significant difference between the two groups ( P>0.05). X-ray re-examination showed that the prosthesis was in good position, and no prosthesis loosening or sinking occurred. HKA, MPTA, and PCA significantly improved in both groups at 3 months after operation ( P<0.05) except LDFA. There was no significant difference in HKA, LDFA, and MPTA between the two groups ( P>0.05). PCA in trial group was significantly smaller than that in control group ( t=2.635， P=0.010). CONCLUSION: RATKA can not only correct knee deformity, relieve pain, improve the quality of life, but also achieve the goal of restoring accurate femoral rotation alignment. There was no adverse event after short-term follow-up and the effectiveness was satisfactory.

[Application and research progress of robotic-arm in total knee arthroplasty].

OBJECTIVE: To summarize the application and research progress of robotic-arm in total knee arthroplasty (TKA). METHODS: Relevant literature at home and abroad was extensively reviewed to analyze the advantages and disadvantages of robotic-arm assisted TKA (RATKA). RESULTS: Accurate reconstruction of lower extremity alignment and rotation alignment, accurate osteotomy and implant prosthesis in TKA are very important to improve the effectiveness and prolong the life of the prosthesis. Traditional TKA deviations occur in key links such as osteotomy due to operator's operation. RATKA solves the above problems to a certain extent and can assist accurate osteotomy and implant prosthesis, and protect the soft tissues around the knee joint. Patients' satisfaction after RATKA is high, and the operator's learning curve is shorter, which improves the efficiency of the operation. But it also has disadvantages such as prolonged operation time, increased complications and medical costs. CONCLUSION: Preliminary clinical application studies have shown that RATKA has satisfactory effectiveness, but its definite advantages compared with traditional TKA need to be confirmed by a large number of randomized controlled trials and long-term follow-up.