Carbene-Catalyzed Enantioselective Addition of Sulfinate to Ketones.

A carbene-catalyzed enantioselective addition of sulfinate to ketones between 2-benzoylbenzaldehyde and sulfonyl chloride is disclosed. Up to now, the carbon and heteroatom nucleophiles have effectively undergone catalytic enantioselective addition to carbonyl molecules to introduce functionalities and chirality. Sulfone, as an important class of sulfur-containing functional groups, represents highly valuable motifs in medicines and natural products. It remains undeveloped for the catalytic asymmetric addition of sulfinate to carbonyls. Herein we disclosed the first catalytic enantioselective addition of sulfinate to ketones for the synthesis of sulfones via N-heterocyclic carbene (NHC) catalysis. The sulfonyl chloride behaves both as an oxidant and as a nucleophilic substrate in this carbene-catalyzed process. Experimental studies suggested that the Breslow intermediate can be SET oxidized by sulfonyl chloride to generate the sulfonyl radical. This novel synthetic approach for the asymmetric addition of sulfinate to carbonyls can also be used to modify the commercially available functional molecules.

A viral protein competitively bound to rice CIPK23 inhibits potassium absorption and facilitates virus systemic infection in rice.

Potassium (K+) plays a crucial role as a macronutrient in the growth and development of plants. Studies have definitely determined the vital roles of K+ in response to pathogen invasion. Our previous investigations revealed that rice plants infected with rice grassy stunt virus (RGSV) displayed a reduction in K+ content, but the mechanism by which RGSV infection subverts K+ uptake remains unknown. In this study, we found that overexpression of RGSV P1, a specific viral protein encoded by viral RNA1, results in enhanced sensitivity to low K+ stress and exhibits a significantly lower rate of K+ influx compared to wild-type rice plants. Further investigation revealed that RGSV P1 interacts with OsCIPK23, an upstream regulator of Shaker K+ channel OsAKT1. Moreover, we found that the P1 protein recruits the OsCIPK23 to the Cajal bodies (CBs). In vivo assays demonstrated that the P1 protein competitively binds to OsCIPK23 with both OsCBL1 and OsAKT1. In the nucleus, the P1 protein enhances the binding of OsCIPK23 to OsCoilin, a homologue of the signature protein of CBs in Arabidopsis, and facilitates their trafficking through these CB structures. Genetic analysis indicates that mutant in oscipk23 suppresses RGSV systemic infection. Conversely, osakt1 mutants exhibited increased sensitivity to RGSV infection. These findings suggest that RGSV P1 hinders the absorption of K+ in rice plants by recruiting the OsCIPK23 to the CB structures. This process potentially promotes virus systemic infection but comes at the expense of inhibiting OsAKT1 activity.

Adherence to oxidative balance score is inversely associated with the prevalence of stroke: results from National Health and Nutrition Examination Survey 1999-2018.

Introduction: The relationship between oxidative balance score (OBS), an emerging integrative metric for assessing individual redox homeostasis, and the prevalence of stroke in the general population remains unknown. We aimed to explore these relationships in the National Health and Nutrition Examination Survey (NHANES). We investigated the relationship between the oxidative balance score (OBS) and stroke prevalence using NHANES data from 1999-2018. Methods: We included eligible individuals from NHANES 1999-2018. OBS calculations were based on previously validated methods, and stroke diagnoses were based on self-reports in questionnaires. Multivariable logistic regression analyses were used to examine the independent associations of overall, dietary, and lifestyle OBS with stroke prevalence. In addition, restricted cubic spline (RCS), stratified analysis, and sensitivity analysis were used. Results: We included 25,258 participants aged 20-85 years, in which the prevalence of stroke was 2.66%. After adjusting for all confounders, overall and dietary OBS, but not lifestyle OBS, were inversely associated with the prevalence of stroke [odds ratios and 95% confidence intervals of 0.97 (0.96, 0.99) and 0.98 (0.96, 0.99) for overall and dietary OBS, respectively, both p < 0.05]. In addition, there was a dose-response relationship between overall and dietary OBS and stroke prevalence. The RCS showed that these relationships were linear. Stratified analyses indicated that socioeconomic status (SES) significantly influenced the relationship between all OBS and stroke prevalence. Conclusion: Dietary OBS, but not lifestyle OBS, had an inverse relationship with the prevalence of stroke in the general population. SES significantly influenced the protective effect of OBS against stroke. These findings emphasize the importance of integrated antioxidant properties from diet for stroke prevention.

Carbene-catalyzed and Pnictogen Bond-assisted Access to PIII-Stereogenic Compounds.

Intermolecular pnictogen bonding (PnB) catalysis has received increased interest in non-covalent organocatalysis. It has been demonstrated that organic electron-deficient pnictogen atoms can act as prospective Lewis acids. Here, we present a catalytic approach for the asymmetric synthesis of chiral PIII compounds by combining intramolecular PnB interactions and carbene catalysis. Our design features a pre-chiral phosphorus molecules bearing two electron-withdrawing benzoyl groups, resulting in the formation of a σ-hole at the P atom. X-ray and non-covalent interaction (NCI) analysis indicate that these phosphorus substrates exhibit intrinsic PnB interactions between the oxygen atom of the formyl group and the phosphorus atom. This induces a conformational locking effect, leading to the crystallization of the phosphorus substrates in a preferred conformation (P212121 chiral group). Under the catalysis of N-heterocyclic carbene, the aldehyde moiety activated by the pnictogen bond selectively reacts with an alcohol to yield the corresponding chiral monoester/phosphorus products with excellent enantioselectivity. This Lewis acidic phosphorus center, aroused by the non-polarized intramolecular pnictogen bond interaction, assists in conformational and selective regulations, providing unique opportunities for catalysis and beyond.

P-limitation regulates the accumulation of soil aggregates organic carbon during the restoration of Pinus tabuliformis forest.

Artificial forest restoration is widely recognized as a crucial approach to enhance the potential of soil carbon sequestration. Nevertheless, there is still limited understanding regarding the dynamics of aggregate organic carbon (OC) and the underlying mechanisms driving these dynamics after artificial forest restoration. To address this gap, we studied Pinus tabuliformis forests and adjacent farmland in three recovery periods (13, 24 and 33 years) in the Loess Plateau region. Samples of undisturbed soil from the surface layer were collected and divided into three aggregate sizes: >2 mm (large aggregate), 0.25-2 mm (medium aggregate), and <0.25 mm (small aggregate). The aim was to examine the distribution of OC and changes in enzyme activity within each aggregate size. The findings revealed a significant increase in OC content for all aggregate sizes following the restoration of Pinus tabuliformis forests. After 33 years of recovery, the OC of large aggregates, medium aggregates and micro-aggregates increased by (30.23 ± 9.85)%, (36.71 ± 21.60)% and (37.88 ± 16.07)% respectively compared with that of farmland. Moreover, the restoration of Pinus tabuliformis forests lead to increased activity of hydrolytic enzymes and decreased activity of oxidative enzymes. It is noteworthy that the regulation of carbon in all aggregates is influenced by soil P-limitation. In large aggregates, P-limitation promotes the enhancement of hydrolytic enzyme activity, thereby facilitate OC accumulation. Conversely, in medium and small aggregates, P-limitation inhibits the increase in oxidative enzyme activity, resulting in OC accumulation. The results emphasize the importance of P-limitation in regulating OC accumulation during the restoration of Pinus tabulaeformis forest, in which large aggregates play a leading role.

Tumor treating fields in glioblastoma: long-term treatment and high compliance as favorable prognostic factors.

Introduction: Tumor treating fields (TTFields) have earned substantial attention in recent years as a novel therapeutic approach with the potential to improve the prognosis of glioblastoma (GBM) patients. However, the impact of TTFields remains a subject of ongoing debate. This study aimed to offer real-world evidence on TTFields therapy for GBM, and to investigate the clinical determinants affecting its efficacy. Methods: We have reported a retrospective analysis of 81 newly diagnosed Chinese GBM patients who received TTFields/Stupp treatment in the Second Affiliated Hospital of Zhejiang University. Overall survival (OS) and progression-free survival (PFS) were analyzed using Kaplan-Meier method. Cox regression models with time-dependent covariates were utilized to address non-proportional hazards and to assess the influence of clinical variables on PFS and OS. Results: The median PFS and OS following TTFields/STUPP treatment was 12.6 months (95% CI 11.0-14.1) and 21.3 months (95% CI 10.0-32.6) respectively. Long-term TTFields treatment (>2 months) exhibits significant improvements in PFS and OS compared to the short-term treatment group (≤2 months). Time-dependent covariate COX analysis revealed that longer TTFields treatment was correlated with enhanced PFS and OS for up to 12 and 13 months, respectively. Higher compliance to TTFields (≥ 0.8) significantly reduced the death risk (HR=0.297, 95%CI 0.108-0.819). Complete surgical resection and MGMT promoter methylation were associated with significantly lower risk of progression (HR=0.337, 95% CI 0.176-0.643; HR=0.156, 95% CI 0.065-0.378) and death (HR=0.276, 95% CI 0.105-0.727; HR=0.249, 95% CI 0.087-0.710). Conclusion: The TTFields/Stupp treatment may prolong median OS and PFS in GBM patients, with long-term TTFields treatment, higher TTFields compliance, complete surgical resection, and MGMT promoter methylation significantly improving prognosis.

Effect of Preoperative Nutritional Status on Postoperative Functional Recovery of Hip Joint in Elderly Patients with Intertrochanteric Fractures.

Objective: The state of nutrition of senior patients with intertrochanteric fracture of femur before operation affects the patients' tolerance to the operation,the body recovery, healing of the wound and clinical prognosis. For these patients, the poor state of nutrition may lengthen the time of being in hospital, leading to poor hip recovery and clinical outcome. But currently, the relationship between functional recovery of hip joint after operation of intertrochanteric fracture in elderly patients and camp condition has not been reported. To investigate the effect of preoperative nutritional status on postoperative recovery of hip joint function in elderly patients with intertrochanteric fractures. Methods: Retrospective analysis was performed on the data of 96 elderly patients with intertrochanteric fracture of the femur treated with closed reduction PFNAfrom January 2021 to January 2022 in Dongying People's Hospital Trauma Orthopedics Department. There were 36 male patients and 60 female patients aged from 65 to 92.The patients were divided into the normal nutrition group (GNRI ≥ 92, n = 46) and the malnutrition group (GNRI < 92, n = 50). The general clinical data, time from injury to operation, intraoperative and postoperative allogeneic blood transfusion rate, postoperative complication rate, postoperative mortality 1 year, and Harris hip function score at 3, 6, 9 months and the last follow-up were compared between the two groups. Results: All patients were followed up for 9 to 15 months(mean,13.9 months) after surgery. The preoperative hemoglobin levels in the normal and malnutrition groups were 8.6-13.2 and 7.4-11.2 g/dL, respectively (P < .05). The time from injury to surgery in the normal nutrition group was significantly shorter than that in the malnutrition group (P < .01). The preoperative hemoglobin level in the normal nutrition group was significantly higher than that in the malnutrition group. The time from injury to operation in normal nutrition group and malnutrition group are respectively (1.1-5.2), (4.3-6.6)d; the intraoperative and postoperative allogeneic blood transfusion rates are respectively 47.8%(22/46), 92%(46/50);the incidence of postoperative complications are respectively 6.52%(3/46), 32%(16/50); the mortality rates within 1 year after operation are respectively 2.17%(1/46), 12%(6/50). In contrast, the postoperative allogeneic blood transfusion, postoperative complication, and postoperative complication rates in the normal nutrition group were significantly lower than those in the malnutrition group (P < .05). 3 months after surgery, the Harris hip function scores of patients in normal nutrition group and malnutrition group are respectively (75.26±4.02), (64.28±3.82); 6 months after surgery, the Harris hip function scores of them are respectively (80.42±3.86), (70.14±5.06).During the last follow-up, scores are (82.23±2.98), (72.12±4.62). At the 3, 6, and last follow-up after surgery, the Harris hip function score in the normal nutrition group was significantly higher than in the malnutrition group (P < .05). Conclusion: Preoperative malnutrition in elderly patients with intertrochanteric fracture has adverse effects on postoperative hip function recovery, and 1-year postoperative survival rate.GNRI can be used for simple screening. Early assessment of patients' nutritional status.

Age-Related Alterations in Peripheral Immune Landscape with Magnified Impact on Post-Stroke Brain.

Immunosenescence refers to the multifaceted and profound alterations in the immune system brought about by aging, exerting complex influences on the pathophysiological processes of diseases that manifest upon it. Using a combination of single-cell RNA sequencing, cytometry by time of flight, and various immunological assays, we investigated the characteristics of immunosenescence in the peripheral blood of aged mice and its impact on the cerebral immune environment after ischemic stroke. Our results revealed some features of immunosenescence. We observed an increase in neutrophil counts, concurrent with accelerated neutrophil aging, characterized by altered expression of aging-associated markers like CD62L and consequential changes in neutrophil-mediated immune functions. Monocytes/macrophages in aged mice exhibited enhanced antigen-presentation capabilities. T cell profiles shifted from naive to effector or memory states, with a specific rise in T helper 1 cells and T helper 17 cells subpopulations and increased regulatory T cell activation in CD4 T cells. Furthermore, regulatory CD8 T cells marked by Klra decreased with aging, while a subpopulation of exhausted-like CD8 T cells expanded, retaining potent immunostimulatory and proinflammatory functions. Critically, these inherent disparities not only persisted but were further amplified within the ischemic hemispheres following stroke. In summary, our comprehensive insights into the key attributes of peripheral immunosenescence provide a vital theoretical foundation for understanding not only ischemic strokes but also other age-associated diseases.

Selenium-Containing Organic Fertilizer Application Affects Yield, Quality, and Distribution of Selenium in Wheat.

This study was designed to investigate the effect on wheat yield of applying organic fertilizers (OF) with five different selenium (Se) concentrations. The mineral nutrients, cadmium (Cd) content, and the distribution of Se in wheat plants were also measured. The results showed that wheat yields reached a maximum of 9979.78 kg ha-1 in Mengcheng (MC) County and 8868.97 kg ha-1 in Dingyuan (DY) County, Anhui Province, China when the application amount of selenium-containing organic fertilizer (SOF) was up to 600 kg ha-1. Among the six mineral nutrients measured, only the calcium (Ca) content of the grains significantly increased with an increase in the application amount of SOF in the two regions under study. Cd content showed antagonistic effects with the Se content of wheat grains, and when the SOF was applied at 1200 kg ha-1, the Cd content of the grains was significantly reduced by 30.1% in MC and 67.3% in DY, compared with under the Se0 treatment. After application of SOF, the Se content of different parts of the wheat plant ranked root > grain > spike-stalk > glume > leaf > stem. In summary, SOF application at a suitable concentration could increase wheat yields and significantly promote the Ca content of the grains. Meanwhile, the addition of Se effectively inhibited the level of toxic Cd in the wheat grains.

Research to develop a diagnostic ultrasound nomogram to predict benign or malignant lymph nodes in HIV-infected patients.

BACKGROUND: This study aimed to establish an effective ultrasound diagnostic nomogram for benign or malignant lymph nodes in HIV-infected patients. METHODS: The nomogram is based on a retrospective study of 131 HIV-infected patients who underwent ultrasound assess at the Shanghai Public Health Clinical Center from December 2017 to July 2022. The nomogram's predictive accuracy and discriminative ability were determined by concordance index (C-index) and calibration curve analysis. A nomogram combining the lymph node US characteristics were generated based on the multivariate logistic regression results. RESULTS: Predictors contained in the ultrasound diagnostic nomogram included age (OR 1.044 95%CI: 1.014-1.074 P = 0.004), number of enlarged lymph node regions (OR 5.445 95%CI: 1.139-26.029 P = 0.034), and color Doppler flow imaging (CDFI) grades (OR 9.614 95%CI: 1.889-48.930 P = 0.006). The model displayed good discrimination with a C (ROC) of 0.775 and good calibration. CONCLUSIONS: The proposed nomogram may result in more-accurate diagnostic predictions for benign or malignant lymph nodes in patients with HIV infection.

Clinical study on the evaluation of liver fibrosis by ultrasound elastography combined with platelet count model.

OBJECTIVES: To establish the prediction model of liver fibrosis by combining ultrasound elastography and platelet count and evaluates its clinical value. METHODS: 146 patients with chronic liver diseases(CLD) admitted to our hospital from July 2020 to July 2022 were collected for liver biopsy pathological examination, and the results of ultrasound elastography (liver hardness value) and serological indicators were collected. Based on the results of Spearman correlation test and multiple linear regression model, the prediction model of liver fibrosis using ultrasound elastography combined with platelet count was constructed and verified. RESULTS: The AUC of transient elastography combined with platelet count model (FSP) in the diagnosis of S2, S3 and S4 phases of liver fibrosis was 0.665, 0.835 and 0.909, with specificity of 81.5%, 90.0% and 100%. The AUC of sound touch elastography combined with platelet count model (STEP) in diagnosing S2, S3 and S4 phases of liver fibrosis was 0.685, 0.810 and 0884, with specificity of 96.3%, 90.0% and 83.3%, which are higher than APRI, FIB-4, FORNS, AAR and other models. CONCLUSION: Ultrasound elastography combined with platelet count model has good diagnostic efficacy for liver fibrosis.

Amino acid fertilizer strengthens its effect on crop yield and quality by recruiting beneficial rhizosphere microbes.

BACKGROUND: There is currently an increase in the use of new types of fertilizers in modern agriculture. Studies have shown that amino acid fertilizers can improve crop yield and quality. However, their effects on crop rhizosphere ecology and their ecological impacts on crop yield are largely unknown. This study evaluated the effects of a water-soluble amino acid fertilizer (WAAF) on tomatoes and its ecological effects on rhizosphere bacterial communities using greenhouse pot experiments. RESULTS: The results showed that WAAF could promote the growth of tomatoes and improve the quality of fruits more effectively than water-soluble chemical fertilizer controls. Interestingly, WAAF showed a different regulating pattern on root exudates and increased the secretion of 17 major water-soluble root exudates, including hexadecanoic acid and 3-hydroxy-γ-butyrolactone. Water-soluble amino acid fertilizer also affected noticeably the composition, abundance, and beta-diversity of rhizosphere bacterial communities, and strengthened the potential relationships between community members. Water-soluble amino acid fertilizer showed a significant selective enrichment ability and recruited some members of the genera such as Cupriavidus, Ralstonia, Chitinophaga, Gemmatimonas, Mitsuaria, Mucilaginibacter, Paracoccus, Sphingopyxis, and Variovorax. Network analysis and functional prediction implied that, besides fertilizer effects, the recruiting of beneficial microbes involved in chemotaxis and biofilm formation was also a considerable factor in tomato yield and quality improvement. CONCLUSION: Our study revealed ecological and recruiting effects of WAAF on rhizosphere microbes and potentially beneficial microbiota, and provided a basis for the amino acid fertilizer regulation of rhizosphere ecology to improve soil health and further improve crop yield and quality. © 2023 Society of Chemical Industry.

Analysis of the AMT gene family in chili pepper and the effects of arbuscular mycorrhizal colonization on the expression patterns of CaAMT2 genes.

BACKGROUND: Ammonium (NH4+) is a key nitrogen source supporting plant growth and development. Proteins in the ammonium transporter (AMT) family mediate the movement of NH4+ across the cell membrane. Although several studies have examined AMT genes in various plant species, few studies of the AMT gene family have been conducted in chili pepper. RESULTS: Here, a total of eight AMT genes were identified in chili pepper, and their exon/intron structures, phylogenetic relationships, and expression patterns in response to arbuscular mycorrhizal (AM) colonization were explored. Synteny analyses among chili pepper, tomato, eggplant, soybean, and Medicago revealed that the CaAMT2;1, CaAMT2.4, and CaAMT3;1 have undergone an expansion prior to the divergence of Solanaceae and Leguminosae. The expression of six AMT2 genes was either up-regulated or down-regulated in response to AM colonization. The expression of CaAMT2;1/2;2/2;3 and SlAMT2;1/2;2/2;3 was significantly up-regulated in AM fungi-inoculated roots. A 1,112-bp CaAMT2;1 promoter fragment and a 1,400-bp CaAMT2;2 promoter fragment drove the expression of the ß-glucuronidase gene in the cortex of AM roots. Evaluation of AM colonization under different NH4+ concentrations revealed that a sufficient, but not excessive, supply of NH4+ promotes the growth of chili pepper and the colonization of AM. Furthermore, we demonstrated that CaAMT2;2 overexpression could mediate NH4+ uptake in tomato plants. CONCLUSION: In sum, our results provide new insights into the evolutionary relationships and functional divergence of chili pepper AMT genes. We also identified putative AMT genes expressed in AM symbiotic roots.

In-depth characterization of 1,4-butanediol diglycidyl ether substituted hyaluronic acid hydrogels.

BDDE substituted HA hydrogels remain the most commonly used HA product in the biomedical field. The physical and biochemical properties of the hydrogels are dependent on the degree of modification and substitution patterns/positions, thus, characterizing their fine structure is of great importance for quality assurance. In this study, we developed novel LC-MS methods for accurate determination of MoD as well as in-depth characterization of the linkage network. Fragments resulted from enzymatic depolymerization were resolved by a porous graphitic carbon column followed by online tandem-MS for determining the modification site/residue. With high-resolution separation, two types of previously unknown structures were detected in the cross-linked fragments of 2-B-2 and 4-B-2. Based on the feature of resistance to NaBH4 reduction, these structures contain a GlcNAc residue modified at OH1. This special sugar unit likely derived from reducing end of the native polysaccharide could be a signature to discriminate subtle batch to batch variations.

A Review of Vector-Borne Rice Viruses.

Rice (Oryza sativa L.) is one of the major staple foods for global consumption. A major roadblock to global rice production is persistent loss of crops caused by plant diseases, including rice blast, sheath blight, bacterial blight, and particularly various vector-borne rice viral diseases. Since the late 19th century, 19 species of rice viruses have been recorded in rice-producing areas worldwide and cause varying degrees of damage on the rice production. Among them, southern rice black-streaked dwarf virus (SRBSDV) and rice black-streaked dwarf virus (RBSDV) in Asia, rice yellow mottle virus (RYMV) in Africa, and rice stripe necrosis virus (RSNV) in America currently pose serious threats to rice yields. This review systematizes the emergence and damage of rice viral diseases, the symptomatology and transmission biology of rice viruses, the arm races between viruses and rice plants as well as their insect vectors, and the strategies for the prevention and control of rice viral diseases.

Chalcogen bond-guided conformational isomerization enables catalytic dynamic kinetic resolution of sulfoxides.

Conformational isomerization can be guided by weak interactions such as chalcogen bonding (ChB) interactions. Here we report a catalytic strategy for asymmetric access to chiral sulfoxides by employing conformational isomerization and chalcogen bonding interactions. The reaction involves a sulfoxide bearing two aldehyde moieties as the substrate that, according to structural analysis and DFT calculations, exists as a racemic mixture due to the presence of an intramolecular chalcogen bond. This chalcogen bond formed between aldehyde (oxygen atom) and sulfoxide (sulfur atom), induces a conformational locking effect, thus making the symmetric sulfoxide as a racemate. In the presence of N-heterocyclic carbene (NHC) as catalyst, the aldehyde moiety activated by the chalcogen bond selectively reacts with an alcohol to afford the corresponding chiral sulfoxide products with excellent optical purities. This reaction involves a dynamic kinetic resolution (DKR) process enabled by conformational locking and facile isomerization by chalcogen bonding interactions.

Mediation of the APOE Associations With Cognition Through Cerebral Blood Flow: The CIBL Study.

Background: The ε4 allele of the apolipoprotein E (APOE) gene is a strong genetic risk factor for aging-related cognitive decline. However, the causal connection between ε4 alleles and cognition is not well understood. The objective of this study was to identify the roles of cerebral blood flow (CBF) in cognitive-related brain areas in mediating the associations of APOE with cognition. Methods: The multiple linear regression analyses were conducted on 369 subjects (mean age of 68.8 years; 62.9% of women; 29.3% of APOE ε4 allele carriers). Causal mediation analyses with 5,000 bootstrapped iterations were conducted to explore the mediation effects. Result: APOE ε4 allele was negatively associated with cognition (P < 0.05) and CBF in the amygdala, hippocampus, middle temporal gyrus, posterior cingulate, and precuneus (all P < 0.05). The effect of the APOE genotype on cognition was partly mediated by the above CBF (all P < 0.05). Conclusion: CBF partially mediates the potential links between APOE genotype and cognition. Overall, the APOE ε4 allele may lead to a dysregulation of the vascular structure and function with reduced cerebral perfusion, which in turn leads to cognitive impairment.

Genome-wide identification and expression analysis of HAK/KUP/KT potassium transporter provides insights into genes involved in responding to potassium deficiency and salt stress in pepper (Capsicum annuum L.).

In plants, the HAK/KUP/KT family is the largest group of potassium transporters, and it plays an important role in mineral element absorption, plant growth, environmental stress adaptation, and symbiosis. Although these important genes have been investigated in many plant species, limited information is currently available on the HAK/KUP/KT genes for Pepper (Capsicum annuum L.). In the present study, a total of 20 CaHAK genes were identified from the pepper genome and the CaHAK genes were numbered 1 - 20 based on phylogenetic analysis. For the genes and their corresponding proteins, the physicochemical properties, phylogenetic relationship, chromosomal distribution, gene structure, conserved motifs, gene duplication events, and expression patterns were analyzed. Phylogenetic analysis divided CaHAK genes into four cluster (I-IV) based on their structural features and the topology of the phylogenetic tree. Purifying selection played a crucial role in the evolution of CaHAK genes, while whole-genome triplication contributed to the expansion of the CaHAK gene family. The expression patterns showed that CaHAK proteins exhibited functional divergence in terms of plant K+ uptake and salt stress response. In particular, transcript abundance of CaHAK3 and CaHAK7 was strongly and specifically up-regulated in pepper roots under low K+ or high salinity conditions, suggesting that these genes are candidates for high-affinity K+ uptake transporters and may play crucial roles in the maintenance of the Na+/K+ balance during salt stress in pepper. In summary, the results not only provided the important information on the characteristics and evolutionary relationships of CaHAKs, but also provided potential genes responding to potassium deficiency and salt stress. SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s13205-022-03136-z.

Carbene-Catalyzed Enantioselective Sulfonylation of Enone Aryl Aldehydes: A New Mode of Breslow Intermediate Oxidation.

A carbene-catalyzed sulfonylation reaction between enone aryl aldehydes and sulfonyl chlorides is disclosed. The reaction effectively installs sulfone moieties in a highly enantioselective manner to afford sulfone-containing bicyclic lactones. The sulfonyl chloride behaves both as an oxidant and a nucleophilic substrate (via its reduced form) in this N-heterocyclic carbene (NHC)-catalyzed process. The NHC catalyst provides both activation and stereoselectivity control on a very remote site of enone aryl aldehyde substrates. Water plays an important role in modulating catalyst deactivation and reactivation routes that involve reactions between NHC and sulfonyl chloride. Experimental studies and DFT calculations suggest that an unprecedented intermediate and a new oxidation mode of the NHC-derived Breslow intermediate are involved in the new asymmetric sulfonylation reaction.

Genome-wide identification of candidate aquaporins involved in water accumulation of pomegranate outer seed coat.

Aquaporins (AQPs) are a class of highly conserved integral membrane proteins that facilitate the uptake and transport of water and other small molecules across cell membranes. However, little is known about AQP genes in pomegranate (Punica granatum L.) and their potential role in water accumulation of the outer seed coat. We identified 38 PgrAQP genes in the pomegranate genome and divided them into five subfamilies based on a comparative analysis. Purifying selection played a role in the evolution of PgrAQP genes and a whole-genome duplication event in Myrtales may have contributed to the expansion of PgrTIP, PgrSIP, and PgrXIP genes. Transcriptome data analysis revealed that the PgrAQP genes exhibited different tissue-specific expression patterns. Among them, the transcript abundance of PgrPIPs were significantly higher than that of other subfamilies. The mRNA transcription levels of PgrPIP1.3, PgrPIP2.8, and PgrSIP1.2 showed a significant linear relationship with water accumulation in seed coats, indicating that PgrPIP1.3/PgrPIP2.8 located in the plasma membrane and PgrSIP1.2 proteins located on the tonoplast may be involved in water accumulation and contribute to the cell expansion of the outer seed coat, which then develops into juicy edible flesh. Overall, our results provided not only information on the characteristics and evolution of PgrAQPs, but also insights on the genetic improvement of outer seed coats.