B(C6F5)3/CPA-Catalyzed Aza-Diels-Alder Reaction of 3,3-Difluoro-2-Aryl-3H-indoles and Unactivated Dienes.

Here we report B(C6F5)3/CPA-catalyzed enantioselective aza-Diels-Alder reaction of 3,3-difluoro-2-Aryl-3H-indoles with unactivated dienes to access chiral 10,10-difluoro-tetrahydropyrido[1,2-a]indoles. This protocol allows the formation of pyrazole-based C2-quaternary indolin-3-ones with high enantioselectivities and regioselectivities. Moreover, gram-scale synthesis of the 10,10-difluoro-tetrahydropyrido[1,2-a]indole skeleton was successfully achieved without any reduction in both yield and enantioselectivity.

Direct Z-scheme system of UiO-66 cubes wrapped with Zn0.5Cd0.5S nanoparticles for photocatalytic hydrogen generation synchronized with organic pollutant degradation.

Optimized fabrication of Z-scheme photocatalyst based on MOF materials offers sustainable energy generation and environmental improvement due to their attractive properties. The Z-scheme heterojunctions consisting of UiO-66 cubes covered with Zn0.5Cd0.5S nanoparticles were fabricated by a facile solvothermal method. Thanks to the Z-scheme carrier transport under simulated sunlight irradiation, UiO-66@Zn0.5Cd0.5S exhibited enhanced photocatalytic performance of H2 generation synchronized with organic pollutant degradation in fluoroquinolone antibiotic wastewater. Synergistically, the highest comprehensive performance was obtained in ciprofloxacin solution. The H2 yield reached 224 µmol∙ g-1∙ h-1 and simultaneously the removal efficiency was up to 83.6 %. The degradation pathways revealed that the process of piperazine ring cleavage and decarboxylation also generates H protons, further promoting the production of H2. Therefore, the effective spatial separation and transfer of the photoinduced carriers are attributed to the good band structure, large specific surface area, and cooperative reduction and oxidation reactions of UiO-66@Zn0.5Cd0.5S, resulting in significant photocatalytic activity. The toxicity assessment of antibiotics and intermediate products during the photocatalytic reaction also verifies the reduction of environmental risk. This study highlights a promising way to expand the application of the MOFs-based photocatalyst in clean energy conversion coupling with water remediation.

Asymmetric Organocatalyzed Cyclization Cascade Reactions of 3,3-Difluoro-2-aryl-3H-indoles and Enamides.

The direct functionalization of ß-C(sp2)-H bonds in enamides has garnered increasing attention within the realm of organic synthesis. However, these remarkable advancements are predominantly dependent on transition metals; limited success has been achieved via organocatalytic catalysis. Herein, we report a CPA-catalyzed ß-C(sp2)-H functionalization of enamides cascade intramolecular cyclization to synthesize the chiral dihydropyrimido[1,6-a]indoles bearing gem-difluoromethylene. Moreover, this methodology enables the synthesis of diverse chiral dihydropyrimido[1,6-a]indoles with outstanding enantioselectivities in moderate to high yields.

[Neuropsychological development of large for gestational age infants at the age of 12 months]. / 大于胎龄儿12æœˆé¾„ç¥žç»å¿ƒç†å‘è‚²çŠ¶å†µç ”ç©¶.

OBJECTIVES: To investigate the level of neuropsychological development in large for gestational age (LGA) infants at the age of 12 months. METHODS: The infants, aged 12 to <13 months, who attended the Outpatient Service of Child Care in the First Affiliated Hospital of Shandong First Medical University from December 2021 to June 2023, were enrolled as subjects. According to the gestational age and birth weight, they were divided into preterm appropriate for gestational age (AGA) group, preterm LGA group, early term AGA group, early term LGA group, full-term AGA group, and full-term LGA group. A modified Poisson regression analysis was used to investigate the association between LGA and neuropsychological development outcome at 12 months of age. RESULTS: After adjustment for confounding factors, compared with the full-term AGA group at the age of 12 months, the full-term LGA group had a significant increase in the risk of language deficit (RR=1.364, 95%CI: 1.063-1.750), the early term LGA group had significant increases in the risk of abnormal gross motor, fine motor, language, and the preterm LGA group had significant increases in the risk of abnormal language, social behavior, and total developmental quotient (P<0.05); also, the early term AGA group had higher risks of developmental delay across all five attributes and in total developmental quotient at the age of 12 months (P<0.05); except for the language attribute, the preterm AGA group had higher risks of developmental delay in the other 4 attributes (P<0.05). CONCLUSIONS: The neuropsychological development of LGA infants with different gestational ages lags behind that of full-term AGA infants at 12 months of age, and follow-up and early intervention of such infants should be taken seriously in clinical practice.

A DNA barcode library for woody plants in tropical and subtropical China.

The application of DNA barcoding has been significantly limited by the scarcity of reliable specimens and inadequate coverage and replication across all species. The deficiency of DNA barcode reference coverage is particularly striking for highly biodiverse subtropical and tropical regions. In this study, we present a comprehensive barcode library for woody plants in tropical and subtropical China. Our dataset includes a standard barcode library comprising the four most widely used barcodes (rbcL, matK, ITS, and ITS2) for 2,520 species from 4,654 samples across 49 orders, 144 families, and 693 genera, along with 79 samples identified at the genus level. This dataset also provides a super-barcode library consisting of 1,239 samples from 1,139 species, 411 genera, 113 families, and 40 orders. This newly developed library will serve as a valuable resource for DNA barcoding research in tropical and subtropical China and bordering countries, enable more accurate species identification, and contribute to the conservation and management of tropical and subtropical forests.

Quantitative detection of the Ralstonia solanacearum species complex in soil by qPCR combined with a recombinant internal control strain.

IMPORTANCE: DNA-based detection and quantification of soil-borne pathogens, such as the Ralstonia solanacearum species complex (RSSC), plays a vital role in risk assessment, but meanwhile, precise quantification is difficult due to the poor purity and yield of the soil DNA retrieved. The internal sample process control (ISPC) strain RsPC we developed solved this problem and significantly improved the accuracy of quantification of RSSC in different soils. ISPC-based quantitative PCR detection is a method especially suitable for the quantitative detection of microbes in complex matrices (such as soil and sludge) containing various PCR inhibitors and for those not easy to lyse (like Gram-positive bacteria, fungi, and thick-wall cells like resting spores). In addition, the use of ISPC strains removes additional workload on the preparation of high-quality template DNA and facilitates the development of high-throughput quantitative detection techniques for soil microbes.

Highly Enantioselective Synthesis of 3a-Fluorofuro[3,2-b]indolines via Organocatalytic Aza-Friedel-Crafts Reaction/Selective C-F Bond Activation.

Fluoroalkylated compounds are of high interest in drug discovery and have inspired the evolution of diverse C-F bond activation methodologies. However, the selective activation of polyfluorinated compounds remains challenging. Herein, we describe an unprecedented strategy for synthesizing enantioenriched fluorofuro[3,2-b]indolines through the organocatalytic aza-Friedel-Crafts reaction coupled with selective C-F bond activation. These reactions feature excellent enantioselectivities (≤96% ee) and yields (≤96%) as well as good functional group compatibility. Mechanistic investigations by means of 19F nuclear magnetic resonance experiments provided sufficient support for silica gel as the key medium in this transformation.

Enantioselective Alkynylation of 2-Aryl-3H-indol-3-ones via Cooperative Catalysis of Copper/Chiral Phosphoric Acid.

A facile enantioselective alkynylation of cyclic ketimines attached to a neutral functional group utilizing the dual Cu(I)-CPA catalysis is described. The strategy of the alkynylation of 2-aryl-3H-indol-3-one directly to chiral propargylic amines containing indolin-3-one moiety in good yields and enantioselectivities. Moreover, gram-scale synthesis of chiral propargylamines based C2-quaternary indolin-3-ones was performed. The synthetic applications were confirmed by transformations of the products with no decrease in the yield and enantioselectivity.

Non-thermal plasma activated peroxide and percarbonate for tetracycline and oxytetracycline degradation: Synergistic performance, degradation pathways, and toxicity evaluation.

Tetracycline (TC) and Oxytetracycline (OTC) are common antibiotics increasingly detected in the environment, posing a potential risk to human and aquatic lives. Although conventional methods such as adsorption and photocatalysis are used for the degradation of TC and OTC, they are inefficient in removal efficiency, energy yield, and toxic byproduct generation. Herein, a falling-film dielectric barrier discharge (DBD) reactor coupled with environmentally friendly oxidants (hydrogen peroxide (HPO), sodium percarbonate (SPC), and HPO + SPC) was applied, and the treatment efficiency of TC and OTC was investigated. Experimental results showed that moderate addition of the HPO and SPC exhibited a synergistic effect (SF > 2), significantly improving the antibiotic removal ratio, total organic removal ratio (TOC), and energy yield by more than 50%, 52%, and 180%, respectively. After 10 min of DBD treatment, the introduction of 0.2 mM SPC led to a 100% antibiotic removal ratio and a TOC removal of 53.4% and 61.2% for 200 mg/L TC and 200 mg/L OTC, respectively. Also, 1 mM HPO dosage led to 100% antibiotic removal ratios after 10 min of DBD treatment and a TOC removal of 62.4% and 71.9% for 200 mg/L TC and 200 mg/L OTC, respectively. However, the DBD + HPO + SPC treatment method had a detrimental effect on the performance of the DBD reactor. After 10 min of DBD plasma discharge, the removal ratios for TC and OTC were 80.8% and 84.1%, respectively, when 0.5 mM HPO + 0.5 mM SPC was added. Moreover, principal component and hierarchical cluster analysis confirmed the differences between the treatment methods. Furthermore, the concentration of oxidant-induced in-situ generated ozone and hydrogen peroxide were quantitatively determined, and their indispensable roles during the degradation process were established via radical scavenger tests. Finally, the synergetic antibiotic degradation mechanisms and pathways were proposed, and the toxicities of the intermediate byproducts were evaluated.

B(C6F5)3-catalyzed ß-C(sp3)-H alkylation of tertiary amines with 2-aryl-3H-indol-3-ones.

The ß-C-H functionalization of amines is one of the most powerful tools for the synthesis of saturated nitrogen-containing heterocycles in organic synthesis. However, the ß-C-H functionalization of amines via redox-neutral addition with cyclic-ketimines is still unprecedented. Herein, the ß-C-H functionalization of tertiary amines is described, providing the corresponding 1,3-diamines containing the indolin-3-one moiety in high yields via the B(C6F5)3-catalyzed borrowing hydrogen strategy. According to the experimental results, a possible catalytic cycle has been proposed to rationalize the process of this reaction. Notably, the ß-C-H alkylation of amines is external oxidant- and transition-metal-free, which makes a significant contribution to promoting economical chemical synthesis.

Organocatalyzed Enantioselective Aza-Morita-Baylis-Hillman Reaction of Cyclic Ketimine with α,ß-Unsaturated γ-Butyrolactam.

The enantioselective aza-MBH reaction is an efficient strategy for constructing novel carbon-carbon bonds, providing access to multitudinous chiral densely functionalized MBH products. However, the enantioselective aza-MBH reaction of cyclic-ketimines that would generate a versatile synthon is still missing and challenging. Herein, we developed a challenging direct organocatalytic asymmetric aza-MBH reaction involving cyclic ketimines attached to a neutral functional group. Moreover, the α,ß-unsaturated γ-butyrolactam was utilized as a rare nucleophile alkene in this work. The reactions provide enantiomerically enriched 2-alkenyl-2-phenyl-1,2-dihydro-3H-indol-3-ones, bearing with a tetra-substituted stereogenic center. Moreover, this reaction features high α-selectivities, high enantioselectivities (up to 99% ee), and good yields (up to 80%).

Fabrication of CdLa2S4@La(OH)3@Co3S4 Z-scheme heterojunctions with dense La, S-dual defects for robust photothermal assisted photocatalytic performance.

Optimize the separation and transport mechanism of photogenerated carriers in heterojunction composites, and make full use of the active sites of each material are key factors to enhance photocatalytic activity. Herein, we successfully synthesize defective CdLa2S4@La(OH)3@Co3S4 (CLS@LOH@CS) Z-scheme heterojunction photocatalysts through a facile solvothermal method, which show broad-spectrum absorption and excellent photocatalytic activity. La(OH)3 nanosheets not only greatly increase the specific surface area of photocatalyst, but also can be coupled with CdLa2S4 (CLS) and form Z-scheme heterojunction by converting irradiation light. In addition, Co3S4 with photothermal properties is obtained by in-situ sulfurization method, which can release heat to improve the mobility of photogenerated carriers, and also be used as a cocatalyst for hydrogen production. Most importantly, the formation of Co3S4 leads to a large number of sulfur vacancy defects in CLS, and thus improving the separation efficiency of photogenerated electrons and holes, and increasing the catalytic active sites. Consequently, the maximum hydrogen production rate of CLS@LOH@CS heterojunctions can reach 26.4 mmol g-1h-1, which is 293 times than pristine CLS (0.09 mmol g-1h-1). This work will provide a new horizon for synthesizing high efficiency heterojunction photocatalysts through switching the separation and transport modes of photogenerated carrier.

Solvato-Controlled Assembly and Structural Transformation of Emissive Poly-NHC-Based Organometallic Cages and Their Applications in Amino Acid Sensing and Fluorescence Imaging.

Stimuli-induced structural transformation of supramolecular cages has drawn increasing attention because of their sensitive feature to external variations as model systems to simulate biological processes. However, combining structural transformation and useful functions has remained a difficult task. This study reports the solvato-controlled self-assembly of two unique topologies with different emission characteristics, a water-soluble Ag8 L4 cage (A) and an Ag4 L2 cage (B), produced from the same sulfonate-pendant tetraphenylethene (TPE) bridged tetrakis-(1,2,4-triazolium) ligand. Both cages show interesting solvent-responsive reversible structural transformation, and the change of fluorescence signals can efficiently track the process. Additionally, water-soluble cage A exhibits unique properties in thermochromism, thiol amino acid sensing, and subcellular imaging in aqueous media.

Advances of non-thermal plasma discharge technology in degrading recalcitrant wastewater pollutants. A comprehensive review.

With development and urbanization, the amount of wastewater generated due to human activities drastically increases yearly, causing water pollution and intensifying the already worsened water crisis. Although convenient, conventional wastewater treatment methods such as activated sludge, stabilization ponds, and adsorption techniques cannot fully eradicate the complex and recalcitrant contaminants leading to toxic byproducts generation. Recent advancements in wastewater treatment techniques, specifically non-thermal plasma technology, have been extensively investigated for the degradation of complex pollutants in wastewater. Non-thermal plasma is an effective alternative for degrading and augmenting the biodegradability of recalcitrant pollutants due to its ability to generate reactive species in situ. This article critically reviews the non-thermal plasma technology, considering the plasma discharge configuration and reactor types. Furthermore, the influence of operational parameters on the efficiency of the plasma systems and the reactive species generated by the system during discharge has gained significant interest and hence been discussed. Also, the application of non-thermal plasma technology for the degradation of pharmaceuticals, pesticides, and dyes and the inactivation of microbial activities are outlined in this review article. Additionally, optimistic applications involving the combination of non-thermal plasma and catalysts and pilot and industrial-scale projects utilizing non-thermal plasma technology have been addressed. Concluding perceptions on the challenges and future perspectives of the non-thermal technology on wastewater treatment are accentuated. Overall, this review outlines a comprehensive understanding of the non-thermal plasma technology for recalcitrant pollutant degradation from a scientific perspective providing detailed instances for reference.

Asymmetric aza-Friedel-Crafts Reaction of Cyclic Ketimines with 5-Aminopyrazole Derivatives: Expedient Access to Pyrazole-Based C2-quaternary Indolin-3-Ones.

A chiral phosphoric acid-catalyzed enantioselective aza-Friedel-Crafts reaction of 5-aminopyrazole derivatives with cyclic ketimines attached to a neutral functional group is reported. This protocol allows the formation of pyrazole-based C2-quaternary indolin-3-ones with high enantioselectivities and regioselectivities. Moreover, gram-scale synthesis of the 5-aminopyrazole-based C2-quaternary indolin-3-ones was performed, with no decrease in the yield and enantioselectivity.

Chiral phosphoric acid-catalyzed enantioselective aza-Friedel-Crafts reaction of naphthols and electron-rich phenols with 2-aryl-3H-indol-3-ones.

The enantioselective aza-Friedel-Crafts reaction is one of the most straightforward and efficient strategies for constructing a new carbon-carbon bond bearing quaternary stereocenter in organic synthesis, but the catalytic asymmetric aza-Friedel-Crafts reaction of naphthols/phenols with cyclic-ketimines attached to a neutral functional group remains still relatively unexplored. Herein, a highly enantioselective aza-Friedel-Crafts reaction of cyclic-ketimines and naphthols/phenols has been realized using a chiral phosphoric acid catalyst. A variety of chiral aminonaphthols (chiral indolin-3-ones) containing a quaternary stereocenter at the C2 position were obtained with excellent outcomes (up to 97% yield, 98% ee). Moreover, the synthetic utility of the enantiomerically enriched chiral aminonaphthols was demonstrated in some efficient transformations. According to the experimental results, a possible transition state model has been proposed to rationalize the origin of asymmetric induction.

Ultra-Fast Construction of Novel S-Scheme CuBi2O4/CuO Heterojunction for Selectively Photocatalytic CO2 Conversion to CO.

Herein, step-scheme (S-scheme) CuBi2O4/CuO (CBO/CuO) composite films were successfully synthesized on glass substrates by the ultra-fast spraying-calcination method. The photocatalytic activities of the obtained materials for CO2 reduction in the presence of H2O vapor were evaluated under visible light irradiation (λ > 400 nm). Benefiting from the construction of S-scheme heterojunction, the CO, CH4 and O2 yields of the optimal CBO/CuO composite reached 1599.1, 5.1 and 682.2 µmol/m2 after irradiation for 9 h, and the selectivity of the CO product was notably enhanced from below 18.5% to above 98.5% compared with those of the bare samples. In the sixth cycling experiment, the yields of main products decreased by less than 15%, and a high CO selectivity was still kept. The enhanced photocatalytic performance of CO2 reduction was attributed to the efficient separation of photogenerated charge carriers. Based on the photocatalytic activity, band structure and in situ-XPS results, the S-scheme charge transfer mechanism was conformed. The study provides an insight into the design of S-scheme photocatalysts for selective CO2 conversion.

Differences in Postnatal Growth of Preterm Infants in Northern China Compared to the INTERGROWTH-21st Preterm Postnatal Growth Standards: A Retrospective Cohort Study.

Background: The INTERGROWTH-21st preterm postnatal growth standards (IPPGS) have increasingly been used to evaluate the growth of preterm infants worldwide. However, the validity of IPPGS's application to specific preterm populations remains controversial. This retrospective cohort study aimed to formulate reference growth charts for a preterm cohort in northern China and compare them to the IPPGS. Methods: A total of 1,827 healthy preterm infants with follow-up visits before 70 weeks of postmenstrual age (PMA) were retrospectively sampled from a preterm cohort (N = 2,011) born between 1 January 2011 and 28 February 2021, at the First Affiliated Hospital of Shandong First Medical University. Using the Generalized Additive Models for Location, Scale, and Shape method, 5,539 sets of longitudinal data were used to construct percentile and Z-score charts of length, weight, and head circumference (HC) at 40-64 weeks of PMA. Z-scores of length, weight, and HC (LAZ, WAZ, and HCZ) before 64 weeks were calculated using the IPPGS. Differences in the 50th percentile values between preterm infants and IPPGS (dLength, dWeight, and dHC) were calculated. Z-scores were assigned to six PMA clusters: 40-44, 44-48, 48-52, 52-56, 56-60, and 60-64 weeks for comparison between sexes. Results: For eligible infants, the mean PMA and weight at birth were 33.93 weeks and 2.3 kg, respectively. Boys, late preterm infants, twins, and infants with exclusively breastfeeding accounted for 55.8, 70.6, 27.8, and 45.9%, respectively. Compared to IPPGS, preterm infants were longer and heavier, especially for dLength in girls (range, 2.19-2.97 cm), which almost spanned the 50th and 90th percentiles of IPPGS. The dHC tended to narrow with PMA for both sexes. The mean LAZ, WAZ, and HCZ of both sexes at all PMA clusters were >0, especially for LAZ and WAZ (about 1.0 relative to IPPGS), indicating higher levels than the IPPGS at 40-64 weeks. Girls had larger LAZ at each PMA cluster, larger WAZ at 40-44 weeks, and lower HCZ after 56 weeks than boys. HCZ declined with PMA for both sexes. Conclusion: Postnatal growth of this preterm cohort was considerably higher than that of the IPPGS at 40-64 weeks of PMA with sex differences.

A New Birthweight Reference by Gestational Age: A Population Study Based on the Generalized Additive Model for Location, Scale, and Shape Method.

Background: It is important to choose a suitable birthweight reference to assess newborns, especially those that are small for gestational age (SGA). Currently, there is no regional standard reference for the north of China or for Shandong province. Methods: A total of 130,911 data records of singleton, live neonates born at 24-42 weeks of gestation were collected from 2016 to 2018 in Shandong province. A new birthweight-for-gestational age percentile reference was constructed based on the Generalized Additive Model for Location, Scale and Shape (GAMLSS) package in R version 3.5. The established gestational age weight curve was compared separately with the Fenton curve, INTERGROWTH-21st curve, and the Chinese Neonatal Network Standard curve of 2015. Results: We established the reference values of birthweight by gestational age at the 3rd, 10th, 25th, 50th, 75th, 90th, and 97th percentiles. Newborns had much heavier birthweights than those in the INTERGROWTH-21st and Fenton curves at most gestational ages. Although the newborns' birthweight references were closer to the Chinese Neonatal Network Standard except a few for gestational age, this study and INTERGROWTH-21st had similar birthweight curve shapes. Conclusions: There are obvious differences among the criteria for newborn birthweights. Therefore, it is more accurate to assess newborns using the local birthweight reference.

Plastome-based phylogeny improves community phylogenetics of subtropical forests in China.

Phylogenetic trees have been extensively used in community ecology. However, how the phylogeny construction affects ecological inferences is poorly understood. In this study, we constructed three different types of phylogenetic trees (a synthetic-tree generated using V.PhyloMaker, a barcode-tree generated using rbcL+matK+trnH-psbA, and a plastome-tree generated from plastid genomes) that represented an increasing level of phylogenetic resolution among 580 woody plant species from six forest dynamic plots in subtropical evergreen broadleaved forests of China. We then evaluated the performance of each phylogeny in estimations of community phylogenetic structure, turnover and phylogenetic signal in functional traits. As expected, the plastome-tree was most resolved and most supported for relationships among species. For local phylogenetic structure, the three trees showed consistent results with Faith's PD and MPD; however, only the synthetic-tree produced significant clustering patterns using MNTD for some plots. For phylogenetic turnover, contrasting results between the molecular trees and the synthetic-tree occurred only with nearest neighbor distance. The barcode-tree agreed more with the plastome-tree than the synthetic-tree for both phylogenetic structure and turnover. For functional traits, both the barcode-tree and plastome-tree detected phylogenetic signal in maximum height, but only the plastome-tree detected signal in leaf width. This is the first study that uses plastid genomes in large-scale community phylogenetics. Our results highlight the improvement of plastome-trees over barcode-trees and synthetic-trees for the analyses studied here. Our results also point to the possibility of type I and II errors in estimation of phylogenetic structure and turnover and detection of phylogenetic signal when using synthetic-trees.