Furan Dearomatization: A Route to Diverse Fluoroalkyl/Aryl Triazoles.

The 5-fluoroalkyl-1,2,3-triazoles, serving as a pivotal element in medicinal chemistry, hold substantial research significance. In this work, we developed a furan dearomatization reaction for the synthesis of various 5-fluoroalkyl-1,2,3-triazoles, which contains -CF3, -CF2H, -CF2CF3, -CF2CF2CF3, -CF2CO2Et, and -C6F5. This methodology relies on the intermolecular [3 + 2] cycloaddition/furan ring-opening triggered by α-fluoroalkyl furfuryl cation with azides to stereoselectively synthesize a series of (E)-fluoroalkyl enone triazoles. The reaction proceeds without metal participation, exhibits excellent substrate tolerance, and has excellent synthetic utility.

Copper Catalyzed Three-Component Ullmann C-S Coupling in PEG for the Synthesis of 6-Aryl/alkylthio-purines.

To tackle the environmental unfriendly issue in existing synthesis strategies for 6-substitued thiopurine derivatives, such as poor step economy, frequent use of malodorous organic sulfur starting materials, toxic organic solvents, and equivalent dosage of base, we have developed a CuI-catalyzed base-free three-component Ullmann C-S coupling synthetic strategy, featured using inorganic salt Na2S as the sulfur source and nontoxic PEG-600 as the solvent. The newly developed strategy is particularly effective for the synthesis of 6-arylthiopurines. The high catalytic efficiency in PEG-600 can be rationalized by the high soluble ability of CuI catalyst, likely due to the presence of multiple oxygen coordination sites in PEG.

Evidence that carbohydrate-to-fat ratio and taste, but not energy density or NOVA level of processing, are determinants of food liking and food reward.

This virtual (online) study tested the common but largely untested assumptions that food energy density, level of processing (NOVA categories), and carbohydrate-to-fat (CF) ratio are key determinants of food reward. Individual participants (224 women and men, mean age 35 y, 53% with healthy weight, 43% with overweight or obesity) were randomised to one of three, within-subjects, study arms: energy density (32 foods), or level of processing (24 foods), or CF ratio (24 foods). They rated the foods for taste pleasantness (liking), desire to eat (food reward), and sweetness, saltiness, and flavour intensity (for analysis averaged as taste intensity). Against our hypotheses, there was not a positive relationship between liking or food reward and either energy density or level of processing. As hypothesised, foods combining more equal energy amounts of carbohydrate and fat (combo foods), and foods tasting more intense, scored higher on both liking and food reward. Further results were that CF ratio, taste intensity, and food fibre content (negatively), independent of energy density, accounted for 56% and 43% of the variance in liking and food reward, respectively. We interpret the results for CF ratio and fibre in terms of food energy-to-satiety ratio (ESR), where ESR for combo foods is high, and ESR for high-fibre foods is low. We suggest that the metric of ESR should be considered when designing future studies of effects of food composition on food reward, preference, and intake.

Genome-Wide Identification of CHYR Gene Family in Sophora alopecuroides and Functional Analysis of SaCHYR4 in Response to Abiotic Stress.

Sophora alopecuroides has important uses in medicine, wind breaking, and sand fixation. The CHY-zinc-finger and RING-finger (CHYR) proteins are crucial for plant growth, development, and environmental adaptation; however, genetic data regarding the CHYR family remain scarce. We aimed to investigate the CHYR gene family in S. alopecuroides and its response to abiotic stress, and identified 18 new SaCHYR genes from S. alopecuroides whole-genome data, categorized into 3 subclasses through a phylogenetic analysis. Gene structure, protein domains, and conserved motifs analyses revealed an exon-intron structure and conserved domain similarities. A chromosome localization analysis showed distribution across 12 chromosomes. A promoter analysis revealed abiotic stress-, light-, and hormone-responsive elements. An RNA-sequencing expression pattern analysis revealed positive responses of SaCHYR genes to salt, alkali, and drought stress. SaCHYR4 overexpression considerably enhanced alkali and drought tolerance in Arabidopsis thaliana. These findings shed light on SaCHYR's function and the resistance mechanisms of S. alopecuroides, presenting new genetic resources for crop resistance breeding.

Simultaneous Loading of Ni2 P Cocatalysts on the Inner and Outer Surfaces of Mesopores P-Doped Carbon Nitride Hollow Spheres for Enhanced Photocatalytic Water-Splitting Activity.

Promoting charge separation, constructing active sites, and improving the utilization of metal atoms are very important for the design of efficient photocatalysts. A simultaneous loading of Ni2 P cocatalysts on the inner and outer surfaces of mesoporous P-doped carbon nitride hollow nanospheres (PCNHS) to construct a Ni2 P@PCNHS@Ni2 P photocatalyst is reported. Ni2 P cocatalysts loading provides enough active sites on both the inner and outer surfaces for proton reduction, and the formed heterojunctions simultaneously promote the migration and separation of the photogenerated charges on the inner and outer surfaces. The photocatalytic reaction proceeds simultaneously on the inner and outer surfaces of Ni2 P@PCNHS@Ni2 P, which leads to a significantly improved photocatalytic water splitting performance and enhanced atomic utilization. Notably, the hydrogen evolution rate of Ni2 P@PCNHS@Ni2 P is 2.4 times higher than that of Pt-loaded PCNHS. The findings guide the design of hollow nanostructured composites with high-boosting photocatalytic performance.

Regulating CO and H2 Ratios in Syngas Produced from Photocatalytic CO2/H2O Reduction by Cu and Co Dual Active Centers on Carbon Nitride Hollow Nanospheres.

For photocatalytic CO2 reduction to produce syngas, there are challenges in achieving a high catalytic efficiency and precise control over the product ratio. In this study, two non-noble metal complexes Cobpy and Cubpy (bpy = 2,2'-bipyridine) as cocatalysts for CO2 reduction and hydrogen evolution, respectively, were in situ supported on carbon nitride hollow nanospheres to construct a hybrid system for photocatalytic syngas production. The resulting CO/H2 ratio can be precisely regulated within a wide range of 0:1-9:1 by accurately controlling the content of the two complexes. The presence of the two complexes promotes the migration of photogenerated electrons of the carbon nitride. CO2 can be reduced to CO on the photoreduced species Co(bpy)2+ of Cobpy on CNHS, and H+ can be reduced to H2 on the photoreduced species Cu(bpy)2+ of Cubpy. Furthermore, this method is also applicable to other photocatalysts, such as CdS and TiO2 for generating syngas and regulating product ratios.

Furan ring opening reaction for the synthesis of 2,5-dicarbonyl-3-ene-phosphates.

Furan ring opening reactions are essential in organic synthesis, enabling the incorporation of diverse functional groups and the construction of complex molecular structures. A highly efficient and practical method for synthesizing 2,5-dicarbonyl-3-ene-phosphates from readily available biomass furan and dialkyl phosphonates is reported. The reaction, catalyzed by FeCl3, demonstrated wide substrate scope and high synthetic efficiency. Gram-scale synthesis was achieved, and a one-pot reaction provided a quick access route to the desired compounds. Additionally, a successful Diels-Alder reaction highlighted the versatility of the methodology.

Synthesis, Biological Evaluation and Action Mechanism Study of New Mitochondria-Targeted Curcumin Derivative as Potential Antitumor Drugs.

Mitochondria have emerged as important targets in cancer therapy due to their key role in regulating energy supply, maintaining redox homeostasis, and intrinsic apoptosis. Curcumin (CUR) has shown promise in inhibiting the proliferation and metastasis of cancer cells by inducing apoptosis and arresting cell cycle. However, the clinical application of CUR has been limited by its low stability and poor tumor selectivity. To address these issues, the novel mitochondria-targeted curcumin derivatives were synthesized through the unilateral coupling (CUR-T) or bilateral coupling (CUR-2T) of curcumin's phenolic hydroxy groups with triphenyl phosphorus via ester bond. The aim was to achieve better stability, higher tumor selectivity, and stronger curative efficacy. The results of stability and biological experiments indicated that both stability and cytotoxicity were arranged in descending order of CUR-2T>CUR-T>CUR. In ovarian cancer cells (A2780 cells), CUR-2T showed well-defined preferential selectivity towards cancer cells and exhibited efficient anticancer efficacy due to its superior mitochondria accumulation ability. Subsequently, the mitochondrial redox balance was disrupted, accompanied by increased ROS levels, decreased ATP levels, dissipated MMP, and increased G0 /G1 phase arrest, leading to a higher apoptotic rate. In summary, the results of this study suggest that CUR-2T holds substantial promise for further development as a potential agent for the treatment of ovarian cancer.

A General Synthesis of Cross-Conjugated Enynones through Pd Catalyzed Sonogashira Coupling with Triazine Esters.

The palladium-catalyzed Sonogashira coupling of α, ß-unsaturated acid derivatives offers a diversity-oriented synthetic strategy for cross-conjugated enynones. However, the susceptibility of the unsaturated C-C bonds adjacent to the carbonyl group toward Pd catalysts makes the direct conversion of α, ß-unsaturated derivatives as acyl electrophiles to cross-conjugated ketones rare. This work presents a highly selective C-O activation approach to prepare cross-conjugated enynones using α, ß-unsaturated triazine esters as acyl electrophiles. Under base and phosphine ligand-free conditions, NHC-Pd(II)-Allyl precatalyst alone catalyzed the cross-coupling of α, ß-unsaturated triazine esters with terminal alkynes efficiently, yielding 31 cross-conjugated enynones with diverse functional groups. This method demonstrates the potential of triazine-mediated C-O activation for preparing highly functionalized ketones.

Heterointerface Engineered Core-Shell Fe2O3@TiO2 for High-Performance Lithium-Ion Storage.

The rational design of the heterogeneous interfaces enables precise adjustment of the electronic structure and optimization of the kinetics for electron/ion migration in energy storage materials. In this work, the built-in electric field is introduced to the iron-based anode material (Fe2O3@TiO2) through the well-designed heterostructure. This model serves as an ideal platform for comprehending the atomic-level optimization of electron transfer in advanced lithium-ion batteries (LIBs). As a result, the core-shell Fe2O3@TiO2 delivers a remarkable discharge capacity of 1342 mAh g-1 and an extraordinary capacity retention of 82.7% at 0.1 A g-1 after 300 cycles. Fe2O3@TiO2 shows an excellent rate performance from 0.1 A g-1 to 4.0 A g-1. Further, the discharge capacity of Fe2O3@TiO2 reached 736 mAh g-1 at 1.0 A g-1 after 2000 cycles, and the corresponding capacity retention is 83.62%. The heterostructure forms a conventional p-n junction, successfully constructing the built-in electric field and lithium-ion reservoir. The kinetic analysis demonstrates that Fe2O3@TiO2 displays high pseudocapacitance behavior (77.8%) and fast lithium-ion reaction kinetics. The capability of heterointerface engineering to optimize electrochemical reaction kinetics offers novel insights for constructing high-performance iron-based anodes for LIBs.

Dual Roles of Azide: Dearomative Dimerization of Furfuryl Azides.

A dearomative dimerization of furfuryl azides for the construction of furfuryl triazoles is developed. As a rare leaving group, azide is capable of initiating the generation of a furfuryl cation under the Lewis acid-catalyzed conditions, followed by reacting with the other azide to realize an intermolecular [3 + 2] cycloaddition/furan ring-opening cascade. By extending the reaction time, a fragmentation reaction of resulting furfuryl triazoles occurs to afford 1H-triazoles in high yield. Control studies demonstrated that key furfuryl cations also can be obtained from furfuryl triazoles. Furthermore, a chemoselective cross-cycloaddition can be achieved between furfuryl azides and a benzyl azide.

Two Structurally Similar Co5 Cluster-Based Metal-Organic Frameworks Containing Open Metal Sites for Efficient C2H2/CO2 Separation.

To reasonably design and synthesize metal-organic frameworks (MOFs) with high stability and excellent adsorption/separation performance, the pore configuration and functional sites are very important. Here, we report two structurally similar cluster-based MOFs using a pyridine-modified low-symmetry ligand [H4L = 2,6-bis(2',5'-dicarboxyphenyl)pyridine], [(NH2Me2)2][Co5(L)2(OCH3)2(µ3-OH)2·2DMF]·2DMF·2H2O (1) and [Co5(L)2(µ3-OH)2(H2O)2]·2H2O·4DMF (2). The structures of 1 and 2 are built from Co5 clusters, which have one-dimensional open channels, but their microporous environments are different due to the different ways in which ligands bind to the metals. Both MOFs have extremely high chemical stabilities over a wide pH range (2-12). The two MOFs have similar adsorption capacities of C2H2 (144.0 cm3 g-1 for 1 and 141.3 cm3 g-1 for 2), but 1 has a higher C2H2/CO2 selectivity of 3.5 under ambient conditions. The difference in gas adsorption and separation between the two MOFs has been compared by a breakthrough experiment and theoretical calculation, and the influence of the microporous environment on the gas adsorption and separation performance of MOFs has been further studied.

One-Dimensional Perovskite-like Cu(I)-Halides with Ideal Bandgap Based on Quantum-Well Structure.

Low-dimensional halide perovskites with quantum-well structures are promising materials for electronics and optoelectronics because of their excellent optoelectronic properties. This work concerns two novel, lead-free, one-dimensional organic-inorganic hybrid perovskite-like Cu(I) halides, (MV)Cu2X4 (MV = methyl viologen; X = Br, I), for optoelectronic applications. Both Cu(I) halides exhibited good stability under ambient conditions. The optical bandgaps of (MV)Cu2Br4 and (MV)Cu2I4 are 1.4 and 1.5 eV, respectively, which are in the ideal bandgap range for solar cells. (MV)Cu2Br4 possessed a characteristic quantum-well structure in which [CuBr4]n3n- chains with a nanowire-like structure were rolled up and isolated by tightly packed organic cations. Thanks to quantum confinement in the unique structure, the optical bandgap of (MV)Cu2Br4 fell in the ideal bandgap range for solar cells and was superior to that of (MV)Cu2I4. The good photoresponse properties of these Cu(I) halides suggest their great potential for application as light-harvesting materials in solar cells.

The construction of phosphonate triazolyl by copper(II)-catalyzed furan dearomatized [3 + 2] cycloaddition.

Triazole phosphonates are valuable structural motifs in chemical biology and the subject of growing recent interest. A novel methodology to synthesize triazolyl phosphonates starting from furfuryl phosphonate alcohols and organo-azides was developed. This method involved an intermolecular copper-catalyzed dearomatized [3 + 2] cycloaddition/furan ring-opening cascade reaction. A strategy involving a three-component reaction was realized for quick access to triazole phosphonates.

Effects of osteoporosis on the biomechanics of various supplemental fixations co-applied with oblique lumbar interbody fusion (OLIF): a finite element analysis.

BACKGROUND: Oblique lumbar interbody fusion (OLIF) is an important surgical modality for the treatment of degenerative lumbar spine disease. Various supplemental fixations can be co-applied with OLIF, increasing OLIF stability and reducing complications. However, it is unclear whether osteoporosis affects the success of supplemental fixations; therefore, this study analyzed the effects of osteoporosis on various supplemental fixations co-applied with OLIF. METHODS: We developed and validated an L3-S1 finite element (FE) model; we assigned different material properties to each component and established models of the osteoporotic and normal bone lumbar spine. We explored the outcomes of OLIF combined with each of five supplemental fixations: standalone OLIF; OLIF with lateral plate fixation (OLIF + LPF); OLIF with translaminar facet joint fixation and unilateral pedicle screw fixation (OLIF + TFJF + UPSF); OLIF with unilateral pedicle screw fixation (OLIF + UPSF); and OLIF with bilateral pedicle screw fixation (OLIF + BPSF). Under the various working conditions, we calculated the ranges of motion (ROMs) of the normal bone and osteoporosis models, the maximum Mises stresses of the fixation instruments (MMSFIs), and the average Mises stresses on cancellous bone (AMSCBs). RESULTS: Compared with the normal bone OLIF model, no demonstrable change in any segmental ROM was apparent. The MMSFIs increased in all five osteoporotic OLIF models. In the OLIF + TFJF + UPSF model, the MMSFIs increased sharply in forward flexion and extension. The stress changes of the OLIF + UPSF, OLIF + BPSF, and OLIF + TFJF + UPSF models were similar; all stresses trended upward. The AMSCBs decreased in all five osteoporotic OLIF models during flexion, extension, lateral bending, and axial rotation. The average stress change of cancellous bone was most obvious under extension. The AMSCBs of the five OLIF models decreased by 14%, 23.44%, 21.97%, 40.56%, and 22.44% respectively. CONCLUSIONS: For some supplemental fixations, the AMSCBs were all reduced and the MMSFIs were all increased in the osteoporotic model, compared with the OLIF model of normal bone. Therefore, the biomechanical performance of an osteoporotic model may be inferior to the biomechanical performance of a normal model for the same fixation method; in some instances, it may increase the risks of fracture and internal fixation failure.

Screening and identification of salt-tolerance genes in Sophora alopecuroides and functional verification of SaAQP.

MAIN CONCLUSION: Overexpression of SaAQP can improve the salt tolerance of transgenic soybean hairy roots and A. thaliana. Salt stress severely affects crop yield and food security. There is a need to improve the salt tolerance of crops, but the discovery and utilization of salt-tolerance genes remains limited. Owing to its strong stress tolerance, Sophora alopecuroides is ideal for the identification of salt-tolerance genes. Therefore, we aimed to screen and identify the salt-tolerance genes in S. alopecuroides. With a yeast expression library of seedlings, salt-tolerant genes were screened using a salt-containing medium to simulate salt stress. By combining salt-treatment screening and transcriptome sequencing, 11 candidate genes related to salt tolerance were identified, including genes for peroxidase, inositol methyltransferase, aquaporin, cysteine synthase, pectinesterase, and WRKY. The expression dynamics of candidate genes were analyzed after salt treatment of S. alopecuroides, and salt tolerance was verified in yeast BY4743. The candidate genes participated in the salt-stress response in S. alopecuroides, and their overexpression significantly improved the salt tolerance of yeast. Salt tolerance mediated by SaAQP was further verified in soybean hairy roots and Arabidopsis thaliana, and it was found that SaAQP might enhance the salt tolerance of A. thaliana by participating in a reactive oxygen species scavenging mechanism. This result provides new genetic resources in plant breeding for salt resistance.

Manganese-Catalyzed Achmatowicz Rearrangement Using Green Oxidant H2O2.

Oxidation reactions have been extensively studied in the context of the transformations of biomass-derived furans. However, in contrast to the vast literature on utilizing the stoichiometric oxidants, such as m-CPBA and NBS, catalytic methods for the oxidative furan-recyclizations remain scarcely investigated. Given this, we report a means of manganese-catalyzed oxidations of furan with low loading, achieving the Achmatowicz rearrangement in the presence of hydrogen peroxide as an environmentally benign oxidant under mild conditions with wide functional group compatibility.

Comparative radiological outcomes and complications of sacral-2-alar iliac screw versus iliac screw for sacropelvic fixation.

PURPOSE: To compare the outcomes of sacropelvic fixation (SPF) using sacral-2-alar iliac (S2AI) screw with SPF using iliac screw (IS). METHODS: A comprehensive search of PubMed, EMBASE, Cochrane Central Register of Controlled Trials and Scopus was performed for comparative studies between S2AI and IS for SPF. Two independent investigators selected qualified studies and extracted data indispensably. With 95% confidence intervals (CI), the odds ratio (OR) was applied to dichotomous outcomes and standardized mean difference (SMD) was applied to continuous outcomes for each item. RESULTS: We included data from thirteen studies involving 722 patients (S2AI, 357 patients; IS, 365 patients). In the pediatric population, the S2AI group had a smaller pelvic obliquity (PO) than the IS group at final follow-up (SMD, - 0.38; 95% CI, - 0.72 to - 0.04). Patients who underwent S2AI screws showed reduced rates of re-operation (S2AI, 13%; IS, 28%), implant failure (S2AI, 12%; IS, 26%) [screw loosening (S2AI, 8%; IS, 20%); screw breakage (S2AI, 2%; IS, 12%)], implant prominence (S2AI, 2%; IS, 14%), pseudarthrosis (S2AI, 3%; IS, 15%), wound infection (S2AI, 8%; IS, 22%) and less blood loss (S2AI, 2035.4 ml; IS, 2708.4 ml). CONCLUSION: Radiological outcomes indicate an effective maintenance of the correction and arrest of progression of deformity by S2AI, which is equal or better than IS. SPF with S2AI screw has obviously lower incidence of postoperative complications and less blood loss. Given these advantages, the S2AI screw seems to be a beneficial alternative to IS.

Analysis of Phytohormone Signal Transduction in Sophora alopecuroides under Salt Stress.

Salt stress seriously restricts crop yield and quality, leading to an urgent need to understand its effects on plants and the mechanism of plant responses. Although phytohormones are crucial for plant responses to salt stress, the role of phytohormone signal transduction in the salt stress responses of stress-resistant species such as Sophora alopecuroides has not been reported. Herein, we combined transcriptome and metabolome analyses to evaluate expression changes of key genes and metabolites associated with plant hormone signal transduction in S. alopecuroides roots under salt stress for 0 h to 72 h. Auxin, cytokinin, brassinosteroid, and gibberellin signals were predominantly involved in regulating S. alopecuroides growth and recovery under salt stress. Ethylene and jasmonic acid signals may negatively regulate the response of S. alopecuroides to salt stress. Abscisic acid and salicylic acid are significantly upregulated under salt stress, and their signals may positively regulate the plant response to salt stress. Additionally, salicylic acid (SA) might regulate the balance between plant growth and resistance by preventing reduction in growth-promoting hormones and maintaining high levels of abscisic acid (ABA). This study provides insight into the mechanism of salt stress response in S. alopecuroides and the corresponding role of plant hormones, which is beneficial for crop resistance breeding.

Divergent Biomimetic Total Syntheses of Ganocins†A-C, Ganocochlearins†C and D, and Cochlearol†T.

A divergent synthetic approach to six Ganoderma meroterpenoids, namely ganocins A-C, ganocochlearins C and D, and cochlearol T, has been developed for the first time. This synthetic route features a two-phase strategy which includes early-stage rapid construction of a common planar tricyclic intermediate followed by highly selective late-stage transformations into various Ganoderma meroterpenoids. Key to the strategy are a bioinspired intramolecular hetero-Diels-Alder reaction and Stahl-type oxidative aromatization, allowing efficient formation of the common tricyclic phenol intermediate. A nucleophilic dearomatization of the phenol unit, combined with a regioselective 1,4-reduction of the resulting dienone, enabled rapid access to ganocins B and C. Additionally, site-selective Mukaiyama hydration, followed by an intramolecular oxa-Michael addition/triflation cascade, served as a key strategic element in the chemical synthesis of ganocin A.