Advances in Defect Engineering of Metal Oxides for Photocatalytic CO2 Reduction.

Photocatalytic CO2 reduction technology, capable of converting low-density solar energy into high-density chemical energy, stands as a promising approach to alleviate the energy crisis and achieve carbon neutrality. Semiconductor metal oxides, characterized by their abundant reserves, good stability, and easily tunable structures, have found extensive applications in the field of photocatalysis. However, the wide bandgap inherent in metal oxides contributes to their poor efficiency in photocatalytic CO2 reduction. Defect engineering presents an effective strategy to address these challenges. This paper reviews the research progress in defect engineering to enhance the photocatalytic CO2 reduction performance of metal oxides, summarizing defect classifications, preparation methods, and characterization techniques. The focus is on defect engineering, represented by vacancies and doping, for improving the performance of metal oxide photocatalysts. This includes advancements in expanding the photoresponse range, enhancing photogenerated charge separation, and promoting CO2 molecule activation. Finally, the paper provides a summary of the current issues and challenges faced by defect engineering, along with a prospective outlook on the future development of photocatalytic CO2 reduction technology.

Infrared spectra and electronic structural changes of DNTF under high pressure: experimental and theoretical studies.

3,4-Bis(3-nitrofurazan-4-yl)furoxan (DNTF) is a novel energetic material with an excellent performance and has attracted considerable attention. Motivated by recent theories and experiments, we had carried out experimental and theoretical studies on the high-pressure responses of vibrational characteristics, in conjunction with structural and electronic characteristics. It is found that all observed infrared spectra peaks seem to shift towards higher frequencies. And the peaks attributed to N-Oc (coordinated oxygen atom) stretching vibrations become broader due to the decrease of lattice constants and the free region of DNTF crystals with the increase of pressure, where the a-direction is more sensitive to pressure. In addition, the non-covalent interaction between adjacent DNTF molecules in the same layer changes from the van der Waals interaction to the steric effect with the increase of pressure, and that between layers also changes from the van der Waals interaction to the π-π stacking interaction. More importantly, these results highlight that the increase of pressure may lead to the stability decrease and impact the sensitivity increase of DNTF. This study can deepen the understanding of the energetic material DNTF under high pressure and is of great significance for blasting and detonation applications of DNTF.

Image fusion-based low-dose CBCT enhancement method for visualizing miniscrew insertion in the infrazygomatic crest.

Digital dental technology covers oral cone-beam computed tomography (CBCT) image processing and low-dose CBCT dental applications. A low-dose CBCT image enhancement method based on image fusion is proposed to address the need for subzygomatic small screw insertion. Specifically, firstly, a sharpening correction module is proposed, where the CBCT image is sharpened to compensate for the loss of details in the underexposed/over-exposed region. Secondly, a visibility restoration module based on type II fuzzy sets is designed, and a contrast enhancement module using curve transformation is designed. In addition to this, we propose a perceptual fusion module that fuses visibility and contrast of oral CBCT images. As a result, the problems of overexposure/underexposure, low visibility, and low contrast that occur in oral CBCT images can be effectively addressed with consistent interpretability. The proposed algorithm was analyzed in comparison experiments with a variety of algorithms, as well as ablation experiments. After analysis, compared with advanced enhancement algorithms, this algorithm achieved excellent results in low-dose CBCT enhancement and effective observation of subzygomatic small screw implantation. Compared with the best performing method, the evaluation metric is 0.07-2 higher on both datasets. The project can be found at: https://github.com/sunpeipei2024/low-dose-CBCT .

SnRK2.4-mediated phosphorylation of ABF2 regulates ARGININE DECARBOXYLASE expression and putrescine accumulation under drought stress.

Arginine decarboxylase (ADC)-mediated putrescine (Put) biosynthesis plays an important role in plant abiotic stress response. SNF1-related protein kinases 2s (SnRK2s) and abscisic acid (ABA)-response element (ABRE)-binding factors (ABFs), are core components of the ABA signaling pathway involved in drought stress response. We previously reported that ADC of Poncirus trifoliata (PtrADC) functions in drought tolerance. However, whether and how SnRK2 and ABF regulate PtrADC to modulate putrescine accumulation under drought stress remains largely unclear. Herein, we employed a set of physiological, biochemical, and molecular approaches to reveal that a protein complex composed of PtrSnRK2.4 and PtrABF2 modulates putrescine biosynthesis and drought tolerance by directly regulating PtrADC. PtrABF2 was upregulated by dehydration in an ABA-dependent manner. PtrABF2 activated PtrADC expression by directly and specifically binding to the ABRE core sequence within its promoter and positively regulated drought tolerance via modulating putrescine accumulation. PtrSnRK2.4 interacts with and phosphorylates PtrABF2 at Ser93. PtrSnRK2.4-mediated PtrABF2 phosphorylation is essential for the transcriptional regulation of PtrADC. Besides, PtrSnRK2.4 was shown to play a positive role in drought tolerance by facilitating putrescine synthesis. Taken together, this study sheds new light on the regulatory module SnRK2.4-ABF2-ADC responsible for fine-tuning putrescine accumulation under drought stress, which advances our understanding on transcriptional regulation of putrescine synthesis.

The R2R3-MYB transcription factor FaMYB63 participates in regulation of eugenol production in strawberry.

The biosynthetic pathway of volatile phenylpropanoids, including 4-allyl-2-methoxyphenol (eugenol), has been investigated in petunia (Petunia hybrida). However, the regulatory network for eugenol accumulation in strawberry (Fragaria × ananassa Duch.) fruit remains unclear. Here, an R2R3-type MYB transcription factor (TF; FaMYB63) was isolated from strawberry by yeast one-hybrid (Y1H) screening using the promoter of the FaEGS1 (eugenol synthase 1 [EGS 1]) gene, which encodes the enzyme responsible for the last step in eugenol biosynthesis. FaMYB63 is phylogenetically distinct from other R2R3-MYB TFs, including FaEOBІІ (EMISSION OF BENZENOID II [EOBII]), which also participates in regulating eugenol biosynthesis in strawberry receptacles. Reverse transcription quantitative PCR (RT-qPCR) assays showed that the expression of FaMYB63 was tissue-specific and consistent with eugenol content through strawberry fruit development, was repressed by abscisic acid, and was activated by auxins (indole-3-acetic acid). Overexpression and RNA interference-mediated silencing of FaMYB63 resulted in marked changes in the transcript levels of the biosynthetic genes FaEGS1, FaEGS2, and FaCAD1 (cinnamyl alcohol dehydrogenase 1 [CAD1]) and, thereby, the accumulation of eugenol. Electrophoretic mobility shift, Y1H, GUS activity, and dual-luciferase activity assays demonstrated that the transcript levels of FaEOBІІ and FaMYB10 were regulated by FaMYB63, but not the other way around. Together, these results demonstrate that FaMYB63 directly activates FaEGS1, FaEGS2, FaCAD1, FaEOBІІ, and FaMYB10 to induce eugenol biosynthesis during strawberry fruit development. These findings deepen the understanding of the regulatory network that influences eugenol metabolism in an edible fruit crop.

Propofol Regulates ER Stress to Inhibit Tumour Growth and Sensitize Osteosarcoma to Doxorubicin.

Osteosarcoma is the most common malignant bone tumour affecting children and young adults. The antitumour role of propofol, a widely used intravenous sedative-hypnotic agent, has been recently reported in different cancer types. In this study, we aimed to assess the role of propofol on osteosarcoma and explore the possible mechanisms. Propofol of increasing concentrations (2.5, 5, 10, and 20 µg/ml) was used to treat the MG63 and 143B cells for 72 hours, and the CCK8 assay was applied to evaluate the tumour cell proliferation. Tumour cell migration and invasion were assessed with the transwell assay. The tumour cells were also treated with doxorubicin single agent or in combination with propofol to explore their synergic role. Differential expressed genes after propofol treatment were obtained and functionally assessed with bioinformatic tools. Expression of ER stress markers CHOP, p-eIF2α, and XBP1s was evaluated to validate the activation of ER stress response with western blot and qRT-PCR. The statistical analyses were performed with R v4.2.1. Propofol treatment led to significant growth inhibition in MG63 and 143B cells in a dose-dependent manner (p < 0.05). Osteosarcoma migration (MG63 91.4 (82-102) vs. 56.8 (49-65), p < 0.05; 143B 96.6 (77-104) vs. 45.4 (28-54), p < 0.05) and invasion (MG63 68.6 (61-80) vs. 32 (25-39), p < 0.05; 143B 90.6 (72-100) vs. 39.2 (26-55), p < 0.05) were reduced after propofol treatment. Doxorubicin sensitivity was increased after propofol treatment compared with the control group (p < 0.05). Bioinformatic analysis showed significant functional enrichment in ER stress response after propofol treatment. Upregulation of CHOP, p-eIF2α, and XBP1s was detected in MG63 and 143B secondary to propofol treatment. In conclusion, we found that propofol treatment suppressed osteosarcoma proliferation and invasion and had a synergic role with doxorubicin by inducing ER stress. Our findings provided a novel option in osteosarcoma therapy.

Effects of semidry milling on the properties of highland barley flour and the quality of highland barley bread.

BACKGROUND: This study aimed to investigate the effects of semidry milling on the quality attributes of highland barley flour and highland barley bread. Highland barley flours were prepared by dry (DBF), semidry (SBF), and wet (WBF) milling methods. The properties of different highland barley flours were analyzed, and highland barley breads made from different highland barley flours were evaluated. RESULTS: The results showed that WBF had the lowest damaged starch content (15.2 g kg-1 ), and the contents of damaged starch in SBF-35 and SBF-40 (43.5 g kg-1 and 24.1 g kg-1 respectively) were lower than that of DBF (87.6 g kg-1 ). And SBF-35 and SBF-40 with large particles exhibited low hydration performance. In addition, SBF-35 and SBF-40 had higher pasting viscosity, pasting temperature, ΔH, and relative crystallinity, consequently resulting in better gel properties than other highland barley flours. These properties could help SBF-35 and SBF-40 develop high-quality bread with large specific volume and superior crumb structure and texture that is similar to the bread with WBF. CONCLUSION: Overall, semidry milling not only could improve the characteristics of HBF, but also avoid high starch damage by dry milling and water wasting by wet milling. What is more, highland barley breads with SBF-35 and SBF-40 had preferable appearance and crumb texture. Therefore, semidry milling could be regarded as a feasible way to produce highland barley flour. © 2023 Society of Chemical Industry.

Sequential ultrasound assisted deep eutectic solvent-based protein extraction from Sacha inchi meal biomass: towards circular bioeconomy.

The need for high-quality dietary proteins has risen over the years with improvements in the quality of life. Deep eutectic solvents (DESs) have been regarded as potential green alternatives to conventional organic solvents for protein extraction from press cake biomass, meeting the needs of sustainable development goals. Sacha inchi seed meal (SIM) is generated as a by-product of the seed oil extraction industries containing high protein content. The current study presents a novel ultrasound assisted DES method for the extraction of SIM protein in a sequential manner. Four different DESs were screened, out of which choline chloride (ChCl)/glycerol (1:2) gave promising results in protein recovery and was further selected. The sequential ultrasound-ChCl/glycerol could effectively extract high total crude protein content (77.43%) from SIM biomass compared to alone ultrasound (29.21%) or ChCl/glycerol (58.32%) treatment strategies. The SIM protein extracted from ultrasound-ChCl/glycerol exhibited high solubility (94.39%) at alkaline pH and highest in vitro digestibility (71.16%) by digestive enzymes (pepsin and trypsin). The protein characterization by SDS-PAGE and FTIR elucidated the structural properties and presence of different functional groups of SIM protein. Overall, the sequential ultrasound-ChCl/glycerol revealed its significant potential for one-step biorefining of the waste Sacha inchi meal biomass for circular bioeconomy.

Direct Cyanation of Thiophenols or Thiols to Access Thiocyanates under Electrochemical Conditions.

A novel electrochemical cross-coupling method for the synthesis of thiocyanates via the direct cyanation of readily available thiophenols or thiols with trimethylsilyl cyanide (TMSCN) was developed. This approach was also suitable for selenols. External oxidant-free, transition-metal-free and mild operating conditions were the main advantages of this protocol. A series of thiocyanates and selenocyanates could be obtained in moderate to high yields.

Electrochemical Aerobic Oxygenation and Nitrogenation of Cyclic Alkenes via C═C Bond Cleavage or Oxygenation and Azidation of Open-Chain Alkenes.

An efficient strategy involving electrochemical C═C double-bond cleavage and functionalization of cyclic alkenes for the synthesis of ketonitriles is described. This transformation features environmentally friendly conditions and utilizes relatively safe TMSN3 as the nitrogenation reagent and molecular oxygen as the oxidant. For the open-chain alkenes, the reaction gave 1,2-difunctionalized products. A wide range of cyclic alkenes and open-chain alkenes were found to be compatible, providing the corresponding ketonitriles and α-azido aromatic ketones in moderate to good yields.

N-Heterocyclic Thione-Protected Ag4 Tetrahedra and Ag8 Cubes Cocrystallized in a Single Crystal.

Polynuclear silver clusters have attracted intensive attention in the academic community owing to their rich physicochemical properties. The development of thione-protected silver clusters has been lagging behind the well-explored thiolate-protected silver-sulfide clusters. Herein, we report two N-heterocyclic thione-protected silver clusters: [Ag4(2-TBI)6(SO4)3]2- (Ag4) and [Br@Ag8(2-TBI)12(SO4)2]3+ (Ag8) (2-TBI = 2-thiobenzimidazol), which cocrystallize to form cluster-based molecular crystals with a CaF2-type structure. The cocrystal shows high thermal stability in air. Notably, the two cluster-based layers are alternately assembled to exhibit a unique k-vector-differential crystallographic arrangement. This work may lay a foundation for synthesis of atomically precise and stable silver clusters using readily available N-heterocyclic thione ligands.

Phenanthrenequinone (PQ) catalyzed cross-dehydrogenative coupling of alkanes with quinoxalin-2(1H)-ones and simple N-heteroarenes under visible light irradiation.

A direct and convenient strategy to 3-alkylquinoxalin-2(1H)-ones and other alkyl N-heteroarenes via a photocatalyzed alkylation of quinoxalin-2(1H)-ones and other N-heterocycles with commercially available, low-cost alkanes under ambient conditions using phenanthrenequinone (PQ) as a photocatalyst was developed. This transformation has advantages of environment-friendly protocol, mild conditions, good functional-group tolerance, and high yields of products.

HOAc catalyzed three-component reaction for the synthesis of 3,3'-(arylmethylene)bis(1H-indoles).

An efficient HOAc catalyzed three-component reaction of 2-(arylethynyl)anilines with arylaldehydes has been achieved, which leads to the generation of 3,3'-(arylmethylene)bis(1H-indoles) with good to excellent yields and high regioselectivity under transition-metal-free conditions. Four new C-C and C-N bonds were effectively formed in a one-pot procedure. Subsequent research on the reaction mechanism indicated that the reaction likely involved the processes of intramolecular cyclization and cascade intermolecular dehydration condensation.

Ultrastable Anti-Acid "Shield" in Layered Silver Coordination Polymers.

Surface passivation technology provides noble-metal materials with limited chemical stability, especially under highly acidic condition. To design effective strategy to enhance stability of noble-metal particles, an understanding of their surface anticorrosion mechanism at the atomic level is desirable by using two-dimensional (2D) noble-metal coordination polymer (CP) as an ideal model for their interfacial region. With the protection of 2-thiobenzimidazole (TBI), we isolated two Ag-based 2D CPs, {Ag14 (TBI)12 X2 }n (S-X, where S denotes sheet and X=Cl or Br). These compounds exhibited excellent chemical stability upon immersion in various common solvents, boiling water, boiling ethanol, 10 % hydrogen peroxide, concentrated acid (12 M HCl), and concentrated alkali (19 M NaOH). Systematic characterization and DFT analyses demonstrate that the superior stability of S-X was attributed to the hydrophobic organic shell and dynamic proton buffer layer acting as a double protective "shield".

Transcranial brain atlas-based optimization for functional near-infrared spectroscopy optode arrangement: Theory, algorithm, and application.

The quality of optode arrangement is crucial for group imaging studies when using functional near-infrared spectroscopy (fNIRS). Previous studies have demonstrated the promising effectiveness of using transcranial brain atlases (TBAs), in a manual and intuition-based way, to guide optode arrangement when individual structural MRI data are unavailable. However, the theoretical basis of using TBA to optimize optode arrangement remains unclear, which leads to manual and subjective application. In this study, we first describe the theoretical basis of TBA-based optimization of optode arrangement using a mathematical framework. Second, based on the theoretical basis, an algorithm is proposed for automatically arranging optodes on a virtual scalp. The resultant montage is placed onto the head of each participant guided by a low-cost and portable navigation system. We compared our method with the widely used 10/20-system-assisted optode arrangement procedure, using finger-tapping and working memory tasks as examples of both low- and high-level cognitive systems. Performance, including optode montage designs, locations on each participant's scalp, brain activation, as well as ground truth indices derived from individual MRI data were evaluated. The results give convergent support for our method's ability to provide more accurate, consistent and efficient optode arrangements for fNIRS group imaging than the 10/20 method.

FvMYB24, a strawberry R2R3-MYB transcription factor, improved salt stress tolerance in transgenic Arabidopsis.

Salinity is one of the major environmental stresses that limit crop growth and productivity. In this study, the FvMYB24 gene that encodes an R2R3-type MYB transcription factor was cloned and characterized. An expression analysis showed that FvMYB24 had a tissue- and stage-specific profile and was induced by salt treatment. Arabidopsis plants that overexpressed transgenic FvMYB24 exhibited a higher germination rate, fresh weight, chlorophyll content, and longer root length than the wild type (WT) under salt stress. The transgenic plants had higher activities of superoxide dismutase (SOD), peroxidase (POD), and catalase (CAT) and the accumulation of proline, while these plants accumulated lower amounts of malondialdehyde (MDA) compared with the WT. Furthermore, our results also revealed that the overexpression of FvMYB24 up-regulated the expression of several stress-related genes (AtSOS1, AtSOS2, AtSOS3, AtSOD, AtPOD, AtCAT1, AtNHX1, and AtLEA3) in response to salt stress, thus, enhancing the tolerance of transgenic Arabidopsis. An analysis of the cis-acting elements in the SOS1, SOS2, and SOS3 promoters revealed MYB-binding sites. However, FvMYB24 could only bind to the SOS1 promoter to mediate salt tolerance but not to the SOS2 and SOS3 promoters. These findings suggest that FvMYB24 could potentially be used as a positive regulator in transgenic plant breeding to improve the tolerance of strawberry plants to salt.

Electrochemical Oxidative Difunctionalization of Alkenes to Access α-Oxygenated Ketones.

Dioxygenation of alkenes was developed by the combination of electrochemical synthesis and aerobic oxidation, leading to easy accessibility of α-oxygenated ketones in an eco-friendly fashion. Using air as the oxygen source and the absence of transition metals were the critical features of this protocol. A wide range of alkenes and N-hydroxyimides were found to be compatible and provided α-oxygenated ketones in moderate to high yields.

Electrochemical Oxidative Regioselective C-H Cyanation of Imidazo[1,2-a]pyridines.

Electrochemical oxidative regioselective C-H cyanation of imidazo[1,2-a]pyridines was developed using readily available TMSCN as the cyano source. The KH2PO4/K2HPO4 buffer was essential for this transformation. This protocol was compatible with a broad range of substituted imidazo[1,2-a]pyridines and provided the C3 cyanated products in moderate to excellent yields.

Targeting brain functions from the scalp: Transcranial brain atlas based on large-scale fMRI data synthesis.

Transcranial brain mapping techniques, such as functional near-infrared spectroscopy (fNIRS) and transcranial magnetic stimulation (TMS), have been playing an increasingly important role in studies of human brain functions. Given a brain function of interest, fNIRS probes and TMS coils should be properly placed on the scalp to ensure that the function is effectively measured or modulated. However, since brain activity is inside the skull and invisible to the researcher during placement, this blind targeting may cause the device to partially or completely miss the functional target, resulting in inconsistent experimental results and divergent clinical outcomes, especially when participants' structural MRI data are not available. To address this issue, we propose here a framework for targeting a designated function directly from the scalp. First, a functional brain atlas for the targeted brain function is constructed via a meta-analysis of large-scale functional magnetic resonance imaging datasets. Second, the functional brain atlas is presented on the scalp surface by using a transcranial mapping previously established from an structural MRI dataset (n â€‹= â€‹114), resulting in a novel functional transcranial brain atlas (fTBA). Finally, a low-cost, portable scalp-navigation system is used to localize the transcranial device on the individual's scalp with the guidance of the fTBA. To demonstrate the feasibility of the targeting framework, both fNIRS and TMS mapping experiments were conducted. The results show that fTBA-guided fNIRS positioning can detect functional activity with high sensitivity and specificity for working memory and motor systems; Moreover, compared with traditional TMS targeting approaches (e.g. the International 10-20 System and the conventional 5-cm rule), the fTBA suggested motor stimulation site is closesr to both the motor hotspot and the center of gravity of motor evoked potentials (MEP-COG). In summary, the proposed method unblinds the transcranial function targeting process using prior information, providing an effective and straightforward approach to transcranial brain mapping studies, especially those without participants' structural MRI data.

Iron-mediated deuterium addition cascade cyano insertion/cyclization of N-arylacrylamides to access deuterium-labelled phenanthridines.

Deuterated molecules feature important biological activities and pharmacokinetic properties for the design of pharmaceuticals. Radical cyclization cascades involving the deuteration of alkenes to form heterocyclic compounds have rarely been reported. Herein, a deuterium addition cascade cyano insertion/cyclization of N-arylacrylamides to synthesize deuterated phenanthridines is described. Cheap Fe(NO3)3·9H2O enables the generation of a deuterium radical from NaBD4in situ. These reactions proceed under mild conditions in a short time and a variety of functional groups are well tolerated.