ABSTRACT
Ultracold assembly of diatomic molecules has enabled great advances in controlled chemistry, ultracold chemical physics and quantum simulation with molecules1-3. Extending the ultracold association to triatomic molecules will offer many new research opportunities and challenges in these fields. A possible approach is to form triatomic molecules in a mixture of ultracold atoms and diatomic molecules by using a Feshbach resonance between them4,5. Although ultracold atom-diatomic-molecule Feshbach resonances have been observed recently6,7, using these resonances to form triatomic molecules remains challenging. Here we report on evidence of the association of triatomic molecules near the Feshbach resonance between 23Na40K molecules in the rovibrational ground state and 40K atoms. We apply a radio-frequency pulse to drive the free-bound transition in ultracold mixtures of 23Na40K and 40K and monitor the loss of 23Na40K molecules. The association of triatomic molecules manifests itself as an additional loss feature in the radio-frequency spectra, which can be distinguished from the atomic loss feature. The observation that the distance between the association feature and the atomic transition changes with the magnetic field provides strong evidence for the formation of triatomic molecules. The binding energy of the triatomic molecules is estimated from the measurements. Our work contributes to the understanding of the complex ultracold atom-molecule Feshbach resonances and may open up an avenue towards the preparation and control of ultracold triatomic molecules.
ABSTRACT
Kinesin motors play a fundamental role in development by controlling intracellular transport, spindle assembly, and microtubule organization. In humans, patients carrying mutations in KIF11 suffer from an autosomal dominant inheritable disease called microcephaly with or without chorioretinopathy, lymphoedema, or mental retardation (MCLMR). While mitotic functions of KIF11 proteins have been well documented in centrosome separation and spindle assembly, cellular mechanisms underlying KIF11 dysfunction and MCLMR remain unclear. In this study, we generate KIF11-inhibition chick and zebrafish models and find that KIF11 inhibition results in microcephaly, chorioretinopathy, and severe developmental defects in vivo. Notably, loss-of-function of KIF11 causes the formation of monopolar spindle and chromosome misalignment, which finally contribute to cell cycle arrest, chromosome instability, and cell death. Our results demonstrate that KIF11 is crucial for spindle assembly, chromosome alignment, and cell cycle progression of progenitor stem cells, indicating a potential link between polyploidy and MCLMR. Our data have revealed that KIF11 inhibition cause microcephaly, chorioretinopathy, and development disorders through the formation of monopolar spindle, polyploid, and cell cycle arrest.
Subject(s)
Facies , Lymphedema , Microcephaly , Retinal Diseases , Retinal Dysplasia , Animals , Cell Cycle Checkpoints/genetics , Chromosomal Instability , Developmental Disabilities , Kinesins/genetics , Kinesins/metabolism , Microcephaly/genetics , Phenotype , Zebrafish/genetics , Zebrafish/metabolismABSTRACT
Hypertensive heart disease (HHD) presents a substantial global health burden, spanning a spectrum from subtle cardiac functional alterations to overt heart failure. In this comprehensive review, we delved into the intricate pathophysiological mechanisms governing the onset and progression of HHD. We emphasized the significant role of neurohormonal activation, inflammation, and metabolic remodeling in HHD pathogenesis, offering insights into promising therapeutic avenues. Additionally, this review provided an overview of contemporary imaging diagnostic tools for precise HHD severity assessment. We discussed in detail the current potential treatments for HHD, including pharmacologic, lifestyle, and intervention devices. This review aimed to underscore the global importance of HHD and foster a deeper understanding of its pathophysiology, ultimately contributing to improved public health outcomes.
ABSTRACT
Polymeric membrane ion-selective electrodes (ISEs) have been widely used in environmental monitoring. However, in complicated marine environments, marine biofouling usually becomes a sticky problem for these electrodes. Herein, for the first time, a novel maintenance-free antifouling potentiometric marine sensor based on a self-polishing coating (SPC) is proposed. The SPC is synthesized by using the seeded emulsion polymerization method based on the triisopropylsilyl methacrylate monomer as the regulator of the self-renewal rate. This coating can be simply modified onto the electrode surface by drop-casting. The silyl acrylate side groups of the obtained SPC on the sensor surface can be hydrolyzed in the marine alkaline medium. The shear movement of seawater driven by sea waves, wind, gravity, or vibration removes the leftover (fouled) brittle polymer backbone and thus the fouling marine microorganisms. As a proof-of-concept experiment, a polymeric membrane Ca2+-ISE is chosen as a model. Compared to the unmodified electrode, the SPC-coated Ca2+-ISE exhibits remarkable improved antifouling properties in terms of superior anti-adhesive abilities towards marine microorganisms, such as bacterial cells and algae and excellent long-term stability even in the presence of high levels of marine microorganisms. Since no additional manual maintenance is required for maintaining the antifouling abilities of the sensor, the proposed self-polishing sensor may lay an important foundation for construction of unattended long-term potentiometric monitoring systems in real marine environments.
ABSTRACT
BACKGROUND: Accurate reporting of outcomes is crucial for interpreting the results of randomized controlled trials (RCTs). However, selectively reporting outcomes in publications to achieve researchers' anticipated results still occurs frequently. This study aims to investigate the prevalence of selective reporting of outcomes in RCTs on treating acute ischemic stroke (AIS), identify factors contributing to this issue, and assess its potential impact on the degree and direction of intervention effect. METHODS: A search was conducted in MEDLINE, Embase, and the Cochrane Library to collect interventional RCTs on AIS published from 2020 to 2022. Full texts of RCTs were reviewed, and only those reporting International Clinical Trials Registry Platform primary registry numbers were included. Registration information of the RCTs was extracted from the registry platforms and compared with the publications' details to assess the selective reporting of outcomes. Bayesian multilevel logistic regression was used to analyze the reasons behind selective reporting. RESULTS: Among the total of 159 AIS RCTs identified, 82 (51.6%) were ultimately included, as they reported registration numbers, which encompassed 819 outcomes. Among them, 72 RCTs (87.8%) and 497 outcomes (60.7%) exhibited selective reporting. Omission-type selective reporting (downgrading, omitting, or ambiguously reporting) accounted for 36.4%, while addition-type selective reporting (upgrading, adding, or altering the measurement scope of outcomes) comprised 63.6%. Omission-type selective reporting correlated with negative results (OR: 7.39; 95% CI: 4.08-13.44), whereas addition-type selective reporting correlated with positive results (OR: 2.07; 95% CI: 1.34-3.26) and publication in journals that are not in the top quartile of the Journal Citation Reports (OR: 2.48; 95% CI: 1.15-5.38). CONCLUSIONS: Registered interventional AIS RCTs still face significant issues regarding selective reporting of outcomes. Therefore, it is necessary to further evaluate the influence of selective reporting bias on the positive results obtained from individual AIS RCTs and the systematic reviews based on these RCTs.
Subject(s)
Randomized Controlled Trials as Topic , Stroke , Humans , Cross-Sectional Studies , Randomized Controlled Trials as Topic/statistics & numerical data , Randomized Controlled Trials as Topic/standards , Randomized Controlled Trials as Topic/methods , Stroke/therapy , Publication Bias/statistics & numerical data , Bayes Theorem , Research Design/standards , Ischemic Stroke/therapy , Registries/statistics & numerical dataABSTRACT
Endohedral metallofullerenes show great promise as molecular-scale memory units due to their robust architecture and protective capability for encapsulated atoms. However, the flat potential-energy surface within the cage often results in a severe disorder of encapsulated atoms. Here, we focused on prototypical systems involving Li@C60 on metallic surfaces, emphasizing the electrode's confinement effect on caged dynamics. We demonstrated that the varying interfacial stabilities induced by Li motion predominantly depend on the synergetic effect of van der Waals forces and covalent bonds rather than the previously assumed electrostatic interactions. We unveiled that the repulsion effect between encapsulated atom and the metal electrode primarily arises from the antibonding states between the metal states below the Fermi level and the degenerated frontier orbitals from HOMO-4 to HOMO. By manipulating orbital interactions, we observed an ordered arrangement of the encapsulated atom on Rec-Pt(111) at room temperature. Furthermore, our findings underscore the disruptive influence of electric fields on the stability of distinct Li positions, a phenomenon closely tied to the dipole moment induced by Li motion. This research provides a new perspective on the confined internal dynamics of endohedral metallofullerenes by manipulating cage-electrode interactions, contributing to precisely controlled molecular electronics.
ABSTRACT
Zwitterionic thiolate ligands have the potential to introduce novel assembly modes and functions for noble metal clusters. However, their utilization in the synthesis of silver clusters remains understudied, particularly for the clusters containing reductive Ag(0) species. In this article, we report the first synthesis of a mixed-valence silver(0/I) cluster protected by zwitterionic Tab as thiolate ligands (Tab = 4-(trimethylammonio)benzenethiolate), denoted as [Ag22(Tab)24](PF6)20·16CH3OH·6Et2O (Ag22·16CH3OH·6Et2O), alongside an Ag(I) cluster [Ag20(Tab)12(PhCOO)10(MeCN)2(H2O)](PF6)10·11MeCN (Ag20·11MeCN). Ag22 has a distinct hierarchical supratetrahedral structure with a central {Ag6} kernel surrounded by four [Ag4(Tab)6]4+ units. High-resolution electrospray ionization mass spectra demonstrate that Ag22 has two free electrons, indicating a superatomic core. Ag20 has a drum-like [Ag12(Tab)6(PhCOO)6(H2O)]6+ inner core capped by two tetrahedral-like [Ag4(Tab)3(PhCOO)2(MeCN)]2+ units. Ag20 can be transformed into Ag22 after its reaction with NaBH4 in solution. Antibacterial measurements reveal that Ag22 has a significantly lower minimum inhibitory concentration than that of the Ag20 cluster. This work not only extends the stabilization of silver(0/I) clusters to neutral thiol ligands but also offers new materials for the development of novel antibacterial materials.
ABSTRACT
Developing fluorescence switching as functional system is highly desirable for potential applications in the fields of light-responsive materials or devices. Attempt to construct fluorescence switching system tend to focus on the high fluorescence modulation efficiency, especially in solid state. Herein, a photo-controlled fluorescence switching system was constructed with photochromic diarylethene and trimethoxysilane modified zinc oxide quantum dots (Si-ZnO QDs) successfully. It was verified by the measurement of modulation efficiency, fatigue resistance as well as theoretical calculation. Upon irradiation with UV/Vis lights, the system exhibited excellent photochromic property and photo-controlled fluorescence switching performance. Furthermore, the excellent fluorescence switching characters could also be realized in solid state and the fluorescence modulation efficiency was determined to be 87.4%. The results will provide new strategies to the construction of reversible solid-state photo-controlled fluorescence switching for the application in the fields of optical data storage and security labels.
ABSTRACT
As a new type of zero-dimensional nanomaterial, carbon dots are widely applied in various fields. However, most of the carbon dots have aggregation fluorescence quenching properties, which limited their practical applications. In this study, a novel sulfur-doped carbon dots (S-CDs) was prepared by solvothermal method. The properties of the S-CDs in ethanol solution and in solid state were investigated respectively. The results showed that the S-CDs have an excited wavelength dependent emission of blue fluorescence in ethanol solution, and have orange fluorescence emission in solid state and composite films, indicating the prepared S-CDs has aggregation-induced emission (AIE) performance. The main reason was that the presence of S-S bonds and the intramolecular rotation of aromatic rings were limited in solid state, resulting in its emission of orange fluorescence. Furthermore, the S-CDs could be applied to identify fingerprints, anti-counterfeiting.
ABSTRACT
MnBi2Te4 can generate a variety of exotic topological quantum states, which are closely related to its special structure. We conduct comprehensive multiple-cycle high-pressure research on MnBi2Te4 by using a diamond anvil cell to study its phase transition behaviors under high pressure. As observed, when the pressure does not exceed 15 GPa, the material undergoes an irreversible metal-semiconductor-metal transition, whereas when the pressure exceeds 17 GPa, the layered structure is damaged and becomes irreversibly amorphous due to the lattice distortion caused by compression, but it is not completely amorphous, which presents some nano-sized grains after decompression. Our investigation vividly reveals the phase transition behaviors of MnBi2Te4 under high pressure cycling and paves the experimental way to find topological phases under high pressure.
ABSTRACT
PURPOSE: Desmoplastic fibroma (DF) is an uncommon intermediate bone tumor rarely involving the skull with unidentified pathogenesis. We report the first case of pediatric temporoparietal cranial desmoplastic fibroma (DF) with a CTNNB1 gene mutation and review the previous literature. CASE PRESENTATION: A 3-year-old boy had a firm, painless mass on the right temporoparietal region for 22 months. The cranial CT scan showed isolated osteolytic destruction in the outer plate and diploe of the right temporoparietal bone. Gross total resection of the lesion and cranioplasty were performed. After that, a growing epidural hematoma was observed so another operation was performed to remove the artificial titanium plate. Postoperative pathology indicated a DF diagnosis and molecular pathology suggested a missense mutation in exon 3 of the CTNNB1 gene (c.100G > A,p.Gly34Arg). CONCLUSION: Pediatric cranial DF is rare and easy to be misdiagnosed before operation. For cranial DF, lesion resection can be performed and perioperative management should be strengthened. Mutations in the CTNNB1 gene might be one of the molecular pathologic features of DF.
Subject(s)
Fibroma, Desmoplastic , Skull Neoplasms , beta Catenin , Humans , Male , beta Catenin/genetics , Child, Preschool , Fibroma, Desmoplastic/genetics , Fibroma, Desmoplastic/surgery , Fibroma, Desmoplastic/pathology , Fibroma, Desmoplastic/diagnostic imaging , Skull Neoplasms/genetics , Skull Neoplasms/surgery , Skull Neoplasms/diagnostic imaging , Skull Neoplasms/pathology , Mutation , Tomography, X-Ray ComputedABSTRACT
Sclerotinia sclerotiorum (Ss) is one of the most devastating fungal pathogens, causing huge yield loss in multiple economically important crops including oilseed rape. Plant resistance to Ss pertains to quantitative disease resistance (QDR) controlled by multiple minor genes. Genome-wide identification of genes involved in QDR to Ss is yet to be conducted. In this study, we integrated several assays including genome-wide association study (GWAS), multi-omics co-localization, and machine learning prediction to identify, on a genome-wide scale, genes involved in the oilseed rape QDR to Ss. Employing GWAS and multi-omics co-localization, we identified seven resistance-associated loci (RALs) associated with oilseed rape resistance to Ss. Furthermore, we developed a machine learning algorithm and named it Integrative Multi-Omics Analysis and Machine Learning for Target Gene Prediction (iMAP), which integrates multi-omics data to rapidly predict disease resistance-related genes within a broad chromosomal region. Through iMAP based on the identified RALs, we revealed multiple calcium signaling genes related to the QDR to Ss. Population-level analysis of selective sweeps and haplotypes of variants confirmed the positive selection of the predicted calcium signaling genes during evolution. Overall, this study has developed an algorithm that integrates multi-omics data and machine learning methods, providing a powerful tool for predicting target genes associated with specific traits. Furthermore, it makes a basis for further understanding the role and mechanisms of calcium signaling genes in the QDR to Ss.
Subject(s)
Ascomycota , Brassica napus , Calcium Signaling , Disease Resistance , Genome-Wide Association Study , Machine Learning , Plant Diseases , Ascomycota/pathogenicity , Disease Resistance/genetics , Plant Diseases/microbiology , Plant Diseases/genetics , Brassica napus/genetics , Brassica napus/microbiology , Brassica napus/immunology , Calcium Signaling/genetics , Polymorphism, Single Nucleotide , Quantitative Trait Loci , Genomics/methods , MultiomicsABSTRACT
Ion regulation strategy is regarded as a promising pathway for designing transition metal oxide-based electrocatalysts for oxygen evolution reaction (OER) with improved activity and stability. Precise anion conditioning can accurately change the anionic environment so that the acid radical ions (SO4 2- , PO3 2- , SeO4 2- , etc.), regardless of their state (inside the catalyst, on the catalyst surface, or in the electrolyte), can optimize the electronic structure of the cationic active site and further increase the catalytic activity. Herein, we report a new approach to encapsulate S atoms at the tetrahedral sites of the NaCl-type oxide NiO to form a tetraoxo-tetrahedral coordination structure (S-O4 ) inside the NiO (S-NiO -I). Density functional theory (DFT) calculations and operando vibrational spectroscopy proves that this kind of unique structure could achieve the S-O4 and Ni-S stable structure in S-NiO-I. Combining mass spectroscopy characterization, it could be confirmed that the S-O4 structure is the key factor for triggering the lattice oxygen exchange to participate in the OER process. This work demonstrates that the formation of tetraoxygen tetrahedral structure is a generalized key for boosting the OER performances of transition metal oxides.
ABSTRACT
The glycosylation of peptides and proteins can significantly impact their intrinsic properties, such as conformation, stability, antigenicity, and immunogenicity. Current methods for preparing N-linked glycopeptides typically rely on amide bond formation, which can be limited by the presence of reactive functional groups like acids and amines. Late-stage functionalization of peptides offers a promising approach to obtaining N-linked glycopeptides. In this study, we demonstrate the preparation of N-linked glycopeptides through a photoredox-catalyzed site-selective Giese addition between N-glycosyl oxamic acid and peptides containing dehydroalanine (Dha) under visible light conditions. Unlike traditional methods that rely on the coupling of aspartic acid and glycosylamine, this approach utilizes the conjugation of N-glycosylated carbamoyl radicals with Dha, facilitating the straightforward modification of complex peptides.
ABSTRACT
Diabetic neuropathic pain (DNP) is a diabetes complication experienced by many patients. Ventrolateral periaqueductal gray (vlPAG) neurons are essential mediators of the descending pain modulation system, yet the role of vlPAG astrocytes in DNP remains unclear. The present study applied a multidimensional approach to elucidate the role of these astrocytes in DNP. We verified the activation of astrocytes in different regions of the PAG in male DNP-model rats. We found that only astrocytes in the vlPAG exhibited increased growth. Furthermore, we described differences in vlPAG astrocyte activity at different time points during DNP progression. After the 14th day of modeling, vlPAG astrocytes exhibited obvious activation and morphologic changes. Furthermore, activation of Gq-designer receptors exclusively activated by a designer drug (Gq-DREADDs) in vlPAG astrocytes in naive male rats induced neuropathic pain-like symptoms and pain-related aversion, whereas activation of Gi-DREADDs in vlPAG astrocytes in male DNP-model rats alleviated sensations of pain and promoted pain-related preference behavior. Thus, bidirectional manipulation of vlPAG astrocytes revealed their potential to regulate pain. Surprisingly, activation of Gi-DREADDs in vlPAG astrocytes also mitigated anxiety-like behavior induced by DNP. Thus, our results provide direct support for the hypothesis that vlPAG astrocytes regulate diabetes-associated neuropathic pain and concomitant anxiety-like behavior.SIGNIFICANCE STATEMENT Many studies examined the association between the ventrolateral periaqueductal gray (vlPAG) and neuropathic pain. However, few studies have focused on the role of vlPAG astrocytes in diabetic neuropathic pain (DNP) and DNP-related emotional changes. This work confirmed the role of vlPAG astrocytes in DNP by applying a more direct and robust approach. We used chemogenetics to bidirectionally manipulate the activity of vlPAG astrocytes and revealed that vlPAG astrocytes regulate DNP and pain-related behavior. In addition, we discovered that activation of Gi-designer receptors exclusively activated by a designer drug in vlPAG astrocytes alleviated anxiety-like behavior induced by DNP. Together, these findings provide new insights into DNP and concomitant anxiety-like behavior and supply new therapeutic targets for treating DNP.
Subject(s)
Designer Drugs , Diabetes Mellitus , Diabetic Neuropathies , Neuralgia , Male , Rats , Animals , Periaqueductal Gray/physiology , Astrocytes , Nociception/physiology , MotivationABSTRACT
Designing efficient formic acid oxidation reaction (FAOR) catalysts with remarkable membrane electrode assembly (MEA) performance in a direct formic acid fuel cell (DFAFC) medium is significant yet challenging. Herein, we report that the monoclinic-phased platinum-tellurium nanotrepang (m-PtTe NT) can be adopted as a highly active, selective, and stable FAOR catalyst with a desirable direct reaction pathway. The m-PtTe NT exhibits the high specific and mass activities of 6.78 mA cm-2 and 3.2 A mgPt-1, respectively, which are 35.7/22.9, 2.8/2.6, and 3.9/2.9 times higher than those of commercial Pt/C, rhombohedral-phased Pt2Te3 NT (r-Pt2Te3 NT), and trigonal-phased PtTe2 NT (t-PtTe2 NT), respectively. Simultaneously, the highest reaction tendency for the direct FAOR pathway and the best tolerance to poisonous CO intermediate can also be realized by m-PtTe NT. More importantly, even in a single-cell medium, the m-PtTe NT can display a much higher MEA power density (171.4 mW cm-2) and stability (53.2% voltage loss after 5660 s) than those of commercial Pt/C, demonstrating the great potential in operating DFAFC device. The in-situ Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy jointly demonstrate that the unique nanostructure of m-PtTe NT can effectively optimize dehydrogenation steps and inhibit the CO intermediate adsorption, as well as promote the oxidation of noxious CO intermediate, thus achieving the great improvement of FAOR activity, poisoning tolerance, and stability. Density functional theory calculations further reveal that the direct pathway is the most favorable on m-PtTe NT than r-Pt2Te3 NT and t-PtTe2 NT. The higher activation energy to produce CO and the relatively weaker binding with CO of m-PtTe NT result in the better CO tolerance. This work achieves remarkable FAOR and MEA performances of advanced Pt-based anodic catalysts for DFAFCs via a phase engineering strategy.
ABSTRACT
Carbon dots (CDs) as luminescent zero-dimensional carbon nanomaterials have good aqueous dissolution, photostability, high quantum yield, and tunability of emission color. It has great application potential in many fields, including bioimaging, labeling of biological species, drug delivery, and sensing in biomedical. However, controlling the fluorescence emission of carbon dots remains a formidable challenge. Herein, we designed and exploited a photo-controlled fluorescent switching based on photochromic diarylethene (DT) and CDs for bioimaging. It could be modulated reversibly between "ON" and "OFF" under UV/vis light exposure. The fluorescent modulation efficiency was as high as 95.3%. The fluorescent switching could be used to the bioimaging in HeLa cells with low cell toxicity. Therefore, this fluorescent switching could be a promising candidate in many potential application areas, especially in bioimaging.
Subject(s)
Carbon , Coloring Agents , Humans , HeLa Cells , Drug Delivery Systems , FluorescenceABSTRACT
Phospholipase C (PLC) has important biological functions in specific cancer types, immune disorders and neurodegeneration. Here, an ultrasensitive electrochemical sensor for PLC was developed via signal amplification based on breathing atom transfer radical polymerization (ATRP). First, phosphatidylethanolamine (PE) was immobilized on the surface of a gold electrode by L-cysteine and cross-linker. Then, PE was specially hydrolyzed by PLC to obtain the phosphate groups and tethered with the ATRP initiator α-bromophenacetic acid (BPAA) by the coordination action of Zr4+. After the breathing ATRP, a large number of electroactive monomers (ferrocenylmethyl methacrylate, FcMMA) were successfully grafted from BPAA. The experimental results indicated that the detection signal of the obtained electrode (sensor) was proportional to the concentration of PLC. The sensor showed a low detection limit of 0.270 U L-1 and a wide linear range of 1-40 U L-1 (R2 = 0.997). Most importantly, the sensor was successfully applied to detect PLC in breast cancer cells (MCF-7, MDA-MB-231) and nontumor cells (MCF-10A). The value obtained by our electrochemical sensor had no obvious difference from that determined by the commercial ELISA kit. These results showed that the fabricated PLC sensor had acceptable potential in clinical applications.
Subject(s)
Biosensing Techniques , DNA , DNA/analysis , Polymerization , Biosensing Techniques/methods , Limit of Detection , Electrodes , Electrochemical Techniques/methodsABSTRACT
Mimicking the structures and functions of cells to create artificial organelles has spurred the development of efficient strategies for production of hollow nanoreactors with biomimetic catalytic functions. However, such structure are challenging to fabricate and are thus rarely reported. We report the design of hollow nanoreactors with hollow multishelled structure (HoMS) and spatially loaded metal nanoparticles. Starting from a molecular-level design strategy, well-defined hollow multishelled structure phenolic resins (HoMS-PR) and carbon (HoMS-C) submicron particles were accurately constructed. HoMS-C serves as an excellent, versatile platform, owing to its tunable properties with tailored functional sites for achieving precise spatial location of metal nanoparticles, internally encapsulated (Pd@HoMS-C) or externally supported (Pd/HoMS-C). Impressively, the combination of the delicate nanoarchitecture and spatially loaded metal nanoparticles endow the pair of nanoreactors with size-shape-selective molecular recognition properties in catalytic semihydrogenation, including high activity and selectivity of Pd@HoMS-C for small aliphatic substrates and Pd/HoMS-C for large aromatic substrates. Theoretical calculations provide insight into the pair of nanoreactors with distinct behaviors due to the differences in energy barrier of substrate adsorption. This work provides guidance on the rational design and accurate construction of hollow nanoreactors with precisely located active sites and a finely modulated microenvironment by mimicking the functions of cells.
ABSTRACT
Designing polymeric photocatalysts at the molecular level to modulate the photogenerated charge behavior is a promising and challenging strategy for efficient hydrogen peroxide (H2 O2 ) photosynthesis. Here, we introduce electron-deficient 1,4-dihydroxyanthraquinone (DHAQ) into the framework of resorcinol-formaldehyde (RF) resin, which modulates the donor/acceptor ratio from the perspective of molecular design for promoting the charge separation. Interestingly, H2 O2 can be produced via oxygen reduction and water oxidation pathways, verified by isotopic labeling and in situ characterization techniques. Density functional theory (DFT) calculations elucidate that DHAQ can reduce the energy barrier for H2 O2 production. RF-DHAQ exhibits excellent overall photosynthesis of H2 O2 with a solar-to-chemical conversion (SCC) efficiency exceeding 1.2 %. This work opens a new avenue to design polymeric photocatalysts at the molecular level for high-efficiency artificial photosynthesis.