On-surface synthesis of one-dimensional carbyne-like nanostructures with sp-carbon

Carbyne is an infinite one-dimensional carbon chain comprising of sp-hybridized carbons.Due to its high chemical reactivity and extreme instability,the synthesis and structural diversity of carbyne have been much less investigated in the past decades compared to carbon allotropes built with sp^(2)hybridized carbons,such as fullerenes,carbon nanotubes,and graphene.The emerging on-surface synthesis strategy provides an extremely promising approach for the fabrication of novel carbyne-like nanostructures with atomic precision.Herein,we summarize recent exciting progress in the synthesis of carbyne-like nanostructures with one-dimensional sp-carbon on surfaces,including polyynes,cumulenes,and organometallic polyynes.We also point out the scientific challenges and prospects,encouraging scientists to explore the fabrication and characterization of single strands of carbyne in this young and promising research field.

Single-Atom Protecting Group for on-Surface Synthesis of Graphdiyne Nanowires

On-surface synthesis of semiconducting graphdiyne nanowires usually suffer severe side reactions owing to the high reactivity of the butadiynylene units at noble metal surfaces,limiting the production of isolated nanowires. In this work, we report the high-yield synthesis of branchless graphdiyne nanowires [-C≡C-Ph2-C≡C-]nvia on-surface Ullmann coupling of 1,4-bis（4-bromophenyl）-1,3-butadiyne molecules with chemical vapor deposition method.Non-contact atomic force microscopy with single-bond resolution reveals that single gold adatoms act as effective protecting groups for butadiynylene units by forming Au-π ligand bonds, preventing unwanted branched coupling reactions and enabling the synthesis of ultralong isolated graphdiyne nanowires. This study will stimulate further investigation on the role of various surface adatoms in protecting on-surface reactions.

On-Surface Synthesis of Electron-Deficient Bisanthene Tetraimide

Imide-based conjugated molecules have emerged as a highly promising class of building blocks for constructing n-type semiconducting materials with lowlying lowest unoccupied molecular orbitals and exceptional stability.Although imides,such as naphthalene diimides,perylene diimides and their lateral fused analogs,have been synthesized extensively,the design and synthesis of largerπ-extended molecules incorporating more than two imide groups are desirable but still very challenging.Herein,we report the synthesis of an unprecedented electron-deficient bisanthene tetraimide(ATI)containing a bisantheneconjugated core and four five-membered imide groups,which was successfully achieved via a combined approach of solution and on-surface synthesis.The chemical structures,electronic states,formation mechanism and aromaticity of ATI were systematically investigated by scanning tunneling microscopy,noncontact atomic force microscopy,scanning tunneling spectroscopy,and density functional theory calculations.

On-Surface Synthesis of Anthracene-Fused Zigzag Graphene Nanoribbons from 2,7-Dibromo-9,9′-bianthryl Reveals Unexpected Ring Rearrangements

On-surface synthesis has emerged as a powerful strategy to fabricate unprecedented forms of atomically precise graphene nanoribbons(GNRs).However,the on-surface synthesis of zigzag GNRs(ZGNR)has met with only limited success.Herein,we report the synthesis and on-surface reactions of 2,7-dibromo-9,9′-bianthryl as the precursor towardπ-extended ZGNRs.Characterization by scanning tunneling microscopy and high-resolution noncontact atomic force microscopy clearly demonstrated the formation of anthracene-fused ZGNRs.Unique skeletal rearrangements were also observed,which could be explained by intramolecular Diels-Alder cycloaddition.Theoretical calculations of the electronic properties of the anthracene-fused ZGNRs revealed spin-polarized edge-states and a narrow bandgap of 0.20 eV.

On-Surface Synthesis of Na-Porphyrins Using NaCl as a Convenient Na Source

Metallo-porphyrins with different metal centers display unique properties and are essential in various biological and chemical processes.Enormous efforts have been devoted to enriching the family of metallo-porphyrins on surfaces mainly through metalation processes within porphyrins and exogenous pure metals or intrinsic surface adatoms,which have focused on transition elements.However,less attention has been paid to the synthesis of alkali-metal-based porphyrins on a surface.Herein,by a combination of scanning tunneling microscopy(STM)imaging/manipulations and density functional theory(DFT)calculations,we report the fabrication of Na-porphyrins on Au(111)by introducing NaCl,i.e.,two double-layered Na-centered porphyrins.Moreover,the interconversion between them was realized by precise STM manipulations.Our results demonstrate the feasibility of metalation by applying inorganic salt,which would serve as a promising strategy to embed intramolecular metal components into porphyrins for further functionalization and modification.

The structure-directing role of heterologous seeds in the synthesis of zeolite

Zeolites have been widely used as catalysts,ion-exchangers,and adsorbents in chemical industries,detergent industry,steel industry,glass industry,ceramic industry,medical and healthfield,and environmentalfield,and recently applied in energy storage.Seed-assisted synthesis is a very effective approach in promoting the crystallization of zeolites.In some cases,the target zeolite cannot be formed in the absence of seed zeolite.In homologous seed-assisted synthesis,the structure of the seed zeolite is the same to that of the target zeolite,while the structure of the seed zeolite is different to that of the target zeolite in the heterologous seed-assisted synthesis.In this review,we briefly summarized the heterologous seed-assisted syntheses of zeolites and analyzed the structure-directing effect of heterologous seeds and surveyed the“common composite building units(CBUs)hypothesis”and the“common secondary building units(SBUs)hypothesis”.However,both hypotheses cannot explain all observations on the heterologous seed-assisted syntheses.Finally,we proposed that the formation of the target zeolite does need nuclei with the structure of target zeolite and the formation of the nuclei of the target zeolite can be promoted by either the undissolved seed crystals with the same CBUs or SBUs to the target zeolite or by the facilitated appropriate distribution of the specific building units due to the presence of the heterologous seed that does not have any common CBUs and SBUs with the target zeolite.

Templated synthesis of transition metal phosphide electrocatalysts for oxygen and hydrogen evolution reactions

Transition metal phosphides(TMPs)have been regarded as alternative hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)catalysts owing to their comparable activity to those of noble metal-based catalysts.TMPs have been produced in various morphologies,including hollow and porous nanostructures,which are features deemed desirable for electrocatalytic materials.Templated synthesis routes are often responsible for such morphologies.This paper reviews the latest advances and existing challenges in the synthesis of TMP-based OER and HER catalysts through templated methods.A comprehensive review of the structure-property-performance of TMP-based HER and OER catalysts prepared using different templates is presented.The discussion proceeds according to application,first by HER and further divided among the types of templates used-from hard templates,sacrificial templates,and soft templates to the emerging dynamic hydrogen bubble template.OER catalysts are then reviewed and grouped according to their morphology.Finally,prospective research directions for the synthesis of hollow and porous TMP-based catalysts,such as improvements on both activity and stability of TMPs,design of environmentally benign templates and processes,and analysis of the reaction mechanism through advanced material characterization techniques and theoretical calculations,are suggested.

Facile synthesis of hierarchical NaX zeolite from natural kaolinite for efficient Knoevenagel condensation

Zeolite catalysts have found extensive applications in the synthesis of various fine chemicals.However,the micropores of zeolites impose diffusion limitations on bulky molecules,greatly reducing the catalytic efficiency.Herein,we explore an economic and environmentally friendly method for synthesizing hierarchical NaX zeolite that exhibits improved catalytic performance in the Knoevenagel condensation reaction for producing the useful fine chemical 2-cyano-3-phenylacrylate.The synthesis was achieved via a low-temperature activation of kaolinite and subsequent in-situ transformation strategy without any template or seed.Systematic characterizations reveal that the synthesized NaX zeolite has both intercrystalline and intra-crystalline mesopores,smaller crystal size,and larger external specific surface area compared to commercial NaX zeolite.Detailed mechanism investigations show that the inter-crystalline mesopores are generated by stacking smaller crystals formed from in-situ crystallization of the depolymerized kaolinite,and the intra-crystalline mesopores are inherited from the pores in the depolymerized kaolinite.This synthesis strategy provides an energy-saving and effective way to construct hierarchical zeolites,which may gain wide applications in fine chemical manufacturing.

Optimal synthesis of heat-integrated distillation configurations using the two-column superstructure

In the realm of the synthesis of heat-integrated distillation configurations,the conventional approach for exploring more heat integration possibilities typically entails the splitting of a single column into a twocolumn configuration.However,this approach frequently necessitates tedious enumeration procedures,resulting in a considerable computational burden.To surmount this formidable challenge,the present study introduces an innovative remedy:The proposition of a superstructure that encompasses both single-column and multiple two-column configurations.Additionally,a simultaneous optimization algorithm is applied to optimize both the process parameters and heat integration structures of the twocolumn configurations.The effectiveness of this approach is demonstrated through a case study focusing on industrial organosilicon separation.The results underscore that the superstructure methodology not only substantially mitigates computational time compared to exhaustive enumeration but also furnishes solutions that exhibit comparable performance.

Recent advances in cobalt phosphide-based materials for electrocatalytic water splitting:From catalytic mechanism and synthesis method to optimization design

Electrochemical water splitting has long been considered an effective energy conversion technology for trans-ferring intermittent renewable electricity into hydrogen fuel,and the exploration of cost-effective and high-performance electrocatalysts is crucial in making electrolyzed water technology commercially viable.Cobalt phosphide(Co-P)has emerged as a catalyst of high potential owing to its high catalytic activity and durability in water splitting.This paper systematically reviews the latest advances in the development of Co-P-based materials for use in water splitting.The essential effects of P in enhancing the catalytic performance of the hydrogen evolution reaction and oxygen evolution reaction are first outlined.Then,versatile synthesis techniques for Co-P electrocatalysts are summarized,followed by advanced strategies to enhance the electrocatalytic performance of Co-P materials,including heteroatom doping,composite construction,integration with well-conductive sub-strates,and structure control from the viewpoint of experiment.Along with these optimization strategies,the understanding of the inherent mechanism of enhanced catalytic performance is also discussed.Finally,some existing challenges in the development of highly active and stable Co-P-based materials are clarified,and pro-spective directions for prompting the wide commercialization of water electrolysis technology are proposed.

On-surface synthesis of covalent coordination polymers on micrometer scale

On-surface synthesis under ultrahigh vacuum provides a promising strategy to control matter at the atomic level, with important implications for the design of new two-dimensional materials having remarkable electronic, magnetic, or catalytic properties. This strategy must address the problem of limited extension of the domains due to the irreversible nature of covalent bonds, which prevents the ripening of defects. We show here that extended materials can be produced by a controlled co-deposition process. In particular, co-deposition of quinoid zwitterion molecules with iron atoms on a Ag（111） surface held at 570 K allows the formation of micrometer-sized domains based on covalent coordination bonds. This work opens up the construction of micrometer-scale single-layer covalent coordination materials under vacuum conditions.

Nucleosynthesis in the little bang

A new approach based on relativistic kinetic equations is proposed to solve the long-standing puzzle of light cluster formation, also called nucleosynthesis, in high-energy heavy-ion collisions. This method addresses the tension between STAR data and previous studies relying on either statistical equilibrium or coalescence approaches.

Cost-Effective Method of Gene Synthesis by Sequencing from Microchip-Derived Oligos for Droplet Cloning

Gene synthesis has provided important contributions in various fields including genomics and medicine. Current genes are 7 - 30 cents depending on the assembly and sequencing methods performed. Demand for gene synthesis has been increasing for the past few decades, yet available methods remain expensive. A solution to this problem involves microchip-derived oligonucleotides (oligos), an oligo pool with a substantial number of oligo fragments. Microchips have been proposed as a tool for gene synthesis, but this approach has been criticized for its high error rate during sequencing. This study tests a possible cost-effective method for gene synthesis utilizing fragment assembly and golden gate assembly, which can be employed for quicker manufacturing and efficient execution of genes in the near future. The droplet method was tested in two trials to determine the viability of the method through the accuracy of the oligos sequenced. A preliminary research experiment was performed to determine the efficacy of oligo lengths ranging from two to four overlapping oligos through Gibson assembly. Of the three oligo lengths tested, only two fragment oligos were correctly sequenced. Two fragment oligos were used for the second experiment, which determined the efficacy of the droplet method in reducing gene synthesis cost and speed. The first trial utilized a high-fidelity polymerase and resulted in 3% correctly sequenced oligos, so the second trial utilized a non-high-fidelity polymerase, resulting in 8% correctly sequenced oligos. After calculating, the cost of gene synthesis lowers down to 0.8 cents/base. The final calculated cost of 0.8 cents/base is significantly cheaper than other manufacturing costs of 7 - 30 cents/base. Reducing the cost of gene synthesis provides new insight into the cost-effectiveness of present technologies and protocols and has the potential to benefit the fields of bioengineering and gene therapy.

N,S,Br co-doped carbon dots:One-step synthesis and fluorescent detection of 6-mercaptopurine in tablet

6-mercaptopurine(6-MP),a purine derivative(3,7-dihydropurine-6-thione),has been utilized as an effective immunosuppressive drug for clinically treating leukemia and other autoimmune diseases[1].6-MP and its corresponding metabolites can suppress the function of RnaseH,and thus they are cytotoxic and threaten the human health[2].Therefore,the accurate quantification of 6-MP is crucial.To date,researchers continue to expend considerable effort in developing 6-MP detection methods.Fluorescence analysis eliminates disadvantages,such as toxic solvents,expensive equipment.

Synthesis Methods and Property Control of Two-Dimensional Magnetic Materials

Two-dimensional(2D)magnetic materials have been demonstrated to have excellent chemical,optical,electrical,and magnetic properties,particularly in the development of multifunctional electronic and spin electronic devices,showcasing tremendous potential.Therefore,corresponding synthesis techniques for 2D magnetic materials that offer high quality,high yield,low cost,time-saving,and simplicity are highly desired.This review provides a comprehensive overview of recent research advances in preparation of magnetic 2D materials,with a particular focus on the preparation methods employed.Moreover,the characteristics and applications of these magnetic materials are also discussed.Finally,the challenges and prospects of synthesis methods for magnetic 2D materials are briefly addressed.This review serves as a guiding reference for the controlled synthesis of 2D magnetic materials.

Synthesis of mordenite by solvent-free method and its application in the dimethyl ether carbonylation reaction

Mordenite with different Si/Al ratios were synthesized by solvent-free method and used for dimethyl ether(DME)carbonylation reaction.The influence of Si/Al ratio in the feedstock on the structure,porosity and acid sites were systematically investigated.The characterization results showed that with the increase of Si/Al ratio in the feedstock,part of silicon species fail to enter the skeleton and the specific surface area and pore volume of the samples decreased.The amount of weak acid and medium strong acid decreased alongside with the increasing Si/Al ratio,and the amount of strong acid slightly increased.The Al atoms preferentially enter the strong acid sites in the 8 member ring(MR)channel during the crystallization process.The high Si/Al ratio sample had more acid sites located in the 8 MR channel,leading to more active sites for carbonylation reaction and higher catalytic performance.Appropriately increasing the Si/Al ratio was beneficial for the improvement of carbonylation reaction activity over the mordenite(MOR)catalyst.

Synthesis of Silver Nanoparticles from Honeybees and Its Antibacterial Potential

Honeybees (Apis mellifera) are important pollinators of flowering plants and agricultural crops contributing annually to billions of dollars in revenues to crop production. Honeybees have an average lifespan between 8 weeks to 5 years. Dead honeybees are abundantly available in beehives and can be utilized as an alternative source to synthesize nanoparticles. In recent years, biologically synthesized nanoparticles have been preferred over their chemical counterparts. However, honeybee-based-green synthesis of nanoparticles has not been explored yet. Herein, we report the biosynthesis of silver nanoparticles from honeybees and its antibacterial activity. The synthesis of silver nanoparticles was monitored visually through a gradual change in color. Furthermore, the biosynthesized nanoparticles were confirmed and characterized by UV-visible spectroscopy. Scanning Electron Microscope was utilized to analyze the average size and morphologies of the biosynthesized nanoparticles. Subsequently, the antibacterial potential of the biosynthesized silver nanoparticles was tested against selected Gram-positive and Gram-negative bacterial strains. It was found that a distinct color change from yellow to brown in the reaction solution suggested the formation of silver nanoparticles. The biosynthesized nanoparticles exhibited absorption maxima at 430 nm. The SEM analysis confirmed the spherical and cuboidal shape of the biosynthesized silver nanoparticles with a size range between 10 - 40 nm. Furthermore, the biosynthesized silver nanoparticles exhibited strong antimicrobial potential against tested Gram-positive and Gram-negative bacteria strains by aggregating on the cell surface. This study showcases the biomedical and agricultural applications of biosynthesized silver nanoparticles from honeybee wings. .

Rapid Green Synthesis of Silver Nanoparticles by Reishi and Their Antibacterial Activity and Mechanisms

Nanotechnology is a rapidly growing field in biomedical engineering with references to efficiency, safety, and cost-effective approaches. Herein, the objective of this study was to examine an innovative approach to rapidly synthesis silver nanoparticles from an aqueous extract of medicinal mushroom Ganoderma lucidum (also known as reishi). The structural and dimensional dispersion of the biosynthesized silver nanoparticles from reishi was confirmed by UV-Vis spectrophotometer (UV-Vis) and Scanning Electron Microscopy (SEM) analysis. Additionally, the biosynthesized silver nanoparticles from resihi were used to explore their potential antimicrobial activity against Staphylococcus aureus and Micrococcus luteus and Escherichia coli and Klebsiella pneumoniae. The results from this study revealed that the silver nanoparticles mediated by reishi adopted a spherical shape morphology with sizes, less than 100 nm and revealed strong absorption plasmon band at 440 nm. Furthermore, the biosynthesized silver nanoparticles from reishi exhibited antibacterial activity against the tested S. aureus and M. luteus and E. coli and K. pneumoniae by altering their morphology which signifies their biomedical potential.

Transcriptomic and metabolomic analysis provides insights into lignin biosynthesis and accumulation and differences in lodging resistance in hybrid wheat

The use of hybrid wheat is one way to improve the yield in the future.However,greater plant heights increase lodging risk to some extent.In this study,two hybrid combinations with differences in lodging resistance were used to analyze the stem-related traits during the filling stage,and to investigate the mechanism of the difference in lodging resistance by analyzing lignin synthesis of the basal second internode(BSI).The stem-related traits such as the breaking strength,stem pole substantial degree(SPSD),and rind penetration strength(RPS),as well as the lignin content of the lodging-resistant combination(LRC),were significantly higher than those of the lodgingsensitive combination(LSC).The phenylpropanoid biosynthesis pathway was significantly and simultaneously enriched according to the transcriptomics and metabolomics analysis at the later filling stage.A total of 35 critical regulatory genes involved in the phenylpropanoid pathway were identified.Moreover,42%of the identified genes were significantly and differentially expressed at the later grain-filling stage between the two combinations,among which more than 80%were strongly up-regulated at that stage in the LRC compared with LSC.On the contrary,the LRC displayed lower contents of lignin intermediate metabolites than the LSC.These results suggested that the key to the lodging resistance formation of LRC is largely the higher lignin synthesis at the later grain-filling stage.Finally,breeding strategies for synergistically improving plant height and lodging resistance of hybrid wheat were put forward by comparing the LRC with the conventional wheat applied in large areas.

EjGASA6 promotes flowering and root elongation by enhancing gibberellin biosynthesis

The Gibberellic Acid-stimulated Arabidopsis(GASA)gene family is involved in the regulation of gene expression and plant growth,development,and stress responses.To investigate the function of loquat GASA genes in the growth and developmental regulation of plants,a loquat EjGASA6 gene homologous to Arabidopsis AtGASA6 was cloned.EjGASA6 expression was induced by gibberellin,and ectopic transgenic plants containing this gene exhibited earlier bloom and longer primary roots since these phenotypic characteristics are related to higher gibberellin content.Transcriptome analysis and qRT-PCR results showed that the expression levels of GA3ox1 and GA20ox1,which encode key enzymes in gibberellin biosynthesis,were significantly increased.Furthermore,we confirmed that EjGASA6 could promote the expression of GA20ox1 via the luciferase reporter system.Overall,our results suggest that EjGASA6 promotes blooming and main-root elongation by positively regulating gibberellin biosynthesis.These findings broaden our understanding of the role of GASAs in plant development and growth,and lay the groundwork for future research into the functions of EjGASA6 in regulating loquat growth and development.