Synthesis Of Architectures Research Articles

Ultra‐High Metal‐Ion Selectivity Induced by Intramolecular Cation‐π Interactions for the One‐Pot Synthesis of Precise Heterometallic Architectures

AbstractHeterometallic supramolecules, known for their unique synergistic effects, have shown broad applications in photochemistry, host‐guest chemistry, and catalysis. However, there are great challenges to precisely construct heterometallic supramolecules rather than a statistical mixture, due to the limited metal‐ion selectivity of coordination units. In particular, heterometallic architectures precisely encoded with different metal ions usually fail to form in a one‐pot method when only one type of coordinated motif exists due to its poor metal‐ion selectivity. Herein, we propose an effective intramolecular cation‐π (ICπ) strategy and successfully constructed the heterometallic supramolecule Zn2Cu4L34 by the one‐pot self‐assembly of tritopic terpyridyl ligand L3 with Zn(II) and Cu(II), following a clear self‐assembly mechanism in which only thermodynamic dimers ZnL12 and Cu2L22 were constructed with model ligands L1, L2, Zn(II) and Cu(II) with perfect self‐sorting and an ultra‐high metal‐selectivity feature. The successful construction of the heterometallic supramolecule Zn2Cu4L34, in which the definite sequence of metal ions Zn(II) and Cu(II) is encoded in the one‐pot method, will offer a novel approach to precisely construct heterometallic architectures.

Ultra-High Metal-Ion Selectivity Induced by Intramolecular Cation-π Interactions for the One-Pot Synthesis of Precise Heterometallic Architectures.

Heterometallic supramolecules, known for their unique synergistic effects, have shown broad applications in photochemistry, host-guest chemistry, and catalysis. However, there are great challenges to precisely construct heterometallic supramolecules rather than a statistical mixture, due to the limited metal-ion selectivity of coordination units. In particular, heterometallic architectures precisely encoded with different metal ions usually fail to form in a one-pot method when only one type of coordinated motif exists due to its poor metal-ion selectivity. Herein, we propose an effective intramolecular cation-π (ICπ) strategy and successfully constructed the heterometallic supramolecule Zn2Cu4L34 by the one-pot self-assembly of tritopic terpyridyl ligand L3 with Zn(II) and Cu(II), following a clear self-assembly mechanism in which only thermodynamic dimers ZnL12 and Cu2L22 were constructed with model ligands L1, L2, Zn(II) and Cu(II) with perfect self-sorting and an ultra-high metal-selectivity feature. The successful construction of the heterometallic supramolecule Zn2Cu4L34, in which the definite sequence of metal ions Zn(II) and Cu(II) is encoded in the one-pot method, will offer a novel approach to precisely construct heterometallic architectures.

PROTECTS: Progressive Rtl Obfuscation with ThrEshold Control Technique during architectural Synthesis

PROTECTS: Progressive Rtl Obfuscation with ThrEshold Control Technique during architectural Synthesis

The synthesis of N-Trifluoromethyl hydroxylamine from (trifluoromethyl)trimethylsilane

We have presented a straightforward approach for the synthesis of N-CF3 hydroxylamines, utilizing TMSCF3 for the N-trifluoromethylation of nitrosoarenes with the assistance of CsF. This method demonstrates excellent tolerance towards various functional groups and can be applied to a wide range of substrates, highlighting its versatility and utility in synthetic applications. The nucleophilic N-trifluoromethylation pathway for N-CF3 hydroxylamines provides a practical protocol for the synthesis of promising molecular architectures in the field of medicinal chemistry.

Computing Typology: Generative Design for Creating Housing Solutions from Type Analysis in Bogota

AbstractThe article delves into the integration of a typological discourse within contemporary design practice, offering insights into a generative system aimed at processing design scenarios from typological analyses. By identifying architectural types within the context of Bogota’s periphery, this research showcases the potential of computational methods to formalize typological principles in design. It also explores the possibilities of digital design to facilitate the production of customized housing solutions on a mass scale. This study contributes to the debate about the role of typology in design practice, highlighting the possibilities inherent in leveraging computational tools to enhance architectural synthesis. Additionally, it investigates the potential of a digital design framework to offer alternative solutions to the housing crisis, addressing the growing demand for affordable, high-quality housing in Latin America.

Silicon Carbide Nanowire Based Integrated Electrode for High Temperature Supercapacitors.

Silicon carbide (SiC) single crystals have great prospects for high-temperature energy storage due to their robust structural stability, ultrahigh power output, and superior temperature stability. However, energy density is an essential challenge for SiC-based devices. Herein, a facile two-step strategy is proposed for the large-scale synthesis of a unique architecture of SiC nanowires incorporating MnO2 for enhanced supercapacitors (SCs), arising from the synergy effect between the SiC nanowires as a highly conductive skeleton and the MnO2 with numerous active sites. The SiC@MnO2 integrated electrode-based SCs with ionic liquid (IL) electrolytes were assembled and delivered outstanding energy and power density, as well as a great lifespan at 150 °C. This impressive work offers a novel avenue for the practical application of SiC-based electrochemical energy storage devices with high energy density under high temperatures.

Self-Assembly of a Hierarchical Metal-Organic Framework at the Liquid/Liquid Interface via π-π Stacking Manipulations in Organoplatinum(IV) Complexes for Methanol Fuel Cells.

This study focuses on the facile synthesis of the hierarchical architecture of zeolitic imidazolate framework-8 (ZIF-8) films containing an ultrasmall amount of Pt(0) by investigating the synthesis of different organoplatinum complexes and manipulating the π-π stacking effect in these complexes at the liquid/liquid interface. The organometallic Pt(IV) precursors were complexes with a formula of [PtXMe2(R)(bpy)] (bpy = 2,2'-bipyridine; for complex 2, R = CH2CH═CHC6H5 and X = Br; for complex 3, R = CH2CH═CH2 and X = Br; for complex 4, R = Me and X = I) prepared by oxidative addition of cinnamyl bromide, allyl bromide, or methyl iodide to [PtMe2(bpy)] (complex 1). Different thin films were synthesized starting from three organometallic Pt(IV) precursors (i) by reduction of the Pt complexes at the toluene/water interface (TF2-TF4), (ii) by encapsulation of the Pt precursors in a ZIF-8 (TF5-TF7), and (iii) by reduction of the Pt precursors onto a ZIF-8 (TF8-TF10). The self-assembly of ZIF-8 and different organoplatinum precursors at the interface of two immiscible liquids leads to the preparation of films with well-engineered structures such as rhombic dodecahedra, nanorods, hierarchical architectures, and nanowires, which are very difficult and complicated to synthesize under normal conditions. The ultralow loading of platinum complexes with different degrees of π-π stacking of dangling moieties has a great impact on the structure and morphology (directing agent), which in turn drastically changes the catalytic properties. The obtained films were applied as electrocatalysts for methanol oxidation in fuel cells. The electrocatalytic performance of organoplatinum containing a cinnamyl group in hierarchical architecture TF8 was found to be superior to those of nonhierarchical structures.

Ontological model of structure and parameters of components in high-tech product modernization projects

The subject of the article is models representing the structure and parameters of components in high-tech products based on the analysis of technical documentation in modernization projects. The purpose of the proposed research is to enhance the quality of modernization processes of high-tech products by forming an ontological model of the product with innovative components, considering the diversity of information support. The article addresses the following tasks: studying the main methods and technologies of system representation of complex product structure; forming a model of structural-functional decomposition of a high-tech product, creating an ontological model of the structure and parameters of a high-tech product based on technical documentation. The following methods are applied: systemic approach, methods of functional-structural decomposition, set theory, ontology construction methods, semantic models. The following results were obtained: The main methods of system representation of complex product structure were investigated, based on the following principles: decomposition of complex product architecture, layering of complex product representation, multivariate synthesis of component architecture. The main directions and advantages of using 3D technologies for solving design tasks in modernization projects of high-tech product components are considered. The decomposition of a high-tech product into component parts and partial parameters is proposed, taking into account functional, structural, and parametric characteristics. An ontological model of the structure and parameters of a high-tech product is formed based on a set of technical documentation and considering additional heterogeneous sources of information. Innovative elements are identified, the description of which may be fuzzy. Conclusions. The proposed ontological model can serve as a basis for finding similar solutions regarding the design of innovative components in the precedent database, which is properly structured. In the absence of similar design solutions, innovative component design can be carried out using 3D technologies based on supplementing fuzzy information in the semantic model.

Novel Substitution Box Architectural Synthesis for Lightweight Block Ciphers

This paper proposes three novel Substitution box (S-box) architectures for lightweight block ciphers. The proposed S-box architectures are based on Boolean decomposition to achieve the design tradeoffs. Absorption of the Terminal Nodes property, positive Davio expansion, and Shannon decomposition are explored for the three S-box architectures. The proposed S-box variants are included in the SPN layer of the Midori-64 block cipher to validate their utility for a lightweight cipher. Also, to demonstrate the generality of the proposed logic decomposition approaches, the proposed work is expanded to the composite field architectures for the S-box of AES-128. Compared with state-of-the-art designs, the proposed designs exhibit a reduction of 66%, 36%, and 21% for energy, delay, and power metrics.

Hydrophilic Poly(meth)acrylates by Controlled Radical Branching Polymerization: Hyperbranching and Fragmentation.

Topology significantly impacts polymer properties and applications. Hyperbranched polymers (HBPs) synthesized via atom transfer radical polymerization (ATRP) using inimers typically exhibit broad molecular weight distributions and limited control over branching. Alternatively, copolymerization of inibramers (IB), such as α-chloro/bromo acrylates with vinyl monomers, yields HBPs with precise and uniform branching. Herein, we described the synthesis of hydrophilic HB polyacrylates in water by copolymerizing a water-soluble IB, oligo(ethylene oxide) methyl ether 2-bromoacrylate (OEOBA), with various hydrophilic acrylate comonomers. Visible-light-mediated controlled radical branching polymerization (CRBP) with dual catalysis using eosin Y (EY) and copper complexes resulted in HBPs with various molecular weights (M n = 38 000 to 170 000) and degrees of branching (2%-24%). Furthermore, the optimized conditions enabled the successful application of the OEOBA to synthesize linear-hyperbranched block copolymers and hyperbranched polymer protein hybrids (HB-PPH), demonstrating its potential to advance the synthesis of complex macromolecular architecture under environmentally benign conditions. Copolymerization of hydrophilic methacrylate monomer, oligo(ethylene oxide) methyl ether methacrylate (OEOMA500), and inibramer OEOBA was accompanied by fragmentation via β-carbon C-C bond scission and subsequent growth of polymer chains from the fragments. Furthermore, computational studies investigating the fragmentation depending on the IB and comonomer structure supported the experimental observations. This work expands the toolkit of water-soluble inibramers for CRBP and highlights the critical influence of the inibramer structure on reaction outcomes.

Hydrothermal synthesis of high-performance cobalt phosphate nanorod architecture as bifunctional electrocatalysts for rechargeable Zn-air batteries and supercapatteries

Transition metal phosphate bifunctional electrocatalysts demonstrate superior oxygen evolution reaction (OER), oxygen reduction reaction (ORR), and capacitive properties owing to their high electrocatalytic and conductive activities. In this report, cobalt phosphate (Co3P2O8) nanorod (NR) electrocatalytic materials were developed via a facile one-step hydrothermal synthesis, followed by an annealing process. The unique NR structures offer superior electrocatalytic activities, continuous and quick electron transport pathways, short ion diffusion lengths, and rich active sites toward rechargeable zinc-air batteries (ZABs) and supercapatteries (SCs). The self-assembled Co3P2O8 NR electrocatalyst revealed higher current density values during the OER and ORR measurements than the commercially available Pt/C and IrO2 materials. The Co3P2O8 NR electrocatalyst exhibited an excellent OER overpotential of 180 mV. The electocatalyst also showed superior onset and half-wave potentials of 0.92 V and 0.80 V, respectively. Moreover, the fabricated Co3P2O8 NRs-based ZAB exhibited better durability than the Pt/C-based ZAB. Significantly, the Co3P2O8 NR electrode demonstrated an excellent specific capacity of 373 mAh g−1 with outstanding cycling stability of 99% after 5000 cycles. Additionally, the fabricated Co3P2O8 NRs//activated carbon SC demonstrated high specific energy and power densities of 25.62 Wh kg−1 and 2953.12 W kg−1, respectively with remarkable cycling stability of 89% after 7000 cycles. Specifically, the practical applicability of the fabricated Co3P2O8 NRs-based ZAB and SC was tested using a blue light-emitting diode nameplate energized by two devices in series. Overall, the catalytic and energy-storage properties of the Co3P2O8 NR material can provide a new pathway for high-energy electrochemical applications.

Laser‐Induced Graphene Toward Flexible Energy Harvesting and Storage Electronics

AbstractEnergy harvesting and storage devices play an increasingly important role in the field of flexible electronics. Laser‐induced graphene (LIG) with hierarchical porosity, large specific surface area, high electrical conductivity, and mechanical flexibility is an ideal candidate for fabricating flexible energy devices which supply power for other electronic components. Through a simple laser irradiation process with designable routes, abundant precursors (or substrates) rapidly transform into patterned LIG without any other treatments. The structure and physicochemical properties of LIG can be regulated by controlling the processing strategies and parameters, enabling the optimization of device performance. The laser scribing method, as a non‐contact and in situ technique, proves to be efficient in integrating different LIG‐based devices, resulting in all‐in‐one flexible power platforms. Here, a systematic summary of recent advancements in LIG‐based flexible energy electronics is presented. The controllable synthesis of LIG, functional LIG, and 3D architectures are described by elucidating corresponding mechanisms and processing strategies. An overall review of flexible energy conversion and storage devices based on LIG is presented. Eventually, the challenges and opportunities of LIG‐based materials in flexible energy conversion and storage are briefly discussed.

Computational design of myoglobin-based carbene transferases for monoterpene derivatization

Carbene transfer reactions have emerged as pivotal methodologies for the synthesis of complex molecular architectures. Heme protein-catalyzed carbene transfer reactions have shown promising results on model compounds. However, their limited substrate scope has hindered their application in natural product functionalization. Building upon the foundation of previously published work on a carbene transferase-myoglobin variant, this study employs computer-aided protein engineering to design myoglobin variants, using either docking or the deep learning-based LigandMPNN method. These variants were utilized as catalysts in carbene transfer reactions with a selection of monoterpene substrates featuring C–C double bonds, leading to seven target products. This cost-effective methodology broadens the substrate scope for heme protein-catalyzed reactions, thereby opening novel pathways for research in heme protein functionalities and offering fresh perspectives in the synthesis of bioactive molecules.

Noncovalent synthesis of homo and hetero-architectures of supramolecular polymers via secondary nucleation

The synthesis of supramolecular polymers with controlled architecture is a grand challenge in supramolecular chemistry. Although living supramolecular polymerization via primary nucleation has been extensively studied for controlling the supramolecular polymerization of small molecules, the resulting supramolecular polymers have typically exhibited one-dimensional morphology. In this report, we present the synthesis of intriguing supramolecular polymer architectures through a secondary nucleation event, a mechanism well-established in protein aggregation and the crystallization of small molecules. To achieve this, we choose perylene diimide with 2-ethylhexyl chains at the imide position as they are capable of forming dormant monomers in solution. Activating these dormant monomers via mechanical stimuli and hetero-seeding using propoxyethyl perylene diimide seeds, secondary nucleation event takes over, leading to the formation of three-dimensional spherical spherulites and scarf-like supramolecular polymer heterostructures, respectively. Therefore, the results presented in this study propose a simple molecular design for synthesizing well-defined supramolecular polymer architectures via secondary nucleation.

Advances in the Synthesis of Sulfur-Containing Cyclic Architectures via Insertion of SO2

AbstractSulfur-containing heterocycles, where the S(R) moiety is located within the cyclic structure, have found tremendous applications in the fields of chemical, pharmaceutical, and materials sciences due to their unique chemical, biological and pharmaceutical activities. Recent years have witnessed increasing interest in sulfur-containing heterocycles, and new methods for their synthesis have been reported by adopting modern methodologies and technologies through insertion of sulfur dioxide. The main objective of this Account is to overview the latest major developments on the synthesis of sulfur-containing heterocyclic systems, mainly covering thermo-, photo- and electron-induced cyclization through the insertion of sulfur dioxide (SO2). We aim to provide the readership with a comprehensive understanding of this topic and offer a positive outlook on the promising future of this field.1 Introduction2 Thermal-Induced Cyclization3 Photoinduced Radical Cyclization4 Electron-Induced Radical Cyclization5 Conclusion

Acoustic Levitation Synthesis of Ultrahigh-Density Spherical Nucleic Acid Architectures for Specific SERS Analysis.

Controllably regulating the electrostatic bilayer of nanogold colloids is a significant premise for synthesizing spherical nucleic acid (SNA) and building ordered plasmonic architectures. We develop a facile acoustic levitation reactor to universally synthesize SNAs with an ultra-high density of DNA strands, which is even higher than those of various state-of-the-art methods. Results reveal a new mechanism of DNA grafting via acoustic wave that can reconfigure the ligands on colloidal surfaces. The acoustic levitation reactor enables substrate-free three-dimentional (3D) spatial assembly of SNAs with controllable interparticle nanogaps through regulating DNA lengths. This kind of architecture may overcome the plasmonic enhancement limits by blocking electron tunneling and breaking electrostatic shielding in dried aggregations. Finite element simulations support the architecture with 3D spatial plasmonic hotspot matrix, and its ultrahigh surface-enhanced Raman scattering (SERS) capability is evidenced by in situ untargeted tracking of biomolecular events during photothermal stimulation (PTS)-induced cell death process. For biomarker diagnosis, the conjugation of adenosine triphosphate (ATP) aptamer onto SNAs enables in situ targeted tracking of ATP during PTS-induced cell death process. Particularly, the CD71 receptor and integrin α3β1 protein on PL45 cell membrance could be well distinguished by label-free SERS fingerprints when using specific XQ-2d and DML-7 aptamers, respectively, to synthesize SNA architectures. Our current acoustic levitation reactor offers a new method for synthesizing SNAs and enables both targeted and untargeted SERS analysis for tracking molecular events in living systems. It promises great potentials in biochemical synthesis and sensing in future.

A Survey of Wireless Charging System for Electric Vehicles and Fire Protection

Wireless charging for electric vehicles offers convenient power replenishment without physical connections. Fire protection measures are integral to ensure safety during wireless charging, mitigating potential risks of overheating or electrical malfunctions. The integration of wireless charging systems for electric vehicles (evs) alongside effective fire protection measures presents a promising avenue towards enhancing the sustainability and safety of urban transportation. In this survey work, we meticulously examine the state-of-the-art advancements, methodologies, and challenges pertaining to the fusion of wireless charging technologies with robust fire protection mechanisms for evs. In this survey encapsulates a synthesis of methodologies, technical architectures, and regulatory frameworks, providing researchers and practitioners with valuable insights to navigate the intricate landscape of wireless charging systems for evs and fire protection

Progress in photocontrolled radical polymerization for the synthesis of nonlinear polymer architectures

AbstractControlled radical polymerization (CRP) techniques enable the preparation of diverse, chemically tailored polymers with a variety of chain architectures. Separately, light‐mediated polymerization reactions offer a number of advantages over thermal polymerizations in terms of energy efficiency, sustainability, and versatility. Recent work has combined photopolymerization and CRP techniques to advance the synthesis of polymers with nonlinear architectures, including bottlebrush polymers, star polymers, hyperbranched polymers, and cyclic polymers. These photoCRP methods offer novel routes to nonlinear polymers using mild reaction conditions. In this review, we provide an overview of photoCRP techniques for the synthesis of nonlinear polymers. We start with a discussion of photoCRP applied to the synthesis of linear polymers and discuss the underlying reaction mechanisms. Then, we discuss photoCRP applied to the synthesis of bottlebrush, star, hyperbranched, cyclic, and surface‐initiated polymer brushes. For each case, we discuss the synthetic strategy and the unique properties and characteristics of the resulting polymers, and we provide a perspective on potential future directions for research.

Anti-perovskite Co4N nanowhisker rooted on nickel foam to activate peroxymonosulfate for robust degradation of p-nitrophenol via non-radical dominant pathway

The fabrication of metal-nitrogen functional centers that possess features of easy recovery and high performance for degrading organic pollutants through activating peroxymonosulfate (PMS) represents a significant challenge. In this study, we present the synthesis of an anti-perovskite Co4N architecture in a granular nanowhisker form rooted on three-dimensional nickel foam (Co4N/NF) using a hydrothermal method followed by thermal nitridation with ammonia from urea pyrolysis. The resulting Co4N/NF exhibits exceptional efficiency in degrading p-nitrophenol (PNP), achieving a degradation efficiency of 97.8 % and a rate constant of 0.204 min−1 within 20 min. The unique nanostructure of granular nanowhisker Co4N on NF provides abundant surface sites for activating PMS and enhances mass/electron transport, contributing to its excellent degradation capabilities. Additionally, the Co4N/NF material exhibits outstanding stability, easy separation and recovery features, maintaining a degradation efficiency of 90.2 % within 20 min even after five cycles. This study lays the groundwork for developing advanced anti-perovskite nitrides on a 3D substrate to activate PMS for environmental contaminant remediation.

Grafting in Tomato for Improving Abiotic Stress Tolerance, Yield and Quality Traits

Tomato (Solanum lycopersicum L.) is a major vegetable crop worldwide, however, its production is adversely affected by a wide range of abiotic and biotic stresses at various stages of its cultivation. Abiotic stresses, such as drought, salinity, flooding, extreme temperatures and heavy metals can cause morphological, physiological and biochemical changes in the plant, which ultimately affect crop growth, yield and quality. Among various mitigation strategies, grafting technology has emerged as an effective and alternative tool to slow breeding programs to alleviate various biotic and abiotic stresses. Various studies indicated that increased osmolytes accumulation, synthesis of antioxidant enzymes, improved photosynthesis and vigorous root architecture in grafted tomatoes confer tolerance towards abiotic stresses, besides improving plant growth and fruit yields. Moreover, tomato grafting on suitable rootstocks has also a positive effect on the nutritional qualities of fruits, such as, lycopene, β-carotene, ascorbic acid, proteins, etc.). In this review, we have tried to summarize the adverse effects of abiotic stresses in tomatoes and include all possible recent references related to the response of grafted tomatoes using different intra-and/ or inter-specific rootstocks on improving plant growth, yield and quality and alleviation in various abiotic stresses.