Synthesis Of Arrays Research Articles

Robust Organocatalytic Three-Component Approach to 1,3-Diarylallylidene Pyrazolones via Consecutive Double Condensation Reactions.

A robust pyrrolidine-BzOH salt-catalyzed one-pot three-component reaction involving 4-unsubstituted pyrazolones, aryl/heteroarylaldehydes, and aryl methyl ketones is reported for the first time. This catalytic process fortifies an efficient method, allowing for the practical synthesis of a wide array of synthetically useful 1,3-diarylallylidene pyrazolones in good to high yields exclusively in their single geometrical isomer forms. Furthermore, this catalyst facilitates a sequential double condensation reaction under thermal conditions, thereby enabling two consecutive C═C bonds through displacement of aryl groups. Moreover, this organocatalytic technique achieves a 100% carbon atom economy, marking a significant step forward toward efficient and sustainable synthesis.

Reactions of In Situ-Generated Difluorocarbene (:CF2) with Aromatic/Heteroaromatic Alcohols, Thiols, Olefins, and Alkynes under Environmentally Responsible Conditions.

Environmentally respectful methods for generating and utilizing difluorocarbene (:CF2) in the synthesis of a wide array of valuable difluoromethylated compounds are disclosed. In particular, the insertion of the CF2 moiety into aromatic/heteroaromatic alcohols, thiols, olefins, and alkynes under neat or aqueous micellar catalysis conditions is demonstrated. These methods yield both satisfactory results and significantly lower E-Factors compared to traditional synthetic approaches. Key applications of these methodologies include optimization en route to a pantoprazole intermediate and development of a representative one-pot chemoenzymatic sequence. Additionally, analysis via calorimetry indicates no significant safety risk in the context of the developed solvent-free conditions.

Photooxidation of Toluene Derivatives under HAT and ROS Synergy.

The valorization of toluene offers a dual solution by addressing its environmental impact while also facilitating the synthesis of a diverse array of valuable fine chemicals and pharmaceutical intermediates, thus ensuring both ecological sustainability and economic viability. We report herein a synergistic approach that harmonizes hydrogen atom transfer (HAT) process with the generation of reactive oxygen species (ROS) under mild condition and low catalyst loading, which enables the efficient synthesis of a broad spectrum of esteemed benzoic acid derivatives and aryl ketones through the photocatalytic oxidation of toluene derivatives. Mechanistic elucidation reveals that the HAT reagent anthraquinone has both the capabilities to abstract hydrogen atoms and the ability to generate singlet oxygen 1O2 during energy transfer with triplet oxygen 3O2, and the combination of these two potencies significantly improves the catalytic efficiency of the reaction. This study not only introduces the amalgamation of HAT with ROS generation but also delineates a systematic approach for the selection of HAT reagents with energy transfer proficiency for ROS generation in catalytic oxidation reactions.

Efficient side lobe level reduction technique for planar antenna arrays

This paper presents a novel array synthesis technique based on the virtual antenna array (VAA) concept for side lobe level (SLL) reduction of uniform planar antenna arrays (UPAA). The VAA decomposes the (M×N) UPAA into vertical and horizontal uniform linear antenna arrays (V–ULAA and H–ULAA) consisting of M and N antenna elements, respectively. The V-ULAA and H-ULAA are positioned perpendicularly and closely enough apart to form a new (M+N) virtual UPAA. Consequently, the number of antenna elements is significantly reduced, which in turn minimizes the computational complexity and signal processing time required to synthesize the desired radiation pattern. Therefore, instead of reducing the SLL of the entire UPAA, we simply reduce the SLL of each ULAA using the well-known hybrid Method of Moments/Genetic Algorithm (MoM/GA) array synthesis technique, which adjusts both the excitation coefficients and element spacings to achieve low SLL. The MoM/GA results in non-uniform V-LAA and H-LAA having two non-uniform excitation vectors AV and AH, respectively, and much lower SLLs than the corresponding V-ULAA and H-ULAA. Finally, the synthesized excitation vectors AV and AH are used to synthesize either the virtual (M+N) planar antenna array (V-PAA) or the physical (M×N)PAA with more than two-fold reductions in the SLL.

Anodic Synthesis of Highly Ordered TiO2 Nanotube Arrays: Role of Electrolyte Composition on the Structural, Morphological, Optical, and Photo-electrochemical Properties

The fluoride species present in two different anodizing electrolytes were used to produce TiO2 nanotube arrays (TiO2 NTAs) by simultaneous anodic reaction and chemical dissolution. In this investigation, two different electrolytes were used for the preparation; [Eth-TiO2 NAs: 95 ml ethylene glycol+0.5% NH4F+5 ml DI water] and [Gly-TiO2 NAs: 75 ml glycerine+0.5% NH4F+25 ml DI water]. The effects of the prepared electrolytes used in the synthesis of TiO2 nanotube arrays on structural element composition, morphology, and optical properties are the focus of this study and are characterized by X-ray diffraction (XRD), scanning electron microscopy field emission (FE-SEM), energy-dispersive X-ray spectroscopy (EDX) and UV-vis diffusion reflection spectroscopy (DRS), respectively. The photoelectrochemical properties of TiO2 NTAs prepared in different electrolytes were investigated. The photoelectrochemical performance of TiO2 NTAs in Na2SO3 (0.1 M) and Na2S (0.1) was examined under the light of 100 mW/cm2 from a xenon lamp. Comparing the photoelectrochemical (PEC) results of both electrolytes, we find that Eth-TiO2 NTAs contribute a wide surface area resulting in an enhanced PEC response. TiO2 NTs, which were prepared with Eth-TiO2 NTAs, exhibited the highest photocurrent density, 0.326 mA cm–2, and photoconversion efficiency (0.22%).

Cu‐Catalyzed Coupling of Sulfonyl Chlorides with Alkenes: Synthesis of Dienyl Sulfones and β‐Chlorosulfones

This work reports a Cu‐catalyzed coupling technique for synthesizing (E)‐dienyl sulfones and β‐chlorosulfones from 1‐arylbutadienes and styrenes, respectively. By employing easily available and inexpensive reagents, this method enables the synthesis of a diverse array of dienyl sulfones and β‐chlorosulfones with excellent functional group tolerance under base‐ and oxidant‐free conditions. It also proves versatile for the late‐stage functionalization of drug molecules and the scale‐up reactions. The method showcases notable selectivity, gentle reaction conditions, and compatibility with various functional groups as demonstrated through 66 examples with excellent display of regioselectivity.

Application of Single-Frequency Arbitrarily Directed Split Beam Metasurface Reflector in Refractive Index Measurements.

We present a sensor that utilizes a modified single-frequency split beam metasurface reflector to measure the refractive index of materials ranging from one to three. Samples are placed into a cavity between a PCB-etched dielectric and a reflecting ground plane. It is illuminated using a 10.525 GHz free-space transmit horn with reflecting angles measured by sweeping a receiving horn around the setup. Predetermined changes in measured angles determined through simulations will coincide with the material's index. The sensor is designed using the Fourier transform method of array synthesis and verified with FEM simulations. The device is fabricated using PCB milling and 3D printing. The quality of the sensor is verified by characterizing 3D printed dielectric samples of various infill percentages and thicknesses. Without changing the metasurface design, the sensing performance is extended to accommodate larger sample thicknesses by including a modified 3D printed fish-eye lens mounted in front of the beam splitter; this helps to exaggerate changes in reflected angles for those samples. All the methods presented are in agreement and verified with single-frequency index measurements using Snell's law. This device may offer a viable alternative to traditional index characterization methods, which often require large sample sizes for single-frequency measurements or expensive equipment for multi-frequency parameter extraction.

ANN-Assisted Iterative Algorithms for Pattern Synthesis of Conformal Arrays

ANN-Assisted Iterative Algorithms for Pattern Synthesis of Conformal Arrays

Design, Synthesis, and Biological Evaluation of HDAC Inhibitors Containing Natural Product-Inspired N-Linked 2-Acetylpyrrole Cap.

Drawing inspiration from the structural resemblance between a natural product N-(3-carboxypropyl)-2-acetylpyrrole and phenylbutyric acid, a pioneer HDAC inhibitor evaluated in clinical trials, we embarked on the design and synthesis of a novel array of HDAC inhibitors containing an N-linked 2-acetylpyrrole cap by utilizing the pharmacophore fusion strategy. Among them, compound 20 exhibited potential inhibitory activity on HDAC1, and demonstrated notable potency against RPMI-8226 cells with an IC50 value of 2.89 ± 0.43 μM, which was better than chidamide (IC50 = 10.23 ± 1.02 μM). Western blot analysis and Annexin V-FTIC/propidium iodide (PI) staining showed that 20 could enhance the acetylation of histone H3, as well as remarkably induce apoptosis of RPMI-8226 cancer cells. The docking study highlighted the presence of a hydrogen bond between the carbonyl oxygen of the 2-acetylpyrrole cap group and Phe198 of the HDAC1 enzyme in 20, emphasizing the crucial role of introducing this natural product-inspired cap group. Molecular dynamics simulations showed that the docked complex had good conformational stability. The ADME parameters calculation showed that 20 possesses remarkable theoretical drug-likeness properties. Taken together, these results suggested that 20 is worthy of further exploration as a potential HDAC-targeted anticancer drug candidate.

Ammonia controlled synthesis of NiO nanosheet arrays for high-performance electrochromic-supercapacitors

To optimize the synthesis process and improve the electrochromic and energy storage performance of NiO, in this paper, an ammonia hydrothermal method is used to prepare NiO nanosheet array electrodes with dual-functions of electrochromic and energy storage. When the concentration of ammonia reaches pH = 11.5, the prepared electrode exhibits optimal optical modulation capability (79.2 % at 620 nm). Additionally, this electrode also provides a large area specific capacitance (69.5 mF/cm² at 0.2 mA/cm²), good rate capability (maintaining 46.7 mF/cm² at 1.0 mA/cm²), and excellent capacitive stability (retaining 96 % of the initial capacitance after 5000 cycles). These excellent performances are mainly attributed to the hierarchical assembled nanosheets structure, which has a large active surface area and short ion transport paths. Furthermore, the uniform and interlinked self-assembled structure, as well as the preset seed layer significantly enhance the film's structural stability and the adhesion to the substrate. Notably, we also construct electrochromic-supercapacitors (ECSCs). During the charging process, two series-connected ECSCs turn dark brown and light up an LED lamp, while during the discharging process, the ECSCs gradually becomes colorless, and the LED lamp goes out. This study provides directions for the preparation of novel dual-functional visual energy storage materials and boosts the development of dual-functional electrochromic-energy storage devices.

Isolation and characterization of the new Streptomyces phages Kamino, Geonosis, Abafar, and Scarif infecting a broad range of host species.

Streptomyces, a multifaceted genus of soil-dwelling bacteria belonging to the phylum Actinomycetota, features intricate phage-host interactions shaped by its complex life cycle and the synthesis of a diverse array of specialized metabolites. Here, we describe the isolation and characterization of four novel Streptomyces phages infecting a variety of different host species. While phage Kamino, isolated on Streptomyces kasugaensis, is predicted to be temperate and encodes a serine integrase in its genome, phages Geonosis (isolated on Streptomyces griseus) and Abafar and Scarif, isolated on Streptomyces albidoflavus, are virulent phages. Phages Kamino and Geonosis were shown to amplify well in liquid culture leading to a pronounced culture collapse already at low titers. Determination of the host range by testing >40 different Streptomyces species identified phages Kamino, Abafar, and Scarif as broad host-range phages. Overall, the phages described in this study expand the publicly available portfolio of phages infecting Streptomyces and will be instrumental in advancing the mechanistic understanding of the intricate antiviral strategies employed by these multicellular bacteria.IMPORTANCEThe actinobacterial genus Streptomyces is characterized by multicellular, filamentous growth and the synthesis of a diverse range of bioactive molecules. These characteristics also play a role in shaping their interactions with the most abundant predator in the environment, bacteriophages-viruses infecting bacteria. In this study, we characterize four new phages infecting Streptomyces. Out of those, three phages feature a broad host range infecting up to 15 different species. The isolated phages were characterized with respect to plaque and virion morphology, host range, and amplification in liquid culture. In summary, the phages reported in this study contribute to the broader collection of publicly available phages infecting Streptomyces, playing a crucial role in advancing our mechanistic understanding of phage-host interactions of these multicellular bacteria.

Pickering Emulsion Promoted Interfacial Sequential Chemo-Biocatalytic Reaction for the Synthesis of Chiral Alcohols from Styrene.

Chemo-biocatalytic cascades have emerged as a promising approach in the realm of advanced synthesis. However, reconciling the incompatible reaction conditions among distinct catalytic species presents a significant challenge. Herein, we introduce an innovative solution using an emulsion system stabilized by Janus silica nanoparticles, which serve as a bridge for both chemo-catalysts and biocatalysts at the interface. The chemo-catalyst is securely anchored within a hydrophobic polymer matrix, ensuring its residence in an organic environment. Meanwhile, the negatively charged E. coli cells containing enzymes are attracted to the aqueous phase at the interface, facilitating their optimal positioning. We demonstrate the efficacy of this system through a two-step cascade reaction. Initially, the oxidation of styrene to acetophenone using palladium as a chemocatalyst achieves a 6-fold increase in yield compared to the control system. Subsequently, the reduction of achiral acetophenone to its chiral alcohol derivative presents a 17-fold yield enhancement relative to that of the control reaction. Importantly, our system exhibits versatility, accommodating a wide range of substrates for both individual and sequential reactions. This work not only validates the concept but also paves the way for the integration of chemo- and biocatalysts in the synthesis of a broader array of high-value chemical compounds.

Versatile, Modular, and General Strategy for the Synthesis of α-Amino Carbonyls.

Modulating the basicity of alkylamines is a crucial factor in drug design. Consequently, alkylamines with a proximal amide, ester, or ketone have become privileged features in many pharmaceutical candidates. The impact of α-amino carbonyls has made the development of new methods for their preparation a continuous challenge in synthesis. Here, we describe a practical strategy that provides a modular and programmable synthesis of a wide range of α-amino carbonyls. The generality of this process is made possible by an extremely mild method to generate carbamoyl radicals, proceeding via a Lewis acid-visible-light-mediated Norrish type-I fragmentation of a tailored carboxamide reagent and intercepted through addition to in situ generated unbiased imines. Aside from the reaction's broad scope in each component, its capacity to draw on plentiful and diversely populated amine and carbonyl feedstocks is showcased through a two-dimensional array synthesis that is used to construct a library of novel, assay-ready, α-amino amides.

Electrochemical Trioxygenation of Allylarenes

AbstractTrioxygenation is a highly effective method for rapidly increasing molecular complexity by incorporating three C–O bonds from simple, readily available raw materials. In this study, we present an electrochemical trioxygenation protocol for allylarenes, which enables the synthesis of a diverse array of triacetoxylation products without external chemical oxidants. These products, which are difficult to obtain through conventional methods, highlight the potential of electrochemistry in promoting sustainable synthesis.

Regio-, stereo-, and enantioselective ipso- and migratory defluorinative olefin cross-coupling to access highly functionalized monofluoroalkenes

Monofluoroalkenes serve as nonhydrolyzable mimetics of amides and are frequently encountered in drug candidates. Herein we report a regio-, enantio-, and stereoselective NiH-catalyzed ipso- and migratory defluorinative olefin cross-coupling employing readily available olefins and gem-difluoroalkenes under mild conditions. This approach enables the efficient synthesis of a broad array of structurally diverse monofluoroalkenes bearing a tertiary allylic stereogenic center. Mechanistically, the challenging migratory defluorinative olefin cross-coupling process is successfully realized through a ligand relay catalytic strategy, enabling the formal C(sp3)–H/C(sp2)–F activation with high levels of regio-, stereo-, and enantiocontrol.

Synthesis of sparse rectangular planar arrays with weight function and improved grey wolf optimization algorithm

AbstractThe present article proposes a novel hybrid approach for addressing the synthesis problem of rectangular planar arrays under multiple constraints, through joint optimization of the weight function and the improved grey wolf optimization (IGWO) algorithm. Firstly, the grey wolf optimization (GWO) algorithm is improved by using tent chaotic mapping, nonlinear convergence factor, dominant wolf dynamic belief strategy, and opposition‐based learning strategy to increase the population diversity and the ability to jump out of the local optimum. Secondly, the array elements are weighted using the weight function to generate the position distribution matrix, which reduces the thinned matrix optimization time and improves the optimization efficiency. Finally, the position distribution matrix is used to generate the thinned array, and the IGWO algorithm is applied to perform the sparse optimization with multiple constraints. The effectiveness of the method is verified through numerical simulation and full‐wave simulation experiments, demonstrating its capability to enhance array antenna performance and reduce peak sidelobe level (PSLL). These experimental results hold significant engineering implications and provide valuable references for addressing the array distribution problem under multiple constraints.

Facile synthesis of MnMoO4 nanostructures arrays as novel electrode materials for high-performance symmetric and asymmetric supercapacitor

Facile synthesis of MnMoO4 nanostructures arrays as novel electrode materials for high-performance symmetric and asymmetric supercapacitor

Strong support effect induced by MXene for the synthesis of metal sulfides nanosheet arrays with sulfur vacancies towards selective CO2-to-CO photoreduction

Selective CO2-to-CO photoreduction is under intensive research and requires photocatalysts with tuned microstructures to accelerate the reaction kinetics. Here, we report CuInS2 nanosheet arrays with sulfur vacancies (VS) grown on the two-dimensional (2D) support of Ti3C2Tx MXene for CO2-to-CO photoreduction. Our results reveal that the use of Ti3C2Tx induces strong support effect, which causes the hierarchical nanosheet arrays growth of CuInS2 and simultaneously leads to charge transfer from CuInS2 to Ti3C2Tx support, resulting in VS formed in CuInS2. The strong support effect based on Ti3C2Tx is proven to be applicable to prepare a series of different metal indium sulfide arrays with VS. CuInS2 nanosheet arrays with VS supported on Ti3C2Tx benefit the photocatalytic selective reduction of CO2 to CO, manifesting a remarkable over 14.8-fold activity enhancement compared with pure CuInS2. The experimental and computational investigations pinpoint that VS of CuInS2 resulting from the support effect of Ti3C2Tx lowers the barrier of the rate-limiting step of *COOH → *OH + *CO, which is the key to the photoactivity enhancement. This work demonstrates MXene support effects and offers an effective approach to regulate the atomic microstructure of metal sulfides toward enhancing photocatalytic performance.

Isoreticular Covalent Organic Pillars: Engineered Nanotubular Hosts for Tailored Molecular Recognition.

In the realm of nanoscale materials design, achieving precise control over the dimensions of nanotubular architectures poses a substantial challenge. In our ongoing pursuit, we have successfully engineered a novel class of single-molecule nanotubes─isoreticular covalent organic pillars (iCOPs)─by stacking formylated macrocycles through multiple dynamic covalent imine bonds, guided by principles of reticular chemistry. Our strategic selection of rigid diamine linkers has facilitated the synthesis of a diverse array of iCOPs, each retaining a homologous structure yet offering distinct cavity shapes influenced by the linker choice. Notably, three of these iCOP variants feature continuous one-dimensional channels, exhibiting length-dependent host-guest interactions with α,ω-dibromoalkanes, and each presenting a distinct critical guest alkyl chain length threshold for efficient guest encapsulation. This newfound capability not only provides a platform for tailoring nanotubular structures with precision, but also opens new avenues for innovative applications in molecular recognition and the purification of complex mixtures.

Unexplored catalytic potency of a magnetic CoFe2O4/Ni-BDC MOF composite for the one-pot sustainable synthesis of 5-substituted 1-H tetrazoles

Within the domain of materials science and engineering, significant progress has led to the emergence of innovative materials based on magnetic MOFs, positioning them as promising candidates in the field of catalysis. This research aims to elaborate on the development of a finely tailored magnetic MOF composite; Ni-BDC (Nickel benzene-1,4-dicarboxylate) microflakes which was synthesized through a straightforward in-situ solvothermal approach. Extensive investigations into the structural properties of the resultant hybrid composite were carried out using various characterization techniques encompassing X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Brunauer-Emmett-Teller (BET) analysis, atomic absorption spectroscopy (AAS), energy-dispersive X-ray spectroscopy (EDX), thermogravimetric analysis (TGA) and vibrating sample magnetometry (VSM). The developed material demonstrated remarkable efficiency in expediting the synthesis of a diverse array of pharmaceutically active 5-substituted 1H-tetrazole derivatives through a multicomponent coupling reaction involving substituted aldehydes, malononitrile, and sodium azide as key components. A noteworthy feature of this approach is its adherence to environmentally friendly reaction conditions, thus making it superior in comparison to previously established methodologies. Furthermore, a plausible mechanistic pathway has been proposed to elucidate the impressive performance of the developed catalytic system in the targeted reaction. It is anticipated that the current research will not only contribute to the purposeful designing of advanced magnetic MOF-based architectures but will also play a pivotal role in promoting sustainable practices in industrial processes, addressing pressing environmental and economic concerns.