Industrial fault diagnosis faces unique challenges with high-dimensional data, long time-series, and complex couplings, which are characterized by significant information entropy and intricate information dependencies inherent in datasets. Traditional image processing methods are effective for local feature extraction but often miss global temporal patterns, crucial for accurate diagnosis. While deep learning models like Vision Transformer (ViT) capture broader temporal features, they struggle with varying fault causes and time dependencies inherent in industrial data, where adding encoder layers may even hinder performance.
View Article and Find Full Text PDFACS Appl Mater Interfaces
November 2023
Achieving fast and durable potassiation/depotassiation of anode materials for potassium ion batteries (PIB) still remains an elusive yet fascinating goal. Herein, we challenge the conventional wisdom in synthesizing the TiPO superstructure and report a nanocarbon coating on TiPO (TiPO/C) using layered MXene as a Ti source to realize an effective tuning in the TiO and PO building blocks for boosting the K diffusion kinetics in PIB. Experimental investigations coupled with systematic theoretical simulations indicate that the interface interaction between TiPO and coated nanocarbon could induce internal adjustment in individual Ti-O bonding and relieve the local distortions of TiO octahedra, which endows the TiPO/C with favorable regulation in a K hopping manner and significantly reduces the K diffusion barrier via the diffusion propagation along PO blocks with dominant coordination between O/P and K.
View Article and Find Full Text PDFA fluorescent sensor array has been developed based on conjugated polymers (CPs) having six different skeletons for the detection of tetracyclines (TCs), which are known as environmental pollutants. CPs were synthesized from confined nanoreactors in a controlled manner. The fluorescent response occurs through the fluorescence resonance energy transfer (FRET) effect.
View Article and Find Full Text PDFNatural enediyne antibiotics are powerful DNA-cleavage agents due to the presence of the highly reactive hex-3-ene-1,5-diyne units. However, the complicated chemical structure and thermal instability make their synthesis, derivatization, and storage challenging. Heterocycle-fused enediynes, which exhibit strong antineoplastic activity, are promising analogues of natural enediynes for medicinal applications.
View Article and Find Full Text PDFA catalytic heterogenous Suzuki polymerization method was developed by confining the Pd(II)-catalyzed cross coupling reactions to take place exclusively in the nanochannels of dendritic mesoporous silica nanoparticles. Conjugated polymers with various monomer combinations, including donor-acceptor structures, were obtained in high yields. The molecular weights of the obtained polymers were well controlled with narrow molecular weight distributions (PDI value down to 1.
View Article and Find Full Text PDFMyers-Saito cycloaromatization (MSC) is the working mechanism of many natural enediyne antibiotics with high antitumor potency. However, the presence of the equilibrium between diradical and zwitterionic intermediates in MSC severely hinders further improvement in cytotoxicity toward tumor cells. To this end, a series of maleimide-based enediynes with cyclopropane moieties were synthesized for enhanced cytotoxicity toward tumor cells.
View Article and Find Full Text PDFCyclic ethers are important scaffolds employed in the synthesis of various natural products and pharmaceutical ingredients. A novel free radical-initiated reaction between cyclic ethers and maleimide iodides through C-H activation is developed, avoiding the use of transition metallic catalysts. This method provides a simple approach to derive cyclic ethers, which were further applied in various cross coupling reactions.
View Article and Find Full Text PDFCombined photothermal therapy/chemotherapy by co-delivery of a photosensitizer (PS) and a chemotherapeutic drug has demonstrated great potential for cancer treatment. The intrinsic drawbacks of traditional drug delivery systems (DDSs), such as tedious synthetic procedures, side effects originated from the carrier materials, low loading efficiency, and uncontrolled drug release, however, have impaired their further advancement. On the other hand, enediyne antibiotics are highly cytotoxic toward cancer cells through the generation of lethal carbon radicals via thermal-induced cyclization, endowing them with great potential to achieve enhanced synergistic anticancer performance by incorporation with the photothermal effect of PS.
View Article and Find Full Text PDFA controlled polymerization strategy is developed by confining the step-growth polycondensation to take place exclusively in the nanochannels of dendritic mesoporous silica nanoparticles. A variety of conjugated polymers with rich structural patterns were obtained in high yields. The molecular weights were precisely controlled with narrow molecular weight distributions.
View Article and Find Full Text PDFThe follow-up reaction pathways of the diradical species formed from cycloaromatization of enediynes or enyne-allenes determine their ability of H-abstraction from DNA, significantly affecting their biological activity performance. To gain a deeper understanding of subsequent reaction pathways of the diradical intermediates formed from acyclic enediynes based on maleimide-assisted rearrangement and cycloaromatization (MARACA), a maleimide-based enediyne featuring methylene groups adjacent to the propargyl sites of the terminal alkynes was synthesized through the Sonogashira coupling reaction. Three thermal cyclization products after intramolecular hydrogen atom transfer (HAT) were obtained from the thermolysis experiment and their structures were confirmed by 1D and 2D nuclear magnetic resonance spectroscopic analysis.
View Article and Find Full Text PDFACS Appl Mater Interfaces
December 2020
Acyclic enediynes are generally inactive under physiological conditions to be used as antitumor agents like their natural enediyne counterparts. A new mechanism named as maleimide-assisted rearrangement and cycloaromatization (MARACA) is uncovered to trigger the reactivity of acyclic enediynes. Through this mechanism, cascade 1,3-proton transfer processes are accelerated with the maleimide moiety at the ene position to enable the acyclic enediynes to undergo cycloaromatization and generate reactive radicals under physiological conditions.
View Article and Find Full Text PDFGadolinium(iii) complexes are generally considered efficient magnetic resonance imaging (MRI) contrast agents (CAs) and widely used in clinical applications. High relaxivity and stability are two essential criteria for a Gd(iii)-complex to be used as a MRI-CA. One crucial strategy to achieve high relaxivity for small molecular Gd(iii)-based MRI contrast agents is to increase the hydration number q.
View Article and Find Full Text PDFPolylactic acid (PLA) nanoparticles coated with Gd(III)-based metallosurfactants (MS) are prepared using a simple and rapid one-step method, flash nanoprecipitation (FNP), for magnetic resonance imaging (MRI) applications. By co-assembling the Gd(III)-based MS and an amphiphilic polymer, methoxy poly(ethylene glycol)-b-poly(ϵ-caprolactone) (mPEG-b-PCL), PLA cores were rapidly encapsulated to form biocompatible T contrast agents with tunable particle size and narrow size distribution. The hydrophobic property of Gd(III)-based MS were finely tuned to achieve their high loading efficiency.
View Article and Find Full Text PDFEnyne-allene compounds undergo Myers-Saito cyclization at physiological temperature to generate diradical intermediates that are capable of inducing DNA damage and cell death. The high reactivity of enyne-allene however limits their promising prospect as anticancer agents due to the spontaneous cyclization during storage and delivery. Regulating the cyclization process by taking advantage of the characteristics of a tumor cellular microenvironment, such as employing a low pH value to activate the cyclization process, is thus of essential importance.
View Article and Find Full Text PDFA maleimide-based acyclic enediyne with salicylaldiminato substituents at the alkyne termini was synthesized, which was further chelated with three kinds of metal-ions, Cu , Zn , and Mg , and form metalloenediynes. The cycloaromatization of this thermally inactive enediyne ligand was greatly accelerated through the coordination with metal ions. Specifically, the Cu -metalloenediyne showed an extremely low onset temperature of 55 °C and underwent spontaneous cycloaromatization at ambient temperature to produce free radicals, followed by generation of reactive oxygen species in the physiological environment.
View Article and Find Full Text PDFACS Appl Mater Interfaces
March 2019
Light-cross-linked small-molecule micelles with enediyne units are designed for developing efficient drug-delivery systems. Gemcitabine (GEM) is chosen as a model hydrophilic drug and tethered with a maleimide-based enediyne (EDY) as a hydrophobic tail in the preparation of amphiphilic EDY-GEM. The stable micellar particles are obtained by cross-linking the enediyne moieties via photoinduced Bergman cyclization polymerization in aqueous media.
View Article and Find Full Text PDFComplexes of gadolinium(iii) have proven to be especially effective magnetic resonance imaging (MRI) contrast agents. One essential strategy to achieve more sensitive small-molecule gadolinium-based MRI contrast agents is to increase the hydration number q in order to improve the relaxivity. In this work, a series of diethylenetriamine-N-oxide pentaacetic acid-bisamide-based Gd(iii) complexes with 3 coordinated water molecules have been synthesized, in which the hydration numbers are verified by luminescence measurements.
View Article and Find Full Text PDFAn amphiphilic small molecular drug self-delivery system was designed by linking a hydrophilic topoisomerase I inhibitor irinotecan (Ir) with a lipophilic cytotoxic enediyne (EDY) antibiotic through an ester bond. The maleimide-based EDY with a pendant carboxyl group was synthesized in four steps from commercially available reagents. The EDY compound possesses the ability to generate radical intermediates at physiological temperature as demonstrated by electron spin resonance analysis and further causes DNA-cleavage and tumor cell suppression.
View Article and Find Full Text PDFMagnetic resonance imaging (MRI) is one of the most important medical imaging techniques for clinical diagnosis. Contrast agents (CAs) are commonly necessarily used to enhance the imaging quality of MRI and differentiate diseased tissues from normal ones. Herein, we introduced a macromolecular carrier, spherical polyelectrolyte brushes (SPBs), which consists of a solid polystyrene (PS) core and polyacrylic acid (PAA) chains as a brush layer to host Gd(iii) complexes.
View Article and Find Full Text PDFA fluorescence sensing array (or fluorescent electronic nose) is designed on a disposable paper card using 36 sets of soluble conjugated polymeric nanoparticles (SCPNs) as sensors to easily identify wide ranges of volatile analytes, including explosives and toxic industrial chemicals (amines and pungent acids). A 108-dimensional vector obtained from the fluorescent color change in the sensing array is defined and directly treated as an index in a standard chemical library (30 kinds of volatile analytes and a control group). Hierarchical clustering analysis (HCA) and principal component analysis (PCA) indicated the diversity in electronic structures; saturated vapor pressure and miscibility of analytes are keys in differentiating the analytes, with electron-rich arenes and alkylamines enhancing fluorescence and electron-deficient analytes attenuating fluorescence.
View Article and Find Full Text PDFElectrical stimulators are often prescribed to correct foot drop walking. However, commercial foot drop stimulators trigger inappropriately under certain non-gait scenarios. Past researches addressed this limitation by defining stimulation control based on automaton of a gait cycle executed by foot drop of affected limb/foot only.
View Article and Find Full Text PDFGendicine (recombinant human p53 adenovirus), developed by Shenzhen SiBiono GeneTech Co. Ltd., was approved in 2003 by the China Food and Drug Administration (CFDA) as a first-in-class gene therapy product to treat head and neck cancer, and entered the commercial market in 2004.
View Article and Find Full Text PDFThe amidoxime group (-RNHNOH) has long been used to extract uranium from seawater on account of its high affinity toward uranium. The development of tunable sorbent materials for uranium sequestration remains a research priority as well as a significant challenge. Herein, we report the design, synthesis, and uranium sorption properties of bis-amidoxime-functionalized polymeric materials (BAP 1-3).
View Article and Find Full Text PDFTop Curr Chem (Cham)
June 2017
Synthetic polymer chemistry is a fundamental part of polymer science, and highly efficient polymerization reactions are essential for the synthesis of high-performance polymers. Development of new synthetic methods for emerging polymer science is of great importance in this regard. Bergman cyclization is a chemical process in which highly reactive aryl diradicals form from enediyne precursors, having a strong impact in a number of fields including pharmaceutics, synthetic chemistry, and materials science.
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