ABSTRACT
The unique and interesting physical and chemical properties of metal-organic framework (MOF) materials have recently attracted extensive attention in a new generation of photoelectric applications. In this review, we summarized and discussed the research progress on MOF-based photodetectors. The methods of preparing MOF-based photodetectors and various types of MOF single crystals and thin film as well as MOF composites are introduced in details. Additionally, the photodetectors applications for X-ray, ultraviolet and infrared light, biological detectors, and circularly polarized light photodetectors are discussed. Furthermore, summaries and challenges are provided for this important research field.
ABSTRACT
Ficus carica is an economically important horticultural plant. Due to its abundant secondary metabolites, F. carica has gained interest for its applications in medicine and as a nutritional supplement. Both external and internal factors affect the accumulation of secondary metabolites in F. carica. The assembly of the F. carica genome has facilitated functional analysis of key genes and transcription factors associated with the biosynthesis of secondary metabolites, particularly anthocyanin. In this review, we summarize the various types and functions of secondary metabolites, with a particular focus on flavonoids, coumarins, and terpenes. We also explore the factors influencing their biosynthesis and accumulation, including varieties, tissue, environmental factors (e.g., light), stresses (e.g., high temperature, low temperature, drought, nutrient deficiencies, salinity), hormonal treatments, and developmental factors. Furthermore, we discuss the involvement of structural genes and transcription factors in the biosynthesis of secondary metabolites, specifically anthocyanin and furanocoumarins, knowledge of which will promote the breeding and genetic engineering of novel F. carica varieties.
ABSTRACT
As a highly effective broad-spectrum antibacterial agent, triclosan (TCS) is widely used in personal care and medical disinfection products, resulting in its widespread occurrence in aquatic and terrestrial environments, and even in the human body. Notably, the use of TCS surged during the COVID-19 outbreak, leading to increasing environmental TCS pollution pressure. From the perspective of environmental health, it is essential to systematically understand the environmental occurrence and behavior of TCS, its toxicological effects on biota and humans, and technologies to remove TCS from the environment. This review comprehensively summarizes the current knowledge regarding the sources and behavior of TCS in surface water, groundwater, and soil systems, focusing on its toxicological effects on aquatic and terrestrial organisms. Effluent from wastewater treatment plants is the primary source of TCS in aquatic systems, whereas sewage application and/or wastewater irrigation are the major sources of TCS in soil. Human exposure pathways to TCS and associated adverse outcomes were also analyzed. Skin and oral mucosal absorption, and dietary intake are important TCS exposure pathways. Reducing or completely degrading TCS in the environment is important for alleviating environmental pollution and protecting public health. Therefore, this paper reviews the removal mechanisms, including adsorption, biotic and abiotic redox reactions, and the influencing factors. In addition, the advantages and disadvantages of the different techniques are compared, and development prospects are proposed. These findings provide a basis for the management and risk assessment of TCS and are beneficial for the application of treatment technology in TCS removal.
Subject(s)
Triclosan , Triclosan/toxicity , Humans , Anti-Infective Agents, Local , Water Pollutants, Chemical/analysis , Environmental MonitoringABSTRACT
RNA interactomes and their diversified functionalities have recently benefited from critical methodological advances leading to a paradigm shift from a conventional conception on the regulatory roles of RNA in pathogenesis. However, the dynamic RNA interactomes in adenoma-carcinoma sequence of human CRC remain unexplored. The coexistence of adenoma, cancer, and normal tissues in colorectal cancer (CRC) patients provides an appropriate model to address this issue. Here, we adopted an RNA in situ conformation sequencing technology for mapping RNA-RNA interactions in CRC patients. We observed large-scale paired RNA counts and identified some unique RNA complexes including multiple partners RNAs, single partner RNAs, non-overlapping single partner RNAs. We focused on the antisense RNA OIP5-AS1 and found that OIP5-AS1 could sponge different miRNA to regulate the production of metabolites including pyruvate, alanine and lactic acid. Our findings provide novel perspectives in CRC pathogenesis and suggest metabolic reprogramming of pyruvate for the early diagnosis and treatment of CRC.
Subject(s)
Adenoma , Colorectal Neoplasms , MicroRNAs , Pyruvic Acid , RNA, Long Noncoding , Humans , Colorectal Neoplasms/genetics , Colorectal Neoplasms/metabolism , Colorectal Neoplasms/pathology , MicroRNAs/genetics , MicroRNAs/metabolism , Adenoma/genetics , Adenoma/metabolism , Adenoma/pathology , Pyruvic Acid/metabolism , RNA, Long Noncoding/genetics , RNA, Long Noncoding/metabolism , Gene Expression Regulation, Neoplastic , Metabolic ReprogrammingABSTRACT
Ginkgo (Ginkgo biloba L.) is one of the earliest extant species in seed plant phylogeny. Embryo development patterns can provide fundamental evidence for the origin, evolution, and adaptation of seeds. However, the architectural and morphological dynamics during embryogenesis in Ginkgo biloba (G. biloba) remain elusive. Herein, we obtained over 2200 visual slices from three stages of embryo development using micro-computed tomography imaging with improved staining methods. Based on 3D spatio-temporal pattern analysis, we found that a shoot apical meristem with seven highly differentiated leaf primordia, including apical and axillary leaf buds, is present in mature Ginkgo embryos. 3D rendering from the front, top, and side views showed two separate transport systems of tracheids located in the hypocotyl and cotyledon, representing a unique pattern of embryogenesis. Furthermore, the morphological dynamic analysis of secretory cavities indicated their strong association with cotyledons during development. In addition, we identified genes GbLBD25a (lateral organ boundaries domain 25a), GbCESA2a (cellulose synthase 2a), GbMYB74c (myeloblastosis 74c), GbPIN2 (PIN-FORMED 2) associated with vascular development regulation, and GbWRKY1 (WRKYGOK 1), GbbHLH12a (basic helix-loop-helix 12a), GbJAZ4 (jasmonate zim-domain 4) potentially involved in the formation of secretory cavities. Moreover, we found that flavonoid accumulation in mature embryos could enhance post-germinative growth and seedling establishment in harsh environments. Our 3D spatial reconstruction technique combined with multi-omics analysis opens avenues for investigating developmental architecture and molecular mechanisms during embryogenesis and lays the foundation for evolutionary studies of embryo development and maturation.
ABSTRACT
To investigate the efficacy of Ursolic acid in alleviating neuropathic pain in rats with spinal nerve ligation (SNL), the SNL rat model was surgically induced. Different concentrations of Ursolic acid and manipulated target mitogen-activated protein kinase 1 (MAPK1) were administered to the SNL rats. Fecal samples were collected from each group of rats for 16S rDNA analysis to examine the impact of gut microbiota. Molecular docking experiments were conducted to assess the binding energy between Ursolic acid and MAPK1. In vivo studies were carried out to evaluate the expression of inflammatory factors and signaling pathways in spinal cord and colon tissues. Ursolic acid was found to have a beneficial effect on pain reduction in rats by increasing plantar withdrawal latency (PWL) and paw withdrawal threshold (PWT). Comparing the Ursolic acid group with the control group revealed notable differences in the distribution of Staphylococcus, Allobaculum, Clostridium, Blautia, Bifidobacterium, and Prevotella species. Network pharmacology analysis identified MAPK1 and intercellular adhesion molecule-1 (ICAM1) as common targets for Ursolic acid, SNL, and neuropathic pain. Binding sites between Ursolic acid and these targets were identified. Additionally, immunofluorescent staining showed a decrease in GFAP and IBA1 intensity in the spinal cord along with an increase in NeuN following Ursolic acid treatment. Overexpression of MAPK1 in SNL rats led to an increase in inflammatory factors and a decrease in PWL and PWT. Furthermore, MAPK1 counteracted the pain-relieving effects of Ursolic acid in SNL rats. Ursolic acid was found to alleviate neuropathic pain in SNL rats by targeting MAPK1 and influencing gut microbiota homeostasis.
Subject(s)
Antigens, Nuclear , Gastrointestinal Microbiome , Mitogen-Activated Protein Kinase 1 , Nerve Tissue Proteins , Neuralgia , Rats, Sprague-Dawley , Triterpenes , Ursolic Acid , Animals , Neuralgia/drug therapy , Neuralgia/metabolism , Triterpenes/pharmacology , Gastrointestinal Microbiome/drug effects , Male , Mitogen-Activated Protein Kinase 1/metabolism , Rats , Spinal Cord/drug effects , Spinal Cord/metabolism , Molecular Docking Simulation , Disease Models, Animal , Spinal Nerves/drug effects , Analgesics/pharmacology , Colon/drug effects , Colon/microbiology , Colon/metabolism , Glial Fibrillary Acidic Protein/metabolismABSTRACT
Redox-responsive hydropersulfide prodrugs are designed to enable a more controllable and efficient hydropersulfide (RSSH) supply and to thoroughly explore their biological and therapeutic applications in oxidative damage. To obtain novel activation patterns triggered by redox signaling, we focused on NAD(P)H: quinone acceptor oxidoreductase 1 (NQO1), a canonical antioxidant enzyme, and designed NQO1-activated RSSH prodrugs. We also performed a head-to-head comparison of two mainstream structural scaffolds with solid quantitative analysis of prodrugs, RSSH, and metabolic by-products by LC-MS/MS, confirming that the perthiocarbamate scaffold was more effective in intracellular prodrug uptake and RSSH production. The prodrug was highly potent in oxidative stress management against cisplatin-induced nephrotoxicity. Strikingly, this prodrug possessed potential feedback activation properties by which the delivered RSSH can further escalate the prodrug activation via NQO1 upregulation. Our strategy pushed RSSH prodrugs one step further in the pursuit of efficient release in biological matrices and improved druggability against oxidative stress.
Subject(s)
NAD(P)H Dehydrogenase (Quinone) , Oxidation-Reduction , Oxidative Stress , Prodrugs , Sulfides , Prodrugs/pharmacology , Prodrugs/chemistry , Oxidative Stress/drug effects , NAD(P)H Dehydrogenase (Quinone)/metabolism , Oxidation-Reduction/drug effects , Sulfides/chemistry , Sulfides/pharmacology , Humans , Animals , Tandem Mass Spectrometry , Cisplatin/pharmacology , Antioxidants/pharmacology , Antioxidants/chemistry , MiceABSTRACT
Cesium lead halide nanostructures have highly tunable optical and optoelectronic properties. Establishing precise control in forming perovskite single-crystal nanostructures is key to unlocking the full potential of these materials. However, studying the growth kinetics of colloidal cesium lead halides is challenging due to their sensitivity to light, electron beam, and environmental factors like humidity. In this study, in situ observations of CsPbBr3-particle dynamics were made possible through extremely low dose liquid cell transmission electron microscopy, showing that oriented attachment is the dominant pathway for the growth of single-crystal CsPbBr3 architectures from primary nanocubes. In addition, oriented assembly and fusion of ligand-stabilized cubic CsPbBr3 nanocrystals are promoted by electron beam irradiation or introduction of polar additives that both induce partial desorption of the original ligands and polarize the nanocube surfaces. These findings advance our understanding of cesium lead halide growth mechanisms, aiding the controlled synthesis of other perovskite nanostructures.
ABSTRACT
Aqueous zinc ion batteries (AZIBs) have emerged as a promising battery technology due to their excellent safety, high capacity, low cost, and eco-friendliness. However, the cycle life of AZIBs is limited by severe side reactions and zinc dendrite growth on the zinc electrode surface, hindering large-scale application. Here, an electrolyte optimization strategy utilizing the simplest dipeptide glycylglycine (Gly-Gly) additive is first proposed. Theoretical calculations and spectral analysis revealed that, due to the strong interaction between the amino group and Zn atoms, Gly-Gly preferentially adsorbs on zinc's surface, constructing a stable and adaptive interfacial layer that inhibits zinc side reactions and dendrite growth. Furthermore, Gly-Gly can regulate zinc ion solvation, leading to a deposition mode shift from dendritic to lamellar and limiting two-dimensional dendrite diffusion. The symmetric cell with the addition of a 20 g/L Gly-Gly additive exhibits a cycle life of up to 1100 h. Under a high current density of 10 mA cm-2, a cycle life of 750 cycles further demonstrates the reliable adaptability of the interfacial layer. This work highlights the potential of Gly-Gly as a promising solution for improving the performance of AZIBs.
ABSTRACT
Various synthetic substances were utilized in large quantities during the recent coronavirus pandemic, COVID-19. Some of these chemicals could potentially enter drinking water sources. Persistent, mobile, and toxic (PMT) substances have been recognized as a threat to drinking water resources. It has not yet been assessed how many COVID-19 related substances could be considered PMT substances. One reason is the lack of high-quality experimental data for the identification of PMT substances. To solve this problem, we applied a machine learning model to identify the PMT substances among COVID-19 related chemicals. The optimal model achieved an accuracy of 90.6% based on external test data. The model interpretation and causal inference indicated that our approach understood causation between PMT properties and molecular descriptors. Notably, the screening results showed that over 60% of the COVID-19 chemicals considered are candidate PMT substances, which should be prioritized to prevent undue pollution of water resources.
ABSTRACT
Ceria nanomaterials with facile CeIII/IV redox behavior are used in sensing, catalytic, and therapeutic applications, where inclusion of CeIII has been correlated with reactivity. Understanding assembly pathways of CeO2 nanoparticles (NC-CeO2) in water has been challenged by "blind" synthesis, including rapid assembly/precipitation promoted by heat or strong base. Here, we identify a layered phase denoted Ce-I with a proposed formula CeIV(OH)3(NO3)·xH2O (x ≈ 2.5), obtained by adding electrolytes to aqueous cerium ammonium nitrate (CAN) to force precipitation. Ce-I represents intermediate hydrolysis species between dissolved CAN and NC-CeO2, where CAN is a commonly used CeIV compound that exhibits unusual aqueous and organic solubility. Ce-I features Ce-(OH)2-Ce units, representing the first step of hydrolysis toward NC-CeO2 formation, challenging prior assertions about CeIV hydrolysis. Structure/composition of poorly crystalline Ce-I was corroborated by a pair distribution function, Ce-L3 XAS (X-ray absorption spectroscopy), compositional analysis, and 17O nuclear magnetic resonance spectroscopy. Formation of Ce-I and its transformation to NC-CeO2 is documented in solution by small-angle X-ray scattering (SAXS) and in the solid-state by transmission electron microscopy (TEM) and powder X-ray diffraction. Morphologies identified by TEM support form factor models for SAXS analysis, evidencing the incipient assembly of Ce-I. Finally, two morphologies of NC-CeO2 are identified. Sequentially, spherical NC-CeO2 particles coexist with Ce-I, and asymmetric NC-CeO2 with up to 35% CeIII forms at the expense of Ce-I, suggesting direct replacement.
ABSTRACT
Cephalotanes are a rare class of diterpenoids occurring exclusively in Cephalotaxus plants. The intriguing structures and promising biological activities for this unique compound class prompt us to investigate C. fortunei var. alpina and C. sinensis, leading to the isolation of six undescribed cephalotane-type diterpenoids and/or norditerpenoids, ceforloids A-F (1-6). Their structures were elucidated by comprehensive analysis of spectroscopic data, including ECD and single-crystal X-ray diffraction studies, as well as quantum chemical calculations. Compound 1 possesses an unprecedented norditerpenoid skeleton featuring an unusual acetophenone moiety, and originated putatively from a disparate biogenetic pathway. Compounds 4 and 5 incorporate a unique 12,13-p-hydroxybenzylidene acetal motif. Compound 6 is a rare cephalotane-type diterpenoid glycoside. Immunosuppressive assays showed that compounds 2 and 6 exhibited mild suppressive activity against the activated T and B lymphocytes proliferation. These findings not only expanded the structural diversity of this small group of diterpenoids, but also explored their potential as novel structures for the development of immunosuppressive agents.
Subject(s)
Cephalotaxus , Diterpenes , Molecular Structure , Cephalotaxus/chemistry , Diterpenes/pharmacology , Diterpenes/chemistry , Immunosuppressive Agents , Crystallography, X-RayABSTRACT
The APETALA2 (AP2) transcription factors play crucial roles in plant growth and stage transition. Ginkgo biloba is an important medicinal plant renowned for the rich flavonoid content in its leaves. In this study, 18 GbAP2s were identified from the G. biloba genome and classified into three clusters. We found that the members of the euAP2 cluster, including four TOEs (GbTOE1a/1b/1c/3), exhibited a higher expression level in most samples compared to other members. Specifically, GbTOE1a may have a positive regulatory role in salt and drought stress responses. The overexpression of GbTOE1a in G. biloba calli resulted in a significant increase in the flavonoid content and upregulation of flavonoid biosynthesis genes, including PAL, 4CL, CHS, F3H, FLSs, F3'Hs, OMT, and DFRs. By contrast, the silencing of GbTOE1a in seedlings decreased the flavonoid content and the expression of flavonoid synthesizing genes. In addition, the silenced seedlings exhibited decreased antioxidant levels and a higher sensitivity to salt and drought treatments, suggesting a crucial role of GbTOE1a in G. biloba salt and drought tolerance. To the best of our knowledge, this was the first investigation into the identification and characterization of GbAP2s in G. biloba. Our results lay a foundation for further research on the regulatory role of the AP2 family in flavonoid synthesis and stress responses.
Subject(s)
Droughts , Ginkgo biloba , Ginkgo biloba/genetics , Drought Resistance , Genome-Wide Association Study , Plant Extracts/metabolism , Flavonoids/metabolism , Sodium Chloride/metabolism , Gene Expression Regulation, Plant , Plant Proteins/genetics , Plant Proteins/metabolismABSTRACT
Ancient trees are natural wonders because of their longevity, having lived for hundreds or thousands of years, and their ability to withstand changing environments and a variety of stresses. These long-lived trees have sophisticated defense mechanisms, such as the production of specialized plant metabolites (SPMs). In this review, we provide an overview of the major biotic and abiotic stresses that long-lived trees often face, as well as an analysis of renowned ancient tree species and their unique protective SPMs against environmental stressors. We also discuss the synthesis and accumulation of defensive SPMs induced by environmental factors and endophytes in these trees. Furthermore, we conducted a comparative genomic analysis of 17 long-lived tree species and discovered significant expansions of SPM biosynthesis gene families in these species. Our comprehensive review reveals the crucial role of SPMs in high resistance in long-lived trees, providing a novel natural resource for plant defense, crop improvement and even the pharmaceutical industry.
Subject(s)
Plants , Trees , Trees/metabolism , LongevityABSTRACT
WRKY transcription factors are one of the largest families of transcription regulators that play essential roles in regulating the synthesis of secondary metabolites in plants. Jasmine (Jasminum sambac), renowned for its aromatic nature and fragrant blossoms, possesses a significant abundance of volatile terpene compounds. However, the role of the WRKY family in terpene synthesis in jasmine remains undetermined. In this study, 72 WRKY family genes of J. sambac were identified with their conserved WRKY domains and were categorized into three main groups based on their structural and phylogenetic characteristics. The extensive segmental duplications contributed to the expansion of the WRKY gene family. Expression profiles derived from the transcriptome data and qRT-PCR analysis showed that the majority of JsWRKY genes were significantly upregulated in fully bloomed flowers compared to buds. Furthermore, multiple correlation analyses revealed that the expression patterns of JsWRKYs (JsWRKY27/33/45/51/55/57) were correlated with both distinct terpene compounds (monoterpenes and sesquiterpenes). Notably, the majority of jasmine terpene synthase (JsTPS) genes related to terpene synthesis and containing W-box elements exhibited a significant correlation with JsWRKYs, particularly with JsWRKY51, displaying a strong positive correlation. A subcellular localization analysis showed that JsWRKY51 was localized in the nucleus. Moreover, transgenic tobacco leaves and jasmine calli experiments demonstrated that overexpression of JsWRKY51 was a key factor in enhancing the accumulation of ß-ocimene, which is an important aromatic terpene component. Collectively, our findings suggest the roles of JsWRKY51 and other JsWRKYs in regulating the synthesis of aromatic compounds in J. sambac, providing a foundation for the potential utilization of JsWRKYs to facilitate the breeding of fragrant plant varieties with an improved aroma.
Subject(s)
Jasminum , Perfume , Jasminum/chemistry , Jasminum/genetics , Jasminum/metabolism , Odorants/analysis , Transcription Factors/genetics , Transcription Factors/metabolism , Phylogeny , Plant Breeding , Terpenes/metabolism , Gene Expression Regulation, Plant , Plant Proteins/genetics , Plant Proteins/metabolismABSTRACT
Terpenoids are the broadest and richest group of chemicals obtained from plants. These plant-derived terpenoids have been extensively utilized in various industries, including food and pharmaceuticals. Several specific terpenoids have been identified and isolated from medicinal plants, emphasizing the diversity of biosynthesis and specific functionality of terpenoids. With advances in the technology of sequencing, the genomes of certain important medicinal plants have been assembled. This has improved our knowledge of the biosynthesis and regulatory molecular functions of terpenoids with medicinal functions. In this review, we introduce several notable medicinal plants that produce distinct terpenoids (e.g., Cannabis sativa, Artemisia annua, Salvia miltiorrhiza, Ginkgo biloba, and Taxus media). We summarize the specialized roles of these terpenoids in plant-environment interactions as well as their significance in the pharmaceutical and food industries. Additionally, we highlight recent findings in the fields of molecular regulation mechanisms involved in these distinct terpenoids biosynthesis, and propose future opportunities in terpenoid research, including biology seeding, and genetic engineering in medicinal plants.
Subject(s)
Plants, Medicinal , Plants, Medicinal/genetics , Terpenes/chemistry , Genetic Engineering , Plant ExtractsABSTRACT
Biomolecules modulate inorganic crystallization to generate hierarchically structured biominerals, but the atomic structure of the organic-inorganic interfaces that regulate mineralization remain largely unknown. We hypothesized that heterogeneous nucleation of calcium carbonate could be achieved by a structured flat molecular template that pre-organizes calcium ions on its surface. To test this hypothesis, we design helical repeat proteins (DHRs) displaying regularly spaced carboxylate arrays on their surfaces and find that both protein monomers and protein-Ca2+ supramolecular assemblies directly nucleate nano-calcite with non-natural {110} or {202} faces while vaterite, which forms first in the absence of the proteins, is bypassed. These protein-stabilized nanocrystals then assemble by oriented attachment into calcite mesocrystals. We find further that nanocrystal size and polymorph can be tuned by varying the length and surface chemistry of the designed protein templates. Thus, bio-mineralization can be programmed using de novo protein design, providing a route to next-generation hybrid materials.
Subject(s)
Calcium Carbonate , Nanoparticles , Calcium Carbonate/chemistry , Crystallization , Ions/chemistryABSTRACT
As a key immune cell in the brain, microglia are essential for protecting the central nervous system (CNS) from viral infections, including HIV. Microglia possess functional Toll-like receptor 3 (TLR3), a key viral sensor for activating interferon (IFN) signaling pathway-mediated antiviral immunity. We, therefore, studied the effect of poly (I:C), a synthetic ligand of TLR3, on the activation of the intracellular innate immunity against HIV in human iPSC-derived microglia (iMg). We found that poly (I:C) treatment of iMg effectively inhibits HIV infection/replication at both mRNA and protein levels. Investigations of the mechanisms revealed that TLR3 activation of iMg by poly (I:C) induced the expression of both type I and type III IFNs. Compared with untreated cells, the poly (I:C)-treated iMg expressed significantly higher levels of IFN-stimulated genes (ISGs) with known anti-HIV activities (ISG15, MxB, Viperin, MxA, and OAS-1). In addition, TLR3 activation elicited the expression of the HIV entry coreceptor CCR5 ligands (CC chemokines) in iMg. Furthermore, the transcriptional profile analysis showed that poly (I:C)-treated cells had the upregulated IFN signaling genes (ISG15, ISG20, IFITM1, IFITM2, IFITM3, IFITM10, APOBEC3A, OAS-2, MxA, and MxB) and the increased CC chemokine signaling genes (CCL1, CCL2, CCL3, CCL4, and CCL15). These observations indicate that TLR3 is a potential therapy target for activating the intracellular innate immunity against HIV infection/replication in human microglial cells. Therefore, further studies with animal models and clinical specimens are necessary to determine the role of TLR3 activation-driven antiviral response in the control and elimination of HIV in infected host cells.
Subject(s)
HIV Infections , Induced Pluripotent Stem Cells , Microglia , Toll-Like Receptor 3 , Humans , Cells, Cultured , Immunity, Innate , Microglia/virology , Poly I-C/pharmacology , Toll-Like Receptor 3/geneticsABSTRACT
The detoxification of lethal organophosphate (OP) residues in the environment is crucial to prevent human exposure and protect modern society. Despite serving as excellent catalysts for OP degradation, natural enzymes require costly preparation and readily deactivate upon exposure to environmental conditions. Herein, we designed and prepared a series of phosphotriesterase mimics based on stable, self-assembled peptoid membranes to overcome these limitations of the enzymes and effectively catalyze the hydrolysis of dimethyl p-nitrophenyl phosphate (DMNP)âa nerve agent simulant. By covalently attaching metal-binding ligands to peptoid N-termini, we attained enzyme mimetics in the form of surface-functionalized crystalline nanomembranes. These nanomembranes display a precisely controlled arrangement of coordinated metal ions, which resemble the active sites found in phosphotriesterases to promote DMNP hydrolysis. Moreover, using these highly programmable peptoid nanomembranes allows for tuning the local chemical environment of the coordinated metal ion to achieve enhanced hydrolysis activity. Among the crystalline membranes that are active for DMNP degradation, those assembled from peptoids containing bis-quinoline ligands with an adjacent phenyl side chain showed the highest hydrolytic activity with a 219-fold rate acceleration over the background, demonstrating the important role of the hydrophobic environment in proximity to the active sites. Furthermore, these membranes exhibited remarkable stability and were able to retain their catalytic activity after heating to 60 °C and after multiple uses. This work provides insights into the principal features to construct a new class of biomimetic materials with high catalytic efficiency, cost-effectiveness, and reusability applied in nerve agent detoxification.
ABSTRACT
In developing low-temperature cofired ceramic (LTCC) technology for high-density packaging or advanced packaged electronics, matching the coefficient of thermal expansion (CTE) among the packaged components is a critical challenge to improve reliability. The CTEs of solders and organic laminates are usually larger than 16.0 ppm of °C1-, while most low-permittivity (εr) dielectric ceramics have CTEs of less than 10.0 ppm °C1-. Therefore, a good CTE match between organic laminates and dielectric ceramics is required for further LTCC applications. In this paper, we propose a high-CTE BaSO4-BaF2 LTCC as a potential solution for high-reliability packaged electronics. The BaSO4-BaF2 ceramics have the advantages of a wide low-temperature sintering range (650-850 °C), low loss, temperature stability, and Ag compatibility, ensuring excellent performance in LTCC technology. The 95 wt %BaSO4-5 wt %BaF2 ceramic has a εr of 9.1, a Q × f of 40,100 GHz @11.03 GHz (Q = 1/tan δ), a temperature coefficient of the resonant frequency of -11.2 ppm °C1-, a CTE of +21.8 ppm °C1-, and a thermal conductivity of 1.3 W mK-1 when sintered at 750 °C. Furthermore, a dielectric resonant antenna using BaSO4-BaF2 ceramics, a typically packaged component of LTCC and laminate, was designed and used to verify the excellent performance by a gain of 6.0 dBi at a central frequency of 8.97 GHz and a high radiation efficiency of 90% over a bandwidth of 760 MHz. Good match and low thermal stress were found in the packaged components of BaSO4-BaF2 ceramics, organic laminates, and Sn-based solders by finite element analysis, proving the potential of this LTCC for high-reliability packaged electronics.