Two mono‐ and dinuclear Bi(III) complexes, Bi(L)2(NO3)2·NO3 (1) and Bi2(L)2Cl8 (2) (L = (2‐(2‐pyridyl)‐4‐methyl‐1,2‐dihydroquinazoline‐N3‐oxide), were obtained via complexation of L with Bi(III) ...nitrate pentahydrate and Bi(III) chloride. L and both complexes were characterized by elemental analyses and spectroscopic methods including FT‐IR, UV–Vis, and fluorescence spectroscopy. Specifically, it clearly manifested that both complexes had good fluorescence emission and showed different fluorescence behaviors in diverse solvents. Both Bi(III) complexes were further determined by X‐ray crystallography, and it was found that the ratio of ligand to metal was 2:1 in 1, whereas 2 was 1:1. Their coordination geometric configurations were significantly different, such as octa‐coordinated complex 1 formed an infinite 1‐D chain‐like, funnel‐shaped 2‐D network, and ladder‐like 3‐D supramolecular framework, whereas hexa‐coordinated complex 2 with a binuclear structure exhibited two slightly distorted octahedral geometric structures; meanwhile, symmetric units came into being an infinite 2‐D layer even and meter‐shaped 3‐D supramolecular skeleton. The optimal geometries, frontier molecular orbital energies, and molecular electrostatic potential diagrams of both complexes were calculated using DFT/B3LYP. The electronic distribution of HOMO‐LUMO rationalized the results of UV–Vis spectra with the help of TD‐DFT calculations. Furthermore, all samples demonstrated excellent antibacterial activities against Escherichia coli and Staphylococcus aureus. In addition, non‐covalent interactions of complexes and their contributions were quantified with Hirshfeld surfaces using CrystalExplorer17 program.
Two 2‐D and 3‐D supramolecular complexes, Bi(L)2(NO3)2NO3 (1) and Bi2(L)2Cl8 (2), were obtained by reaction of L with different metal salts. Both complexes were characterized by X‐ray crystallography, spectroscopic methods such as FT‐IR, UV–Vis, and fluorescence spectroscopy, as well as Hirshfeld surface analysis and DFT studies. The antimicrobial activities of all compounds were also compared.
Early life intervention is important to shape the gut microbiome profiles of adult animals due to the tremendous alteration of diet components. Nevertheless, there is still no unified understanding ...about its long-term effects in lambs. In this study, sixty 20-day-old lambs were assigned into ewe-rearing (ER) and artificial-rearing (AR) treatments to evaluate the effects of AR strategy on ruminal microbiota, fermentation, and morphology of pre-weaning lambs (from 20 to 60 days of age) and its long-term effects in the fattening stage (from 61 to 180 days of age). During the pre-weaning stage, ER lambs were breastfed and supplemented starter, while AR lambs were artificially fed with milk replacer and starter. During the fattening stage, all lambs in both treatments were fed with the same fattening diets. At 60, 120 and 180 days of age, 6 lambs from each group were slaughtered to collect rumen content and tissue samples. Compared with ER lambs, the dry matter feed intakes of AR lambs increased (P<0.05) from 20 to 180 days of age, companying an increased average daily gain (ADG) from 61 to 120 days of age (P<0.05) and from 121 to 180 days of age (0.05<P<0.1). Although there was no difference in short-chain fatty acid (SCFA, including acetate, propionate, and butyrate) between treatments before weaning (P>0.05), it was higher (P<0.05) in AR lambs compared with ER lambs at the fattening stage. The rumen keratin layer of AR lambs was thinner (P<0.05) than that of ER lambs. Along with lamb growth from 60 to 180 days of age, the differences in rumen bacterial diversity between AR and ER treatments grew more distinct (P<0.05). Compared with ER lambs, AR lambs increased (P<0.05) rumen bacteria abundance, such as phylum Spirochaetes and genus Treponema at 60 days of age, phylum Actinobacteria and genus Succiniclasticum at 120 days of age, and phylum Proteobacteria at 180 days of age, but decreased genus Selenomonas from 60 to 180 days of age, and Anaerovibrio at 180 days of age. In summary, the early interventions before weaning could improve dry matter feed intake of lambs, which triggered robust rumen development and produced positive long-term effects on rumen fermentation and noticeable weight gain of fattening lambs. It suggests that the artificial rearing strategy is effective in improving rumen fermentation and microbial maturity of intensive fattening lambs.
Herein, a Janus three-dimensional (3D) DNA nanomachine was constructed for the simultaneous and sensitive fluorescence detection and imaging of dual microRNAs (miRNAs) in cancer cells, which could ...effectively eliminate signal interference in a homogeneous nanoparticle-based 3D DNA nanostructure caused by the proximity of the two different signal probes to achieve accurate co-location in the same position of living cancer cells. In this system, the Janus nanoparticles were synthesized as the carrier for immobilizing two different oligonucleotides on two different functionalized hemispheres of the nanoparticles to form a Janus 3D DNA nanostructure, which could convert trace amounts of miRNA-21 and miRNA-155 targets into massive FAM and Cy5-labeled duplexes to induce two remarkable fluorescence emissions by the catalytic hairpin assembly (CHA) and 3D DNA walker cascade nucleic acid amplification strategy, realizing sensitive detection and imaging of miRNA targets in cancer cells. Impressively, in comparison with current miRNA imaging methods based on nanoparticle assemblies, the proposed strategy could efficiently eliminate "false positive" results obtained in single type miRNA detection and distinctly increase the immobilization concentration of two different signal probes using Janus nanoparticles as the carrier to further enhance fluorescence intensity, resulting in accurate co-location in the same position of living cells. Meanwhile, the proposed fluorescence imaging technology makes it possible to visualize low concentrations of miRNAs with tiny change associated with some cancers, which could significantly improve the accuracy and precision compared to those of the conventional fluorescence
in situ
hybridization (FISH) approach. Therefore, it could serve as persuasive evidence for supplying accurate information to better understand biological processes and investigate mechanisms of various biomolecules and subcellular organelles, resulting in the further validation of their function in tumor proliferation and differentiation. This strategy provided an innovative approach to design new generations of nanomachines with ultimate applications in bioanalysis and clinical diagnoses.
A Janus three-dimensional DNA nanomachine was constructed for the simultaneous and sensitive fluorescent detection and imaging of dual microRNAs in the cancer cells.
The quinazoline‐type ligand 2‐(3‐ethoxy‐2‐hydroxyphenyl)‐4‐methyl‐1,2‐dihydroquinazolin 3‐oxide (HL1, H is the deprotonatable hydrogen) was synthesized. Two mono‐ and dinuclear Cu (II) complexes, ...Cu(L2)2·2CH3OH (1), and Cu4(L2)4(NO3)2 (2) (HL2 = 1‐(2‐{(E)‐(3‐ethoxy‐2‐hydroxybenzylideneamino}phenyl)ethanone oxime), were obtained via complexation of HL1 with Cu (II) acetate monohydrate or Cu (II) nitrate trihydrate in methanol. HL1 and both complexes were characterized by elemental analyses and spectroscopic methods. The structures of complexes were confirmed by single‐crystal X‐ray crystallography and the ratio of ligand to metal in 1 was 2:1 whereas 2 was 1:1. In the crystal structures, hexa‐coordinated Cu (II) complex 1 was assembled into an infinite 1‐D, 2‐D network and 3‐D supramolecular framework. Complex 2 included four deprotonated (L2)− units, four coordinated Cu (II) and two coordinated nitrate anions, forming an infinite 2‐D layer and interesting butterfly‐shaped 3‐D supramolecular skeleton. Specifically, the Cu1 and Cu4 centers were four‐coordinated, while the Cu2 and Cu3 centers were penta‐coordinated in 2. Furthermore, electrochemical properties and antibacterial activities of both complexes were also investigated. In addition, the electron paramagnetic resonance (EPR) spectra of 1 and 2 were also studied. The optimal geometries, HOMO‐LUMO energies and molecular electrostatic potential diagrams of two complexes were calculated using density functional theory (DFT)/B3LYP, and specific electronic transitions in the UV–vis spectra of 1 and 2 were recorded by time‐dependent DFT (TD‐DFT) calculations. Additionally, the noncovalent interactions between both complexes were also confirmed by Hirshfeld surfaces.
Two mono‐ and dinuclear Cu (II) complexes, Cu(L2)2·2CH3OH (1) and Cu4(L2)4(NO3)2 (2) were obtained by reaction of HL1 with different metal salts. Both complexes were characterized by X‐ray crystallography, spectroscopic methods, and molecular electrostatic potential diagrams, as well as Hirshfeld surface analysis and density functional theory (DFT) studies. The antimicrobial activities of all compounds were also compared.
Two complexes Zn(L)2(CH3OH)2(NO3)2 (1) and Ni(L)3·(NO3)2 (2) (L = 2‐2‐imidazolyl‐4‐methyl‐1,2‐dihydroquinazoline‐N3‐oxide) were obtained successfully by means of slow evaporation solution technique ...(SEST) and characterized using elemental analysis, FT‐IR, UV–vis, and fluorescence spectroscopic. X‐ray diffraction revealed that the metal in complex 1 is chelated by two L ligands and two lattice methanol molecules, whereas in 2 by three L ligands, counterbalanced by nitrate ions. The crystal structures of both showed infinite 1‐D, 2‐D, and 3‐D supramolecular architecture due to intermolecular interactions. Most strikingly, Zn (II) complex showed different fluorescence properties in diverse solvents. The antimicrobial activities of all compounds were compared and showed perceptible efficiency against Gram‐negative and Gram‐positive bacteria. Electrostatic potential (ESP) calculation was used to predict the nucleophilic and electrophilic attack sites. Density functional theory (DFT) calculation results showed good agreement with experimental data, as well as the frontier molecular orbital energy gaps were detected by time‐dependent (TD)‐DFT method with HOMO–LUMO calculations. Additionally, the non‐covalent interactions of both complexes were further quantified and explored with the help of Hirshfeld surface analysis.
Two complexes Zn(L)2(CH3OH)2(NO3)2 (1) and Ni(L)3·(NO3)2 (2) were synthesized and characterized by FT‐IR, UV–vis, and fluorescence spectra, as well as X‐ray crystallography. Furthermore, some significant investigations based on density functional theory (DFT) calculation, such as electrostatic potential (ESP) and Hirshfeld surface have been carried out to further analyze and quantify the short interactions of both complexes. The antibacterial properties of all compounds were also compared.
In this paper, a decentralized fault diagnosis approach of complex processes is proposed based on multiblock kernel partial least squares (MBKPLS). To solve the problem posed by nonlinear ...characteristics, kernel partial least squares (KPLS) approaches have been proposed. In this paper, MBKPLS algorithm is first proposed and applied to monitor large-scale processes. The advantages of MBKPLS are: 1) MBKPLS can capture more useful information between and within blocks compared to partial least squares (PLS); 2) MBKPLS gives nonlinear interpretation compared to MBPLS; 3) Fault diagnosis becomes possible if number of sub-blocks is equal to the number of the variables compared to KPLS. The proposed methods are applied to process monitoring of a continuous annealing process. Application results indicate that the proposed decentralized monitoring scheme effectively captures the complex relations in the process and improves the diagnosis ability tremendously.
Ultrafine Ni2P/Co2P nanoparticles encapsulated in hollow porous N-doped carbon nanospheres are synthesized through a facile two-step access. Firstly, metallic Ni and Co coated by hollow N-doped ...spheres as precursors are obtained through a high temperature calcination route of organic polymer and inorganic Ni and Co salts. Then bimetal Ni2P/Co2P supported on N-doped carbon nanospheres are acquired by a facile phosphorization process. It is worth to note that aniline-pyrrole polymer can prevent fast growth and severe aggregation of Ni2P/Co2P, which implies more exposed active sites. Moreover, the calcination of hollow polymer spheres lead to the formation of ultrathin NC shell on the surface of Ni2P/Co2P hybrids, which can tune electronic structures, improve the conductivity and protect active sites from corrosion in harsh conditions. When used as HER catalyst, it displays remarkable catalytic activity in both acidic and alkaline solutions, which needs an onset potential of only 164 mV and 168 mV, respectively. Therefore, this work may propose a new strategy to design unique inorganic-organic heterostructures to combine ultrafine metal phosphides with porous carbon for efficient HER.
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•Bimetal Ni2P/Co2P@NC hybrids are acquired by a facile phosphorization process.•The aniline-pyrrole polymer prevents the growth and aggregation of Ni2P/Co2P.•The calcination leads to the formation of ultrathin NC shell on the surface of Ni2P/Co2P hybrid.•Ni2P/Co2P@NC displays remarkable activity in acidic and alkaline solution.
The reaction of {(HNEt3)2Ag10(tBuC6H4S)12}n, Ag2O, Na2MoO4, and m‐methoxybenzoic acid (Hmbc) in CH3OH/CH2Cl2 led to yellow crystals of Ag4S4 (MoO4)5@Ag66 (SD/Ag70b; SD=SunDi) only, while in the ...presence of DMF, additional dark‐red crystals of Ag10@ (MoO4)7@Ag60 (SD/Ag70a) were obtained. SD/Ag70b consists of five MoO42− ions wrapped by a shell of 66 Ag atoms, while SD/Ag70a contains a rare Ag10 kernel consisting of five tetrahedra sharing faces and edges, surrounded by seven MoO42− ions enclosed in a shell of 60 Ag atoms. The formation of the Ag10 kernel originates from a reduction reaction during the self‐assembly process that involves DMF. This work provides the structural information of a unique Ag10 kernel (five fused Ag4 tetrahedra) and paves an avenue to trap elusive silver species with hierarchical multi‐shell silver nanocluster assemblies with the help of anion templates.
The third layer is the charm: The construction of three‐layer shell structures of hybrid silver nanoclusters is reported. While the majority of the silver atoms usually makes up the outermost shell, an unprecedented Ag10 cluster forms in the innermost shell if DMF is present during synthesis. The work presents an approach to trap elusive embryonic silver species in nanocluster assemblies.
Electrochemiluminescence (ECL), as a sensitive and controllable assay, offers a considerable opportunity for multiple types of biomarkers detection. However, constructing such a biosensor remains a ...significant challenge. Herein, an ultrasensitive and versatile ECL biosensor was constructed to detect multiple types of biomarkers from breast cancer by taking the strategies of nonenzymatic catalytic hairpin assembly (CHA) and hybridization chain reaction (HCR) amplification, as well as aptamer-triggered emitter release. Concretely, with the appearance of target 1 microRNA-21 (miRNA-21), abundant double-stranded DNA (dsDNA) polymers were generated on this biosensing surface via amplification circuits of CHA and HCR, which could be intercalated into substantial (Ru(bpy)2dppzCl2) as ECL indicators to obtain an obvious enhancement of ECL signal for target 1 detection with a detection limit (0.1 fM). Furthermore, in the presence of target 2 human mucin 1 (MUC1) protein, the ECL signal had a distinct decrease, because aptamer recognition induced the release of Ru(bpy)2dppzCl2 from the sensing surface, thus, achieving a sensitive detection for MUC1 with a detection limit (2.4 fg·mL–1). Simultaneously, this sensing platform was applied to monitor the biomarkers from MDA-MB-231 breast cancer cells, suggesting that this method was applicable to detect real samples. Therefore, this platform is an applicable and versatile implement for the determination of multiple types of biomarkers to improve diagnostic accuracy and efficiency.
The rapid, accurate, and robust computation of virtual human figures' "in-between" pose transitions from available and sometimes sparse inputs is of fundamental significance to 3D interactive ...graphics and computer animation. Various methods have been proposed to produce natural lifelike transitions of human pose automatically in recent decades. Nevertheless, conventional pure model-driven methods require heuristic knowledge (e.g., least motion guided by physics laws) and ad-hoc clues (e.g., splines with non-uniform time warp) that are difficult to obtain, learn, and infer. With the fast emergence of large-scale datasets readily available to animators in the most recent years, deep models afford a powerful alternative to tackle the aforementioned challenges. However, pure data-driven methods still suffer from the remaining challenges such as unseen data in practice and less generative power in model/domain/data transfer, and the measurement of the generative power has always been omitted in these works. In essence, data-driven methods solely rely on the qualities and quantities of training datasets. In this paper, we propose a hybrid approach built upon the seamless integration of data-driven and model-driven methods, called Dynamic Motion Transition (DMT), with the following salient modeling advantages: (1) The data augmentation capability based on the limited human locomotion data capture and the concept of force-derived directly from physical laws; (2) Force learning by which skeleton joints are driven to move, and the Conditional Temporal Transformer (CTT) being trained to learn the force change in the local range, both at the fine level; and (3) At the coarse level, the effective and flexible creation of the subsequent step motion using Dynamic Movement Primitives (DMP) until the target is reached. Our extensive experiments have confirmed that our model can outperform the state-of-the-art methods under the newly devised metric by virtue of the least action loss function. In addition, our novel method and system are of immediate benefit to many other animation tasks such as motion synthesis and control, and motion tracking and prediction in this bigdata graphics era.
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