Calligraphy of Nanoplasmonic Bioink-Based Multiplex Immunosensor for Precision Immune Monitoring and Modulation.

Immunomodulation therapies have attracted immense interest recently for the treatment of immune-related diseases, such as cancer and viral infections. This new wave of enthusiasm for immunomodulators, predominantly revolving around cytokines, has spurred emerging needs and opportunities for novel immune monitoring and diagnostic tools. Considering the highly dynamic immune status and limited window for therapeutic intervention, precise real-time detection of cytokines is critical to effectively monitor and manage the immune system and optimize the therapeutic outcome. The clinical success of such a rapid, sensitive, multiplex immunoanalytical platform further requires the system to have ease of integration and fabrication for sample sparing and large-scale production toward massive parallel analysis. In this article, we developed a nanoplasmonic bioink-based, label-free, multiplex immunosensor that can be readily "written" onto a glass substrate via one-step calligraphy patterning. This facile nanolithography technique allows programmable patterning of a minimum of 3 µL of nanoplasmonic bioink in 1 min and thus enables fabrication of a nanoplasmonic microarray immunosensor with 2 h simple incubation. The developed immunosensor was successfully applied for real-time, parallel detection of multiple cytokines (e.g., interleukin-6 (IL-6), tumor necrosis factor-alpha (TNF-α), and transforming growth factor-beta (TGF-ß)) in immunomodulated macrophage samples. This integrated platform synergistically incorporates the concepts of nanosynthesis, nanofabrication, and nanobiosensing, showing great potential in the scalable production of label-free multiplex immunosensing devices with superior analytical performance for clinical applications in immunodiagnostics and immunotherapy.

The IBA-ISMO Method for Rolling Bearing Fault Diagnosis Based on VMD-Sample Entropy.

Rolling bearings are important supporting components of large-scale electromechanical equipment. Once a fault occurs, it will cause economic losses, and serious accidents will affect personal safety. Therefore, research on rolling bearing fault diagnosis technology has important engineering practical significance. Feature extraction with high price density and fault identification are two keys to overcome in the field of fault diagnosis of rolling bearings. This study proposes a feature extraction method based on variational modal decomposition (VMD) and sample entropy and also designs an improved sequence minimization algorithm with optimal parameters to identify the fault. Firstly, a variational modal decomposition system based on vibration signals is designed, and the sample entropy of the components is extracted as the eigenvalue of the signal. Secondly, in order to improve the accuracy of fault diagnosis, the sequence minimum optimization algorithm optimized by the bat algorithm is used as the classifier. Certainly, the traditional bat algorithm (BA) and the sequence minimum optimization algorithm (SMO) are improved, respectively. Therefore, a fault diagnosis algorithm based on IBA-ISMO is obtained. Finally, the experimental verification is designed to prove that the algorithm model has a good state recognition rate for bearings.

Selective Reductive Coupling of Vinyl Azaarenes and Alkynes via Photoredox Cobalt Dual Catalysis.

A visible light-induced Co-catalyzed highly regio- and stereoselective reductive coupling of vinyl azaarenes and alkynes has been developed. Notably, Hünig's base together with simple ethanol has been successfully applied as the hydrogen sources instead of commonly used Hantzsch esters in this catalytic photoredox reaction. This approach has considerable advantages for the straightforward synthesis of stereodefined multiple substituted alkenes bearing an azaarene motif, such as excellent regioselectivity (>20 : 1 for >30 examples) and stereoselectivity (>20 : 1 E/Z), broad substrate scope and good functional group compatibility under mild reaction conditions, which has been utilized in the concise synthesis of natural product monomorine I. A reasonable catalytic reaction pathway involving protolysis of the cobaltacyclopentene intermediate has been proposed based on the mechanistic studies.

Pd-catalyzed amidation of 1,3-diketones with CO and azides via a nitrene intermediate.

An efficient Pd-catalyzed amidation of 1,3-diketones has been developed using carbon monoxide and organic azides. This reaction provides a step-economic approach to produce ß-ketoamides from readily available compounds under mild ligand-, oxidant-, and base-free conditions. The mechanistic studies showed that the reaction occurred through an in situ generated isocyanate intermediate.

Effects of Alkaline Cleaning on the Conversion and Transformation of Functional Groups on Ion-Exchange Membranes in Polymer-Flooding Wastewater Treatment: Desalination Performance, Fouling Behavior, and Mechanism.

The aging effects of sodium hydroxide (NaOH) on ion-exchange membranes were systematically studied, including the membrane properties, desalination performance, and fouling behaviors. After aging in NaOH solution, there were minor changes in the cation-exchange membrane (CEM) properties; however, functional groups (i.e., quaternary amines) on the anion-exchange membranes (AEMs) were converted into benzylic alcohol, alkene, and tertiary amines, respectively, by nucleophilic substitution, Hofmann elimination, and ylide formation. These degradations rendered decreased ion-exchange capacity (IEC), increased electrical resistance, lost hydrophilicity, and weakened mechanical strength. Moreover, severe deteriorations of desalination performance were observed due to the little ion-exchange ability of the degraded AEMs. The desalination rates were restored after cultivating the aged AEMs in acid solution, mainly because the tertiary amines transformed from the hydroxide form (OH-form) to the ionic chlorine form (Cl-form). The restored desalination rates indicated that the main degradation products were tertiary amines. In addition, the antifouling performance decreased in the order of aged OH-form > aged Cl-form > original AEMs due to the reduction of foulant-membrane intermolecular interactions after aging in NaOH solution. The results contribute to establishing a more comprehensive understanding of the effects of alkaline cleaning on IEMs and provide new insights into cleaning-process optimization and membrane modification.

Intermolecular C-H Amidation of (Hetero)arenes to Produce Amides through Rhodium-Catalyzed Carbonylation of Nitrene Intermediates.

Amide bond formation is one of the most important reactions in organic chemistry because of the widespread presence of amides in pharmaceuticals and biologically active compounds. Existing methods for amides synthesis are reaching their inherent limits. Described herein is a novel rhodium-catalyzed three-component reaction to synthesize amides from organic azides, carbon monoxide, and (hetero)arenes via nitrene-intermediates and direct C-H functionalization. Notably, the reaction proceeds in an intermolecular fashion with N2 as the only by-product, and either directing groups nor additives are required. The computational and mechanistic studies show that the amides are formed via a key Rh-nitrene intermediate.

Performance and autopsy of nanofiltration membranes at an oil-field wastewater desalination plant.

In this study, the long-term operational performance of an on-site NF facility at a full-scale oil-field wastewater desalination plant was monitored. The NF facility with poor permeability due to membrane fouling enables efficient multivalent salt removal (rejections of Mg2+, Ca2+, Fe3+, and Al3+ were approximately 100%). Moreover, a comparison of the cleaning efficiencies of two on-site cleaning modes indicated that PL-007 cleaning helped to improve the effectiveness of subsequent acid cleaning in the removal of inorganic foulants. Furthermore, a spiral-wound NF membrane module harvested from the plant was unfolded and autopsied. The results showed that both anionic polyacrylamide (APAM) and crude oil were identified as the predominant organic matter on the membrane surface and collectively accounted for a substantial fraction (86.3%) in terms of dry weight. Additionally, dissolved organics with a high molecular weight were prone to accumulation on the membrane surface. Multivalent elements, including Mg, Ca, Al, Fe, and Si, were the primary inorganic species in the fouling layer. Among the inorganic elements, Si occupied a high proportion and existed in the form of SiO2 in the fouling layer. According to the autopsy results, organic fouling combined with inorganics was responsible for the decline in the flux.

Co(II)/Ag(I) Synergistically Catalyzed Monoinsertion Reaction of Isocyanide to Terminal Alkynes with H2O: Synthesis of Alkynamide Derivatives.

A Co(II)/Ag(I) synergistically catalyzed three-component reaction of isocyanide with terminal alkyne and water to afford alkynamide derivatives is reported. The insertion of monoisocyanide into the C-H bond of terminal alkynes is an efficient, straightforward, atom-economical route to alkynamides, which are useful synthons in organic synthesis. This synergistic process achieves the cleavage of a C-H bond and the construction of new C-C and C═O bonds under mild conditions through the reaction of Co(II)-activated isocyanides and a Ag(I)-complex-activated terminal alkyne. This reaction has broad substrate versatility and functional group tolerance.

Antifouling performance of polytetrafluoroethylene and polyvinylidene fluoride ultrafiltration membranes during alkali/surfactant/polymer flooding wastewater treatment: Distinctions and mechanisms.

Alkali/surfactant/polymer (ASP) flooding wastewater is highly caustic, and membrane fouling is the main obstacle during ASP ultrafiltration (UF) treatment. To maintain favorable filtration performance, polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF) membranes were implemented here, and their antifouling properties and mechanisms were investigated based on the threshold flux theory. Compared with the PVDF membranes, the PTFE membranes exhibited superior antifouling properties with lower reductions in flux and smaller hydraulic resistance, and they presented a nearly identical pseudo-stable fouling rate at a later time point. In the fouling layers of the PTFE and PVDF membranes, anion polyacrylamide (APAM) was observed along with divalent/trivalent metal ions. The thermodynamic and molecular mechanisms of membrane fouling by APAM were elucidated using the Extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory and atomic force microscopy (AFM), respectively. The calculated total interfacial free energy (mJ/m2) of adhesion between the APAM and PTFE membranes was positive, and the value between the APAM and PVDF membranes was negative. Furthermore, the values and interaction distances of the measured intermolecular rupture and approaching forces were larger for APAM-PTFE than for APAM-PVDF. For the PTFE membranes, the positive free energies and smaller intermolecular interaction resulted in weaker APAM-PTFE adhesion and adsorption and therefore the lower levels of flux decline and the later achievement of the pseudo-stable fouling rate. Additionally, the total flux recoveries observed after physical cleaning reached 0.78-0.80 and 0.32-0.39 for the PTFE and PVDF membranes, respectively, which showed that the PTFE membranes can be cleaned easily. The PTFE membranes have considerable potential for extensive application in UF treatments for ASP wastewater. These results should promote understanding the essence of the threshold flux and the fouling control of UF membranes.

Co-Catalyzed Synthesis of N-Sulfonylcarboxamides from Carboxylic Acids and Sulfonyl Azides.

A Co-catalyzed effective synthesis of N-sulfonylcarboxamides from the reaction of carboxylic acids and organic azides in the presence of isocyanide has been developed. The protocol has the advantages of short time, low temperature, and being oxidant-free, which provides a new and simple approach for the synthesis of N-sulfonylcarboxamides in good to excellent yields with a broad substrate scope.

The influences of separators on capacitive deionization systems in the cycle of adsorption and desorption.

This research focused on the influence of different separator compartments on the performance of capacitive deionization (CDI) cells in terms of brackish water treatment. For comparison, different separators including filter paper(FP), carbon nanotube (CNT), and stainless steel fiber (SSF) on deionization and desorption rate of salt were examined. The best performance was obtained when the CNT separator was packed, followed by SSF and FP. Reducing the cell voltage from 1.2 to 0.4 V decreased the salt removal and electrode regeneration rate of SSF-CDI. Electrochemical impedance spectrometry (EIS) analysis revealed that the resistance and specific capacitance of separator materials are essential to the desalination and desorption performance of CDI. The electric double layers (EDLs) accelerated the ion transfer in the flow chamber due to storing excess ions, therefore increasing the desalination and electrode regeneration rate.

Cobalt(ii)-catalyzed bis-isocyanide insertion reactions with sulfonyl azides via nitrene radicals: chemoselective synthesis of sulfonylamidyl amide and 3-imine indole derivatives.

A chemoselective Co(ii)-catalyzed effective synthesis of sulfonylamidyl amide and 3-imine indole derivatives by using isocyanides and sulfonyl azides has been developed. This protocol provides a new, environmentally friendly and simple strategy for the efficient synthesis of the sulfonylamidyl amide and 3-imine indole derivatives with a wide range of substrates in the absence of any oxidants and additives.

Cobalt(II)-Catalyzed Isocyanide Insertion Reaction with Sulfonyl Azides in Alcohols: Synthesis of Sulfonyl Isoureas.

A Co(II)-catalyzed isocyanide insertion reaction with sulfonyl azides in alcohols to form sulfonyl isoureas via nitrene intermediate has been developed. This protocol provides a new, environmentally friendly, and simple strategy for the synthesis of sulfonyl isourea derivatives by employing a range of substrates under mild conditions.

Cobalt-Catalyzed Annulation of Amides with Isocyanides via C(sp2)-H Activation.

A cobalt-catalyzed [4 + 1] cycloaddition of easily accessible amides with isocyanides for the efficient synthesis of 3-iminoisoindolinone derivatives in high yield under mild conditions via intramolecular C(sp2)-H activation and isocyanide insertion is reported. The annulation was found to be applicable to a broad range of substrates, including arylamides, heteroarylamides, and acrylamide derivatives. Strongly coordinating N-heterocyclic directing groups such as pyridine, pyrimidine, and even pyrazole were fully tolerated in this cobalt-catalyzed C-H activation reaction.

Microbial Communities Shaped by Treatment Processes in a Drinking Water Treatment Plant and Their Contribution and Threat to Drinking Water Safety.

Bacteria play an important role in water purification in drinking water treatment systems. On one hand, bacteria present in the untreated water may help in its purification through biodegradation of the contaminants. On the other hand, some bacteria may be human pathogens and pose a threat to consumers. The present study investigated bacterial communities using Illumina MiSeq sequencing of 16S rRNA genes and their functions were predicted using PICRUSt in a treatment system, including the biofilms on sand filters and biological activated carbon (BAC) filters, in 4 months. In addition, quantitative analyses of specific bacterial populations were performed by real-time quantitative polymerase chain reaction (qPCR). The bacterial community composition of post-ozonation effluent, BAC effluent and disinfected water varied with sampling time. However, the bacterial community structures at other treatment steps were relatively stable, despite great variations of source water quality, resulting in stable treatment performance. Illumina MiSeq sequencing illustrated that Proteobacteria was dominant bacterial phylum. Chlorine disinfection significantly influenced the microbial community structure, while other treatment processes were synergetic. Bacterial communities in water and biofilms were distinct, and distinctions of bacterial communities also existed between different biofilms. By contrast, the functional composition of biofilms on different filters were similar. Some functional genes related to pollutant degradation were found widely distributed throughout the treatment processes. The distributions of Mycobacterium spp. and Legionella spp. in water and biofilms were revealed by real-time quantitative polymerase chain reaction (qPCR). Most bacteria, including potential pathogens, could be effectively removed by chlorine disinfection. However, some bacteria presented great resistance to chlorine. qPCRs showed that Mycobacterium spp. could not be effectively removed by chlorine. These resistant bacteria and, especially potential pathogens should receive more attention. Redundancy analysis (RDA) showed that turbidity, ammonia nitrogen and total organic carbon (TOC) exerted significant effects on community profiles. Overall, this study provides insight into variations of microbial communities in the treatment processes and aids the optimization of drinking water treatment plant design and operation for public health.

Pd-Catalyzed Intramolecular Heck Reaction, C(sp(2))-H Activation, 1,4-Pd Migration, and Aminopalladation: Chemoselective Synthesis of Dihydroindeno[1,2,3-kl]acridines and 3-Arylindoles.

Palladium-catalyzed intramolecular Heck reaction and aminopalladation of N-(2-(1-phenylvinyl)phenyl)aniline for the efficient synthesis of dihydroindeno[1,2,3-kl]acridines and 3-arylindoles via tuning of the phosphine ligands and solvents under two optimized conditions are reported. The reaction follows a 1,4-Pd migration, aminopalladation, C(sp(2))-H activation, as well as five- and six-membered-ring fusion to form different products. The dihydroindeno[1,2,3-kl]acridine derivatives showed higher triplet energy (ET) levels than common blue phosphorescent dopant and may serve as good host candidates for blue triplet emitters.

The involvement of the trisulfur radical anion in electron-catalyzed sulfur insertion reactions: facile synthesis of benzothiazine derivatives under transition metal-free conditions.

An efficient and practical synthesis of benzothiazine by K2S initiated sulfur insertion reaction with enaminones via electron catalysis is developed. This protocol provides a new, environment-friendly and simple strategy to construct benzothiazine derivatives via formation of two C-S bonds under transition metal-free, additive-free and oxidant-free conditions. K2S not only provides the sulfur insertion source, but also ignites the reaction through the formation of a trisulfur radical anion and electrons in DMF.

tert-Butyl peroxybenzoate (TBPB)-mediated 2-isocyanobiaryl insertion with 1,4-dioxane: efficient synthesis of 6-alkyl phenanthridines via C(sp3)-H/C(sp2)-H bond functionalization.

An efficient method for the construction of 6-alkyl phenanthridines by tert-butyl peroxybenzoate (TBPB)-mediated 2-isocyanobiaryl insertion with 1,4-dioxane was established. Two new C-C bonds were formed in this reaction via a sequential C(sp(3))-H/C(sp(2))-H bond functionalization under metal-free conditions.