Polymer Single-Chain Nanoparticles: Shaping Solid Surfactants.

Polymer single-chain nanoparticles (SCNPs) have found a wide range of applications spanning catalysts, sensors and nanomedicine. The generation of structured SCNPs from star-shaped polymers with diverse architectures and functionalities affords a new avenue to expand the emerging research area. The large-scale synthesis of structured SCNPs is described by the electrostatics-mediated intramolecular crosslinking of three types of 3-armed star-shaped polymers (T-P4VP, T-PS-b-P4VP, and T-P4VP-b-PS), whose configuration is tunable from spherical to cage-shaped to dumbbell-shaped and star-shaped. The structured SCNPs are amphiphilic and can be used as solid surfactants to stabilize different types of emulsions.

Chemo-, regio- and enantioselective hydroformylation of trisubstituted cyclopropenes: access to chiral quaternary cyclopropanes.

Catalytic asymmetric synthesis of polysubstituted chiral cyclopropane presents a significant challenge in organic synthesis due to the difficulty in enantioselective control. Here we report a rhodium-catalyzed highly chemo-, regio- and enantioselective hydroformylation of trisubstituted cyclopropenes affording chiral quaternary cyclopropanes. Importantly, the easy made sterically bulky ligand L1 can effectively suppress hydrogenation and decomposition reactions and give quaternary cyclopropanes with high regio- and enantioselectivities for both aryl and alkyl functionalized substrates. Control experiments and computational studies reveal the sterically hindered well-defined chiral pocket instead of the substrates bearing electron-withdrawing diester groups is important for controlling the enantioselectivity and regioselectivity. Scale-up reaction and follow-up diverse transformations are also presented. Density Functional theory (DFT) computations suggest that the regio- and enantio-selectivities originate from the cyclopropene insertion to the Rh-H bond. The high regioselectivity is found to benefit from the presence of more efficient noncovalent interactions (NCIs) manifesting in the form of C-H···Cl, C-H···N, and l.p(Cl)···π contacts.

A Merger of Relay Catalysis with Dynamic Kinetic Resolution Enables Enantioselective ß-C(sp3)-H Arylation of Alcohols.

The conceptual merger of relay catalysis with dynamic kinetic resolution strategy is reported to enable regio- and enantioselective C(sp3)-H bond arylation of aliphatic alcohols, forming enantioenriched ß-aryl alcohols typically with >90 : 10 enantiomeric ratios (up to 98 : 2 er) and 36-74 % yields. The starting materials bearing neighbouring stereogenic centres can be converted to either diastereomer of the ß-aryl alcohol products, with >85 : 15 diastereomeric ratios determined by the catalysts. The reactions occur under mild conditions, ensuring broad compatibility, and involve readily available aryl bromides, an inorganic base, and commercial Ru- and Pd-complexes. Mechanistic experiments support the envisioned mechanism of the transformation occurring through a network of regio- and stereoselective processes operated by a coherent Ru/Pd-dual catalytic system.

Reconfigurable droplet networks.

Droplet networks stabilized by lipid interfacial bilayers or colloidal particles have been extensively investigated in recent years and are of great interest for compartmentalized reactions and biological functions. However, current design strategies are disadvantaged by complex preparations and limited droplet size. Here, by using the assembly and jamming of cucurbit[8]uril surfactants at the oil-water interface, we show a novel means of preparing droplet networks that are multi-responsive, reconfigurable, and internally connected over macroscopic distances. Openings between the droplets enable the exchange of matter, affording a platform for chemical reactions and material synthesis. Our work requires only a manual compression to construct complex patterns of droplet networks, underscoring the simplicity of this strategy and the range of potential applications.

Numerical study and orthogonal analysis of optimal performance parameters for vertical cooling of sintered ore.

The sinter cooler, essential for cooling hot sintered ore to a specific temperature, has seen recent advancements with the introduction of a vertical sinter cooling furnace. This innovation aims to enhance energy efficiency, reduce emissions, and improve waste heat recovery. Despite significant research, a quantitative analysis of factors impacting its cooling and heat transfer efficiency is lacking. This study utilizes the Euler model and local non-equilibrium thermodynamic theory to identify key factors affecting the gas-solid cooperative cooling process in the vertical cooler. Through an orthogonal experimental approach, the paper determines the optimal structural and operational parameters for the furnace. Key findings include that a gas-solid ratio of 1200m^3/t, inlet air temperature of 50 â„ƒ, cooling section height of 6m, and diameter of 13.25m maximize efficiency, achieving a weighted range normalization value of 0.962. This configuration meets sintered ore cooling requirements while optimizing waste heat recovery. The study reveals that the impact on heat transfer efficiency is influenced primarily by the gas-solid ratio, followed by the cooling section's height, diameter, and inlet air temperature. These insights are crucial for enhancing the vertical sinter cooler's design, contributing to more energy-efficient and environmentally friendly sintering processes.

Circular RNA MAP2K2-modified immunosuppressive dendritic cells for preventing alloimmune rejection in organ transplantation.

Long-term patient and graft survival has been achieved in organ transplantation but at the expense of toxic side effects that are associated with long-term use of nonspecific immunosuppressive drugs. Discovering new regulators of dendritic cells is the key for development of an ideal treatment to prevent immune rejection. We hypothesized that knockdown of circMAP2K2 induces immunosuppressive DCs and that treatment with circMAP2K2 silenced-DCs can prevent alloimmune rejection. DCs were cultured and transfected with siRNA for circMAP2K2. circMAP2K2 levels were measured by qRT-PCR. DC's maturation and immune function were assessed by flow cytometry and mixed lymphocyte reactions. The function of circMAP2K2 was illustrated by a series of RIP and IP. The therapeutics of engineered DCs was tested in a mouse heart transplantation model. We found that circMAP2K2 was highly expressed in mature DCs. Knockdown of circMAP2K2 reduced expression of MHCII, CD40 and CD80, attenuated the ability of DCs to activate allogeneic naïve T cells, and enhanced CD4+CD25+FOXP3+ regulatory T cells (Treg). circMAP2K2-induced immunosuppressive DCs by interacting with SENP3. Treatment with circMAP2K2-knockdown DCs attenuated alloimmune rejection and prolonged allograft survival in a murine heart transplantation model. The immune suppression induced in vivo was donor-antigen specific. In conclusion, knockdown of circMAP2K2 can induce immunosuppressive DCs which are able to inhibit overactive immune response, highlighting a new promising therapeutic approach for immune disorder diseases.

Study on MICP dust suppression technology in open pit coal mine: Preparation and mechanism of microbial dust suppression material.

With the recent increases in energy demands, the dust hazards of coal mining caused by transportation, loading and unloading and other processes are becoming increasingly serious. To control dust in open pit coal mines more environmentally friendly and efficiently, and to promote the use and development of non-in situ high-yield urease microorganisms for dust suppression in coal mines, Bacillus pasteurii was selected for dust suppression experiments in this article. Additionally, the growth of microorganisms in the coal dust microenvironment was simulated, and the effect of microbial mineralization products on the calorific value of upper coal dust was further studied. Our findings indicated that Bacillus pasteurii induced dust suppression by forming a calcite precipitate with non-uniform particle size to coal dust cementation. Moreover, after a single spray, the wind erosion resistance efficiency was 84% when the wind speed was set at 10 m/s. The growth of microorganisms and urease activity in the coal dust leachate were largely equal to those in the control group, reaching a peak at approximately 24 h, that the maximum growth quantity of OD600 was about 1.5, and the maximum urease activity was 11 mmol·L-1·min-1. The difference between the peak heat release rate of mixed coal dust and pure coal was only 4.82 kW/m2, which would not affect the value of coal products. Non in-situ Bacillus pasteurii can be growth metabolized normally in the microenvironment of coal dust. Finally, the mechanism of coal dust suppression by mineralization of microbial bacterial solution to form calcium carbonate was described by a reaction equation, which is important for further application and development of microbial dust suppressants.

Fir sawdust as a low-cost and easily recyclable adsorbent: efficient removal of Pb(II), Cu(II), and Zn(II) contaminants from wastewater.

The main pollution sources of heavy metals are the arbitrary discharge of industrial wastewater and waste residues, which cause serious harm to the water environment, soil environment, and human health. In this study, following the principle of waste utilization, a gel adsorbent (AA-SW-AMPS) was prepared by microwave-assisted chemical cross-linking using fir sawdust as raw material. A scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and swelling dynamic experiments were used to investigate the microstructure, reaction mechanism, and water absorption performance of AA-SW-AMPS. The N2 adsorption-desorption curve shows that the porous structure of AA-SW-AMPS creates 240.75 cm2/g of specific surface area to enable excellent heavy-metal sorption. It was determined by adsorption experiments that the optimal adsorption state was when the dosage of AA-SW-AMPS was 5 g/L, the pH of the solution was 5, the adsorption time was 45 min, and the initial heavy metal ion concentration was 250 mg/L. In addition, the adsorption mechanism was investigated using adsorption dynamics, adsorption isotherm, and Materials Studio simulation. The results show that the maximum adsorption capacities of AA-SW-AMPS for Pb(II), Cu(II), and Zn(II) were 253.49 mg/g, 237.29 mg/g, and 232.15 mg/g, respectively, and the adsorption mechanism is monolayer chemisorption. The adsorbent showed great potential in removing heavy metals from wastewater.

Supramolecular Interfaces and Reconfigurable Liquids Derived from Cucurbit[7]uril Surfactants.

Nanoparticle surfactants (NPSs) offer a powerful means to stabilize the oil-water interface and construct all-liquid devices with advanced functions. However, as the nanoparticle size decreases to molecular-scale, the binding energy of the NPS to the interface reduces significantly, leading to a dynamic adsorption of NPS and "liquid-like" state of the interfacial assemblies. Here, by using the host-guest recognition between a water-soluble small molecule, cucurbit[7]uril (CB[7]) and an oil-soluble polymer ligand, methyl viologen-terminated polystyrene, a supramolecular NPS model, termed CB[7] surfactant, is described. CB[7] surfactants form and assemble rapidly at the oil-water interface, generating an elastic film with excellent mechanical properties. The binding energy of CB[7] surfactant to the interface is sufficiently high to hold it in a jammed state, transforming the interfacial assemblies from a "liquid-like" to "solid-like" state, enabling the structuring of liquids. With CB[7] surfactants as the emulsifier, O/W, W/O and O/W/O emulsions can be prepared in one step. Owing to the guest-competitive responsiveness of CB[7] surfactants, the assembly/disassembly and jamming/unjamming of CB[7] surfactants can be well controlled, leading to the reconfiguration of all-liquid constructs.

Microglia subtypes show substrate- and time-dependent phagocytosis preferences and phenotype plasticity.

Microglia are phagocytosis-competent CNS cells comprising a spectrum of subtypes with beneficial and/or detrimental functions in acute and chronic neurodegenerative disorders. The heterogeneity of microglia suggests differences in phagocytic activity and phenotype plasticity between microglia subtypes. To study these issues, primary murine glial cultures were cultivated in the presence of serum, different growth factors and cytokines to obtain M0-like, M1-like, and M2-like microglia as confirmed by morphology, M1/M2 gene marker expression, and nitric oxide assay. Single-cell analysis after 3 hours of phagocytosis of E.coli particles or IgG-opsonized beads showed equal internalization by M0-like microglia, whereas M1-like microglia preferably internalized E.coli particles and M2-like microglia preferably internalized IgG beads, suggesting subtype-specific preferences for different phagocytosis substrates. Time-lapse live-cells imaging over 16 hours revealed further differences between microglia subtypes in phagocytosis preference and internalization dynamics. M0- and, more efficiently, M1-like microglia continuously internalized E.coli particles for 16 hours, whereas M2-like microglia discontinued internalization after approximately 8 hours. IgG beads were continuously internalized by M0- and M1-like microglia but strikingly less by M2-like microglia. M2-like microglia initially showed continuous internalization similar to M0-like microglia but again discontinuation of internalization after 8 hours suggesting that the time of substrate exposure differently affect microglia subtypes. After prolonged exposure to E.coli particles or IgG beads for 5 days all microglia subtypes showed increased internalization of E.coli particles compared to IgG beads, increased nitric oxide release and up-regulation of M1 gene markers, irrespectively of the phagocytosis substrate, suggesting phenotype plasticity. In summary, microglia subtypes show substrate- and time-dependent phagocytosis preferences and phenotype plasticity. The results suggest that prolonged phagocytosis substrate exposure enhances M1-like profiles and M2-M1 repolarization of microglia. Similar processes may also take place in conditions of acute and chronic brain insults when microglia encounter different types of phagocytic substrates.

Early posttraumatic CSF1R inhibition via PLX3397 leads to time- and sex-dependent effects on inflammation and neuronal maintenance after traumatic brain injury in mice.

BACKGROUND: There is a need for early therapeutic interventions after traumatic brain injury (TBI) to prevent neurodegeneration. Microglia/macrophage (M/M) depletion and repopulation after treatment with colony stimulating factor 1 receptor (CSF1R) inhibitors reduces neurodegeneration. The present study investigates short- and long-term consequences after CSF1R inhibition during the early phase after TBI. METHODS: Sex-matched mice were subjected to TBI and CSF1R inhibition by PLX3397 for 5 days and sacrificed at 5 or 30 days post injury (dpi). Neurological deficits were monitored and brain tissues were examined for histo- and molecular pathological markers. RNAseq was performed with 30 dpi TBI samples. RESULTS: At 5 dpi, CSF1R inhibition attenuated the TBI-induced perilesional M/M increase and associated gene expressions by up to 50%. M/M attenuation did not affect structural brain damage at this time-point, impaired hematoma clearance, and had no effect on IL-1ß expression. At 30 dpi, following drug discontinuation at 5 dpi and M/M repopulation, CSF1R inhibition attenuated brain tissue loss regardless of sex, as well as hippocampal atrophy and thalamic neuronal loss in male mice. Selected gene markers of brain inflammation and apoptosis were reduced in males but increased in females after early CSF1R inhibition as compared to corresponding TBI vehicle groups. Neurological outcome in behaving mice was almost not affected. RNAseq and gene set enrichment analysis (GSEA) of injured brains at 30 dpi revealed more genes associated with dendritic spines and synapse function after early CSF1R inhibition as compared to vehicle, suggesting improved neuronal maintenance and recovery. In TBI vehicle mice, GSEA showed high oxidative phosphorylation, oxidoreductase activity and ribosomal biogenesis suggesting oxidative stress and increased abundance of metabolically highly active cells. More genes associated with immune processes and phagocytosis in PLX3397 treated females vs males, suggesting sex-specific differences in response to early CSF1R inhibition after TBI. CONCLUSIONS: M/M attenuation after CSF1R inhibition via PLX3397 during the early phase of TBI reduces long-term brain tissue loss, improves neuronal maintenance and fosters synapse recovery. Overall effects were not sex-specific but there is evidence that male mice benefit more than female mice.

Rhodium-Catalyzed Chemo-, Regio- and Enantioselective Hydroformylation of Cyclopropyl-Functionalized Trisubstituted Alkenes.

The first rhodium-catalyzed highly chemo-, regio- and enantioselective hydroformylation of cyclopropyl-functionalized trisubstituted alkenes affording useful chiral cyclopropyl entities is reported. Compared to generally used diphosphine ligands for asymmetric catalysis, the modified hybrid phosphorus ligand, named (R,S)-DTBM-Yanphos, can convert a series of readily available cyclopropyl-functionalized trisubstituted alkenes into high-value chiral cyclopropyl-functionalized aldehydes with high selectivities (81-98 % ee). Gram-scale reactions (TON up to 1500) and follow-up transformations to the corresponding alcohol, acid, esters and nitrile are also presented. Finally, a possible hydroformylation mechanism involving ring-open-hydroformylation pathways is proposed based on control and deuteroformylation reactions.

Transition from Nurses to Medicalized Elderly Caregivers: Comparison on Willingness between Traditional and Modern Regions in China.

As China is transitioning to an aging society, the Chinese government has proposed an eldercare pattern, called medicalized elderly care, to help solve the rapid aging and health care problems together. However, the shortage of elderly caregivers is a critical issue, with deficiency both in quantity and quality. This study aims to survey nurses' willingness to transition into medicalized elderly caregivers and compare it between modern and traditional regions. Nurses working in Guangdong (modern region) and Jilin (traditional region) were investigated using a self-administered questionnaire in October 2021. We analyzed the influencing factors through χ²-test, t-test a and binary logistic regression model and further explored the influence of region using propensity score matching (PSM). A total of 1227 nurses were included, with 726 (59.2%) of them showing willingness to transition. Nurses from traditional regions showed a significantly higher willingness to transition after PSM (p = 0.027). Other factors influencing nurses' willingness were age, education, lived with older adults, participated in voluntary activities related to older adults, visited eldercare institutions, attitudes toward older adults, knowledge about older adults, hospice care attitudes and death attitudes. The willingness of nurses to transition was not high enough. To have more willing and skillful human resources for eldercare, we need a more "intimate society for older adults" in the first place.

Research on the wetting mechanism of coal dust by different surfactants: combination of experimental characterization and molecular dynamics simulation.

Surfactants can reduce the surface tension of water and improve the efficiency of spray dust reduction, but the synergistic mechanism of composite surfactant solutions wetting coal dust remains unclear. In this study, sodium dodecyl sulfonate (SDDS)/sodium dodecylbenzene sulfonate (SDBS) solution and SDDS/primary alcohol ethoxylate (AEO-9) solution were prepared to wet three types of coal with different deterioration degrees. The surface tension, contact angle, and functional group composition were measured. The results show that SDDS/AEO-9 solution had lower surface tension and critical micelle concentration than SDDS/SDBS solution at the same mixing ratio. When the ratio of SDDS: SDBS was 2:1, it had the best wetting effect on coal dust. It is found that for SDDS/SDBS solutions, aliphatic hydrocarbons and surface tension have a positive correlation with the contact angle, and hydroxyl groups have a negative correlation with the contact angle. For SDDS/AEO-9 solution, only the surface tension and contact angle show a significant linear relationship. The main factors that affect the wetting change with the combination of surfactants. AEO-9 has an electrostatic shielding effect on SDDS, while SDBS increases the electrostatic repulsion between SDDS solution and electronegative functional groups of coal. The synergism among these surfactants plays an important role in the process of wetting coal.

The effects of filter characteristics of single-filter cartridge on dust removal performance with simulation and experimental analysis.

To obtain the adaptability range of the single-filter cartridge dust collector, a numerical analysis of the key component (filter cartridge) that affects the filter performance of the dust collector is carried out. The study found that the filtration air velocity gradually decreases from the top A to the bottom C of the filter cartridge surface. During the filtration process, along the surface of the filter cartridge from C to A, the pressure first drops and then rises. At C, the negative pressure is the largest, with an average of about 525 Pa. The ineffective filtration area of section A of the upper part of the filter cartridge accounts for 2/5 of the filtration area, and the concentration of the first layer of dust is y = (0.01 ± a) + 0.02 × (0.08 ± b)x exponentially decreasing. The critical particle size range that the filter cartridge can filter dust is M≥1.87 µm, and the best dust removal range of the dust collector is N≥4.625 µm. An agreement between experiment and simulating results proves the validity of simulation model and reliability of the experimental data. Enterprises can choose a reasonable dust removal method based on the research results to optimize the adaptability of the working environment and the dust collector. It also provides a theoretical basis for researchers to solve the problems in the filtration and cleaning process.

Has the Volume-Based Drug Purchasing Approach Achieved Equilibrium among Various Stakeholders? Evidence from China.

Volume-based drug purchasing by China's health insurance system currently represents the largest group purchasing organization worldwide. After exchanging the market that accounted for nearly half of the volume of the healthcare system for the ultra-low-price supply of limited drugs, what are the effects on patient and funding burdens, drug accessibility, and clinical efficacy? We aimed to verify the effectiveness of the policy, explore the reasons behind the problem and identify regulatory priorities and collaborative measures. We used literature and reported data from 2019 to 2021 to conduct a stakeholder analysis and health impact assessment, presenting the benefit and risk share for various dimensions. The analysis method was a multidimensional scaling model, which visualized problematic associations. Seventy-nine papers (61 publications and 18 other resources) were included in the study, with 22 effects and 36 problems identified. The results indicated favorable affordability and poor accessibility of drugs, as well as high risk of reduced drug quality and drug-use rationality. The drug-use demand of patients was guaranteed; the prescription rights of doctors regarding clinical drug use were limited; unreasonable evaluation indicators limited the transformation of public hospitals to value- and service-oriented organizations; the sustainability of health insurance funds and policy promotion were at risk; and innovation by pharmaceutical companies was accelerated. The problems associated with high co-occurrence frequencies were divided into the following clusters: cost control, drug accessibility, system rationality, policy fairness, drug quality, and moral hazards. These findings suggested that China has achieved short-term success in reducing the burden on patients and reducing fund expenditure. However, there were still deficiencies in guaranteed supply, quality control, and efficacy tracking. The study offers critical lessons for China and other low- and middle-income countries.

Multi-Modal Deep Learning for Weeds Detection in Wheat Field Based on RGB-D Images.

Single-modal images carry limited information for features representation, and RGB images fail to detect grass weeds in wheat fields because of their similarity to wheat in shape. We propose a framework based on multi-modal information fusion for accurate detection of weeds in wheat fields in a natural environment, overcoming the limitation of single modality in weeds detection. Firstly, we recode the single-channel depth image into a new three-channel image like the structure of RGB image, which is suitable for feature extraction of convolutional neural network (CNN). Secondly, the multi-scale object detection is realized by fusing the feature maps output by different convolutional layers. The three-channel network structure is designed to take into account the independence of RGB and depth information, respectively, and the complementarity of multi-modal information, and the integrated learning is carried out by weight allocation at the decision level to realize the effective fusion of multi-modal information. The experimental results show that compared with the weed detection method based on RGB image, the accuracy of our method is significantly improved. Experiments with integrated learning shows that mean average precision (mAP) of 36.1% for grass weeds and 42.9% for broad-leaf weeds, and the overall detection precision, as indicated by intersection over ground truth (IoG), is 89.3%, with weights of RGB and depth images at α = 0.4 and ß = 0.3. The results suggest that our methods can accurately detect the dominant species of weeds in wheat fields, and that multi-modal fusion can effectively improve object detection performance.

A concise access to bridged [2,2,1] bicyclic lactones with a quaternary stereocenter via stereospecific hydroformylation.

Chiral bridged [2,2,1] bicyclic lactones are privileged structural units in pharmaceutics and bioactive nature products. However, the synthetic methods for these compounds are rare. Here we report an efficient method for enantioselective construction of bridged [2,2,1] bicyclic lactones bearing a quaternary stereocenter via Rh-catalyzed asymmetric hydroformylation/intramolecular cyclization/pyridium chlorochromate (PCC) oxidation. By employing a hybrid phosphine-phosphite chiral ligand, a series of cyclopent-3-en-1-ols are transformed into corresponding γ-hydroxyl aldehydes with specific syn-selectivity. Then, hemiacetals form in situ and oxidation with PCC in one-pot affords bridged [2,2,1] bicyclic lactones in high yields and excellent enantiomeric excess. Replacing the hydroxyl group by an ester group, cyclopentanecarbaldehydes with a chiral all-carbon quaternary stereocenter in the γ-position can be generated efficiently.

Preparation and characteristics analysis of an ecoenvironmental protection cyclic solidification dust-fixing agent extracted from waste shrimp shells to suppress dust in coal resource-based cities.

There are a lot of coal cinder and dust in the development of coal resource-based cities. Improper handling will cause dust flying, which has a great impact on urban residents and the environment. The purpose of this research is to follow the principle of waste recycling, to use waste shrimp shells to extract chitosan as a raw material, to carry out graft polymerization with acrylic acid and polyvinyl alcohol-1788, and to carry out amidation crosslinking reactions with ethylenediamine tetraacetic acid to produce products. The results showed that the degree of deacetylation of chitosan reached 85% with the optimized extraction method, which greatly shortened the process cycle. Through orthogonal experiments and osmotic wetting experiments, the best preparation process was determined. The reaction process, structure of the product and adhesive structure of the solidified layer were analyzed by FTIR, XPS and SEM. The thermal stability of the product was analyzed by thermogravimetry. Relevant performance tests showed that the product had good adhesion with dust, the hardness of the solidified layer could reach 98 HA, and the dust fixation rate was 92.67% when the wind speed was 15-18 m/s. It has the advantage of circulating dust fixation, which improves the utilization rate of resources.