Polyethylene Materials with Tunable Degradability by Incorporating In-Chain Mechanophores.

Polyolefins are recognized as fundamental plastic materials that are manufactured in the largest quantities among all synthetic polymers. The chemical inertness of the saturated hydrocarbon chains is crucial for storing and using polyolefin plastics, but poses significant environmental challenges related to plastic pollution. Here, we report a versatile approach to creating polyethylene materials with tunable degradability by incorporating in-chain mechanophores. Through palladium-catalyzed coordination/insertion copolymerization of ethylene with cyclobutene-fused comonomers, several cyclobutane-fused mechanophores were successfully incorporated with varied insertion ratios (0.35-26 mol %). The resulting polyethylene materials with in-chain mechanophores exhibit both high thermal stability and remarkable acid resistance. Upon mechanochemical activation by ultrasonication or ball-milling, degradable functional units (imide and ester groups) are introduced into the main polymer chain. The synergy of mechanochemical activation and acid hydrolysis facilitates the efficient degradation of high molecular weight polyethylene materials into telechelic oligomers.

Controllable Synthesis of Chain Center Dye-Labeled Star Polymers for Quantitative Examination of Interchain Conformation by Time-Resolved Fluorescence Resonance Energy Transfer.

Using a "core-first" approach with atom transfer radical polymerization, fluorescent center-functional star polymers of equivalent molecular weight but with varying numbers of arms (di-, tri-, and tetra-arm) were prepared. The sensitivity of fluorescence, combined with a dye-labeling technique introducing a fluorescent donor (carbazole) and an acceptor (anthracene) at the center of poly(methyl methacrylate) (PMMA) chains, enabled the application of time-resolved fluorescence resonance energy transfer to obtain quantitative insights into the conformation of the star polymer chains in the film state. When the results of star-branched polymers were compared with those of linear polymers of identical type and molecular weight, the impact of branching on polymer behavior was isolated for examination. Although the star topology does not alter the average intercoil distance, it affects the distance dispersity. Star polymers with higher arm numbers display decreased dispersity from distance due to reduced intermolecular aggregation at their geometric centers. This study presents the first spectroscopic evidence regarding the distribution of geometric centers in star polymers, offering a physical understanding of chain interpenetration and entanglement within star polymers.

Conservative strip tillage system in maize maintains high yield and mitigates GHG emissions but promotes N2O emissions.

Optimizing N application under straw-covered strip tillage is of great significance to the rational utilization of stover resources as well as ensure food and ecosystem security, and especially N2O emissions from agricultural systems. Quantifying N2O emissions and even the carbon footprint (CF) from agricultural systems is crucial for future protecting agricultural production systems. A two-year field experiment was conducted on black soil in Northeast China, which set up two tillage systems: strip tillage with straw returning (ST) and conventional tillage (control: CT) without straw and three nitrogen rates: 0, farmers' practice (Nfp 240 kg hm-2), and optimized nitrogen fertilizer (Nopt 180 kg hm-2). We examined the characteristics of N2O emissions and CF under the ST and CT systems. Among them, we indirectly calculated GHG emissions using the LCA method. Compared with CT, the ST system significantly reduces indirect GHG emissions, but did significantly increase direct cumulative N2O emissions by 20.7 %, most likely because the higher soil residual nitrate nitrogen content, WFPS, and soil temperature under ST was 13.0 %, 2 % and 5.7 % higher than that under CT. Nopt treatment markedly reduced cumulative N2O emissions by 36.0 %, CFarea, CFyield, and CFNPV by 22.4 %, 23.1 %, and 23.5 % in ST, respectively, compared to Nfp. The reduction in energy use of machinery in ST results in lower fuel consumption and thus generating less CF. What's more, the decrease of CFyield and CFNPV between nitrogen application treatments under ST was 5.2 % and 7.7 % higher than CT, respectively. ST system can effectively achieve higher grain yield and mitigate GHG emissions on black soil in Northeast China compared with CT, but attention should be paid to N2O emissions in the soil during the maize growth period. The sustainability of balancing GHG emissions, and economic and environmental benefits can be achieved by optimizing nitrogen fertilizer manage.

Impacts of maize hybrids with different nitrogen use efficiency on root-associated microbiota based on distinct rhizosphere soil metabolites.

Plant genotypes shape root-associated microbiota that affect plant nutrient acquisition and productivity. It is unclear how maize hybrids modify root-associated microbiota and their functions and relationship with nitrogen use efficiency (NUE) by regulating rhizosphere soil metabolites. Here, two N-efficient (NE) (ZD958, DMY3) and two N-inefficient (NIE) maize hybrids (YD9953, LY99) were used to investigate this issue under low N (60 kg N ha-1 , LN) and high N (180 kg N ha-1 , HN) field conditions. NE hybrids had higher yield than NIE hybrids under LN but not HN. NE and NIE hybrids recruited only distinct root-associated bacterial microbiota in LN. The bacterial network stability was stronger in NE than NIE hybrids. Compared with NIE hybrids, NE hybrids recruited more bacterial taxa that have been described as plant growth-promoting rhizobacteria (PGPR), and less related to denitrification and N competition; this resulted in low N2 O emission and high rhizosphere NO3 - -N accumulation. NE and NIE hybrids had distinct rhizosphere soil metabolite patterns, and their specific metabolites were closely related to microbiota and specific genera under LN. Our findings reveal the relationships among plant NUE, rhizosphere soil metabolites, root-associated microbiota, and soil nutrient cycling, and this information is informative for breeding NE crops.

Boron-Cluster Embedded Necklace-Shaped Nanohoops.

The combination of carbon-based nanohoops with other functional organic molecular structures should lead to the design of new molecular configurations with interesting properties. Here, necklace-like nanohoops embedded with carborane were synthesized for the first time. The unique deboronization of o-carborane has led to the facile preparation of ionic nanohoop compounds. Nanohoops functionalized by nido-o-carborane show excellent fluorescence emission, with a solution quantum yield of up to 90.0 % in THF and a solid-state quantum efficiency of 87.3 %, which opens an avenue for the applications of the nanohoops in OLEDs and bioimaging.

Heterobimetallic block copolymers with a combined main-chain/side-chain topology.

We report for the first time the synthesis of heterobimetallic block copolymers with a combined main-chain/side-chain topology. The photophysical, electrochemical, and thermal properties and ring-opening metathesis polymerization-induced crystallization-driven self-assembly (ROMPI-CDSA) behavior of these polymers can be significantly modulated by switching the metal identity.

The Influence of Thermal Treatments on Anchor Effect in NMT Products.

The anchor effect in nanomolding technology (NMT) refers to the effect that polymer nanorods in nanopores on metal surfaces act as anchors to firmly bond the outside polymer components onto the metal surface. In this work, the influences of thermal treatments on the anchor effect are studied at microscopic level from the perspective of interfacial interaction by a model system (poly(n-butyl methacrylate) (PBMA) and alumina nanopore composite). The differential scanning calorimeter and fluorescence results indicate that the formation of a dense polymer layer in close contact with the pore walls after proper thermal treatments is the key for a strong interfacial interaction. Such polymer layers were formed in NMT products composed of PBMA and aluminum after slow cooling or annealing, with an up to eighteen-fold improvement of the interfacial bonding strength. The polymer chains near the nanopore walls eliminate the thermal stress induced by the mismatch of thermal expansion coefficients through relaxation over time and remain in close proximity with the pore walls during the cooling process of nanomolding. The above dynamic behaviors of the polymer chains ensure the formation of stable interfacial interaction, and then lead to the formation of the anchor effect.

The Mechanochemistry of Carboranes.

We developed o-carborane as a new mechanophore by showing that the o-carborane cluster is the preferred scission site in chain-centered polymers through ultrasonication mechanochemistry. Mechanistic studies are consistent with a predominately homolytic mechanism of chain scission. The mechanically generated monocarbaborane fragments are highly reactive toward alcohol nucleophiles. By contrast, carborane with a different regiochemistry (m-carborane) maintained its high mechanical stability. DFT simulations provide insights into the origins of carborane's mechanical lability. This fundamental research provides a new stimulus for carborane cage activation.

Construction and application of psychological support training program for palliative care specialist nurses / 中国实用护理杂志

Objective:To construct a psychological support training program for palliative care specialist nurses based on positive psychology theory and make a preliminary application.Methods:From August to September, 2020, 142 palliative nursing specialist nurses in Hunan Provincial Palliative Nursing Specialist Training Base were selected as the research objects. Based on positive psychology therapy, using literature review and analysis, semi-structured interviews, expert group meetings and other methods to construct the program, and the work stress, psychological resilience and subjective well-being scores of nurses before and after 8 weeks of psychological support training were compared.Results:The program included three dimensions: cognition, emotion and behavior. After the psychological support training for 8 weeks, the nursing staff′s work stress score 80.76 ± 20.43 was lower than that before the psychological support training 84.70 ± 19.88, the difference was statistically significant( t=6.59, P<0.05), and the psychological resilience score 64.40 ±14.26 was higher than that before the psychological support training 60.19 ±15.85, the difference was statistically significant ( t=-7.39, P<0.05), and the subjective well-being score 75.70 ± 7.70 was higher than that before the psychological support training 74.13 ± 5.98, the difference was statistically significant ( t=-3.52, P<0.05). Conclusions:The psychological support training program based on positive psychology theory can reduce the the work stress, improve psychological resilience and increase subjective well-being of palliative care specialist nurses.

Mechanochemistry of Cationic Cobaltocenium Mechanophore.

Recent research on the mechanochemistry of metallocene mechanophores has shed light on the force-responsiveness of these thermally and chemically stable organometallic compounds. In this work, we report a combination of experimental and computational studies on the mechanochemistry of main-chain cobaltocenium-containing polymers. Ester derivatives of the cationic cobaltocenium, though isoelectronic to neutral ferrocene, are unstable in the nonmechanical control experimental conditions that were accommodated by their ferrocene analogs. Replacing the electron withdrawing C-ester linkages with electron-donating C-alkyls conferred the necessary stability and enabled the mechanochemistry of the cobaltocenium to be assessed. Despite their high bond dissociation energy, cobaltocenium mechanophores are found to be selective sites of main chain scission under sonomechanical activation. Computational CoGEF calculations suggest that the presence of a counterion to cobaltocenium plays a vital role by promoting a peeling mechanism of dissociation in conjunction with the initial slipping.

Color-tunable and Highly Emissive Solid Materials Constructed from Tetraphenylethylene-o-carborane-based Building Blocks: Synthesis, Aggregation-induced emission, and Photophysics.

A novel kind of expanded tetraphenylethylene (TPE)-carborane-TPE pentad has been synthesized by using two adjacent carborane moieties as central bridges and three TPE units in lateral positions. Its solid-state fluorescence quantum yield was substantially increased to 68.2% by expanding the number of bridges between carborane and TPE. Subsequently, the emission color shifted from blue to orange-yellow (126 nm). Mechanical insights into the electronic structure of the extended TPE-carborane-TPE pentads were obtained from density functional theory (DFT) calculations.

Effectsof growth-promoting rhizobacteria on maize growth and rhizosphere microbial community under conservation tillage in Northeast China.

Conservation tillage in conjunction with straw mulching is a sustainable agricultural approach. However, straw mulching reduces the soil temperature, inhibits early maize growth and reduces grain yield in cold regions. To address this problem, we investigated the effects of inoculation of plant growth-promoting rhizobacteria (PGPR) on maize growth and rhizosphere microbial communities under conservation tillage in Northeast China. The PGPR strains Sinorhizobium sp. A15, Bacillus sp. A28, Sphingomonas sp. A55 and Enterobacter sp. P24 were isolated from the maize rhizosphere in the same area and inoculated separately. Inoculation of these strains significantly enhanced maize growth, and the strains A15, A28 and A55 significantly increased grain yield by as much as 22%-29%. Real-time quantitative PCR and high-throughput sequencing showed that separate inoculation with the four strains increased the abundance and species richness of bacteria in the maize rhizosphere. Notably, the relative abundance of Acidobacteria_Subgroup_6, Chloroflexi_KD4-96, and Verrucomicrobiae at the class level and Mucilaginibacter at the genus level were positively correlated with maize biomass and yield. Inoculation with PGPR shows potential for improvement of maize production under conservation tillage in cold regions by regulating the rhizosphere bacterial community structure and by direct stimulation of plant growth.

Analysis of hot spots in emergency medicine research from 2015 to 2019--visualization analysis based on CiteSpace / 中华急诊医学杂志

Objective:To analyze the knowledge graph of the papers published in the core journals of emergency medicine from 2015 to 2019, to present the overall situation of the research in the field of emergency medicine, to highlight the important contents in the research progress, and to unearth the research hotspots reported in the journals of emergency medicine.Methods:The relevant literatures of 7 core journals of emergency medicine were retrieved and exported from CNKI and Wanfang databases published in 2015-2019. A total of 7753 valid literatures were included. The visualization software CiteSpace was used to analyze the information of authors, institutions and keywords in the exported literatures to generate visual graphs.Results:By analyzing the knowledge graph from 2015 to 2019, it is found that Yu Xuezhong, Zhu Huadong, Zhang Jinsong, Zhang Mao, Liu Xinwei, Liu Yin, Xu Jun, and Nie Sinnan were the backbone of the author group in the field of emergency medicine. Emergency Department of Peking Union Medical College Hospital, Beijing Chaoyang Hospital Affiliated to Capital Medical University, Emergency Department of PLA General Hospital, Emergency Medicine Department of Eastern Theater General Hospital, Emergency Department of Xijing Hospital, and Emergency Medicine Department of Shenyang Military Region General Hospital were the institutions with the most publications. In recent 5 years, the core journals of emergency medicine focused on the topics on mortality, acute lung injury, cardiac arrest, prognosis, mechanical ventilation, acute myocardial infarction and hemoperfusion.Conclusions:The visual graphs generated by CiteSpace helps to intuitively understand the critical path, development trend and frontier hot spots of the evolution of the research field of emergency medicine, and provides more basis for future related research.

Distal conformational locks on ferrocene mechanophores guide reaction pathways for increased mechanochemical reactivity.

Mechanophores can be used to produce strain-dependent covalent chemical responses in polymeric materials, including stress strengthening, stress sensing and network remodelling. In general, it is desirable for mechanophores to be inert in the absence of force but highly reactive under applied tension. Metallocenes possess potentially useful combinations of force-free stability and force-coupled reactivity, but the mechanistic basis of this reactivity remains largely unexplored. Here, we have used single-molecule force spectroscopy to show that the mechanical reactivities of a series of ferrocenophanes are not correlated with ring strain in the reactants, but with the extent of rotational alignment of their two cyclopentadienyl ligands. Distal attachments can be used to restrict the mechanism of ferrocene dissociation to proceed through ligand 'peeling', as opposed to the more conventional 'shearing' mechanism of the parent ferrocene, leading the dissociation rate constant to increase by several orders of magnitude at forces of ~1 nN. It also leads to improved macroscopic, multi-responsive behaviour, including mechanochromism and force-induced cross-linking in ferrocenophane-containing polymers.

Synthesis of Site-specific Charged Metallopolymers via Reversible Addition-Fragmentation Chain Transfer (RAFT) Polymerization.

Site-specific cobaltocenium-labeled polymers are synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization using cobaltocenium-labeled chain transfer agents. These chain transfer agents show counterion-dependent solubility. Based on the chemical structure of the chain transfer agents, single cobaltocenium moieties are dictated to be in predetermined locations at either the center or terminals of the polymer chains. Polymerization of hydrophobic monomers (methyl methacrylate, methyl acrylate and styrene) and hydrophilic monomers (2-(dimethylamino)ethyl methacrylate and methacrylic acid) is demonstrated to follow a controlled manner based on kinetic studies. Cobaltocenium-labeled polymers with molecular weights greater than 100,000 Da can be prepared by using a difunctional chain transfer agent. Photophysical properties, electrochemical properties, thermal properties and morphology of the cobaltocenium-labeled polymers are also investigated.

The long-term therapeutic effects of His-Purkinje system pacing on bradycardia and cardiac conduction dysfunction compared with right ventricular pacing: A systematic review and meta-analysis.

AIMS: His-Purkinje system pacing has been demonstrated as a synchronized ventricular pacing strategy via pacing His-Purkinje system directly, which can decrease the incidence of adverse cardiac structure alteration compared with right ventricular pacing (RVP). The purpose of this meta-analysis was to compare the effects of His-Purkinje system pacing and RVP in patients with bradycardia and cardiac conduction dysfunction. METHODS: PubMed, Embase, Cochrane Library, and Web of Science were systematically searched from the establishment of databases up to 15 December 2019. Studies on long-term clinical outcomes of His-Purkinje system pacing and RVP were included. Chronic paced QRS duration, chronic pacing threshold, left ventricular ejection fraction (LVEF), left ventricular end-diastolic volume (LVEDV), left ventricular end-systolic volume (LVESV), all-cause mortality, and heart failure hospitalization were collected for meta-analysis. RESULTS: A total of 13 studies comprising 2348 patients were included in this meta-analysis. Compared with RVP group, patients receiving His-Purkinje system pacing showed improvement of LVEF (mean difference [MD], 5.65; 95% confidence interval [CI], 4.38-6.92), shorter chronic paced QRS duration (MD, - 39.29; 95% CI, - 41.90 to - 36.68), higher pacing threshold (MD, 0.8; 95% CI, 0.71-0.89) and lower risk of heart failure hospitalization (odds ratio [OR], 0.65; 95% CI, 0.44-0.96) during the follow-up. However, no statistical difference existed in LVEDV, LVESV and all-cause mortality between the two groups. CONCLUSION: Our meta-analysis suggests that His-bundle pacing is more suitable for the treatment of patients with bradycardia and cardiac conduction dysfunction.

Rational Synthesis of Metallo-Cations Toward Redox- and Alkaline-Stable Metallo-Polyelectrolytes.

Cations are crucial components in emerging functional polyelectrolytes for a myriad of applications. Rapid development in this area necessitates the exploration of new cations with advanced properties. Herein we describe a combination of computational and experimental design of cobaltocene metallo-cations that have distinct electronic and redox properties. One of the direct outcomes on the first synthesis of a complete set of cation derivatives is to discover highly stable cations, which are further integrated to construct metallo-polyelectrolytes as anion-exchange membranes in solid-state alkaline fuel cells. The device performance of these polyelectrolytes under highly basic and oxidative environments is competitive with many organo-polyelectrolytes.

Generalizing metallocene mechanochemistry to ruthenocene mechanophores.

Recent reports have shown that ferrocene displays an unexpected combination of force-free stability and mechanochemical activity, as it acts as the preferred site of chain scission along the backbone of highly extended polymer chains. This observation raises the tantalizing question as to whether similar mechanochemical activity might be present in other metallocenes, and, if so, what features of metallocenes dictate their relative ability to act as mechanophores. In this work, we elucidate polymerization methodologies towards main-chain ruthenocene-based polymers and explore the mechanochemistry of ruthenocene. We find that ruthenocene, in analogy to ferrocene, acts as a highly selective site of main chain scission despite the fact that it is even more inert. A comparison of ruthenocene and ferrocene reactivity provides insights as to the possible origins of metallocene mechanochemistry, including the relative importance of structural and thermodynamic parameters such as bond length and bond dissociation energy. These results suggest that metallocenes might be privileged mechanophores through which highly inert coordination complexes can be made dynamic in a stimuli-responsive fashion, offering potential opportunities in dynamic metallo-supramolecular materials and in mechanochemical routes to reactive intermediates that are otherwise difficult to obtain.

ROMPI-CDSA: ring-opening metathesis polymerization-induced crystallization-driven self-assembly of metallo-block copolymers.

Polymerization-induced self-assembly (PISA) and crystallization-driven self-assembly (CDSA) are among the most prevailing methods for block copolymer self-assembly. Taking the merits of scalability of PISA and dimension control of CDSA, we report one-pot synchronous PISA and CDSA via ring-opening metathesis polymerization (ROMP) to prepare nano-objects based on a crystalline poly(ruthenocene) motif. We denote this self-assembly methodology as ROMPI-CDSA to enable a simple, yet robust approach for the preparation of functional nanomaterials.

Crystallization-Driven Self-Assembly of Metallo-Polyelectrolyte Block Copolymers with a Polycaprolactone Core-Forming Segment.

We report crystallization-driven self-assembly (CDSA) of metallo-polyelectrolyte block copolymers that contain cationic polycobaltocenium in the corona-forming block and crystallizable polycaprolactone (PCL) as the core-forming block. Dictated by electrostatic interactions originating from the cationic metalloblock and crystallization of the PCL, these amphiphilic block copolymers self-assembled into two-dimensional platelet nanostructures in polar protic solvents. The 2D morphologies can be varied from elongated hexagons to diamonds, and their stability to fragmentation was found to be dependent on the ionic strength of the solution.