Supported Platinum Nanoparticles Catalyzed Carbon-Carbon Bond Cleavage of Polyolefins: Role of the Oxide Support Acidity.

Supported platinum nanoparticle catalysts are known to convert polyolefins to high-quality liquid hydrocarbons using hydrogen under relatively mild conditions. To date, few studies using platinum grafted onto various metal oxide (MxOy) supports have been undertaken to understand the role of the acidity of the oxide support in the carbon-carbon bond cleavage of polyethylene under consistent catalytic conditions. Specifically, two Pt/MxOy catalysts (MxOy = SrTiO3 and SiO2-Al2O3; Al = 3.0 wt %, target Pt loading 2 wt % Pt ∼1.5 nm), under identical catalytic polyethylene hydrogenolysis conditions (T = 300 °C, P(H2) = 170 psi, t = 24 h; Mw = ∼3,800 g/mol, Mn = ∼1,100 g/mol, D = 3.45, Nbranch/100C = 1.0), yielded a narrow distribution of hydrocarbons with molecular weights in the range of lubricants (Mw = < 600 g/mol; Mn < 400 g/mol; D = 1.5). While Pt/SrTiO3 formed saturated hydrocarbons with negligible branching, Pt/SiO2-Al2O3 formed partially unsaturated hydrocarbons (<1 mol % alkenes and ∼4 mol % alkyl aromatics) with increased branch density (Nbranch/100C = 5.5). Further investigations suggest evidence for a competitive hydrocracking mechanism occurring alongside hydrogenolysis, stemming from the increased acidity of Pt/SiO2-Al2O3 compared to Pt/SrTiO3. Additionally, the products of these polymer deconstruction reactions were found to be independent of the polyethylene feedstock, allowing the potential to upcycle polyethylenes with various properties into a value-added product.

Quantitative analyses of products and rates in polyethylene depolymerization and upcycling.

Depolymerization and upcycling are promising approaches to managing plastic waste. However, quantitative measurements of reaction rates and analyses of complex product mixtures arising from depolymerization of polyolefins constitute significant challenges in this emerging field. Here, we detail techniques for recovery and analysis of products arising from batch depolymerization of polyethylene. We also describe quantitative analyses of reaction rates and products selectivity. This protocol can be extended to depolymerization of other plastics and characterization of other product mixtures including long-chain olefins. For complete details on the use and execution of this protocol, please refer to Sun et al.1.

Comparative genomics revealed that Vibrio furnissii and Vibrio fluvialis have mutations in genes related to T6SS1 and T6SS2.

The type VI secretion system (T6SS) is important for interbacterial competition and virulence in Vibrio species. It is generally agreed that T6SS provides a fitness advantage to Vibrios. Some Vibrio species possess one, while others possess two T6SSs. Even within the same Vibrio species, different strains can harbor a variable number of T6SSs. Such is the case in V. fluvialis, an opportunistic human pathogen, that some V. fluvialis strains do not harbor T6SS1. This study found that Amphritea, Marinomonas, Marinobacterium, Vibrio, Photobacterium, and Oceanospirillum species have genes encoding V. fluvialis T6SS1 homologs. The cladogram of T6SS1 genes suggested that these genes appeared to be horizontally acquired by V. fluvialis, V. furnissii, and some other Vibrio species, when compared with the species tree. Codon insertions, codon deletions, nonsense mutations, and the insertion sequence are found in many genes, such as clpV1, tssL1, and tssF1, which encode structure components of T6SS1 in V. furnissii and V. fluvialis. Codon deletion events are more common than codon insertion, insertion sequence disruption, and nonsense mutation events in genes that encode components of T6SS1. Similarly, codon insertions and codon deletions are found in genes relevant to T6SS2, including tssM2, vgrG2 and vasH, in V. furnissii and V. fluvialis. These mutations are likely to disable the functions of T6SSs. Our findings indicate that T6SS may have a fitness disadvantage in V. furnissii and V. fluvialis, and the loss of function in T6SS may help these Vibrio species to survive under certain conditions.

Portable metal-organic framework alginate beads for high-sensitivity fluorescence detection and effective removal of residual pesticides in fruits and vegetables.

Pesticides have been emerged as major organic pollutants in environment, owing to widely spread and intrinsic high toxicity in agricultural productivity. Herein, we designed and synthesized a practicability and portable metal-organic framework (MOF) based composite beads MOF-alginate-Ca2+-polyacrylic acid (kgd-M1@ACPs) consist of biocompatible host material (sodium alginate) and fluorescent center with blue emission (where kgd-M1 stands for {[Cd(tbia)·H2O]·2H2O}n), which was further developed for high-efficiency and naked-eye 2,6-dichloro-4-nitroaniline (DCN) monitoring in fruits and vegetables. Significantly, the kgd-M1@ACPs shows obvious fluorescent quench towards toxic pesticide DCN with a low limit of detection (LOD) of 0.09 µM and high recovery from 98.08 to 104.37%. Moreover, the kgd-M1@ACPs also presents an excellent DCN adsorption ability. This work demonstrates that smart material kgd-M1@ACPs is expected to be a good candidate for detection and removal of DCN in real fruits and vegetables, which will present a broad prospect for monitoring and treating pesticides.

Structural Design of Low Toxicity Metal-Organic Frameworks for Multifunction Detection of Organic and Inorganic Contaminants from Water.

Metal-organic frameworks (MOFs)-based sensors for monitoring toxic substances in wastewater have attracted great attention due to the efficient and reliable performance. Here, we has synthesized two novel zinc-based MOFs [Zn(ttb)2(H2O)2]n (Zn1-ttb) and {[Zn(ttb)2]·0.5CH3CN}n (Zn2-ttb) through changing the polarity of reaction solvents and finally obtained target 2D MOF material [Zn(ttb)(bdc)0.5]n(Zn3-ttb-bdc) by successfully introducing an ancillary ligand H2bdc (Httb = 1-(triazo-1-ly)-4-(tetrazol-5-ylmethyl)benzene, H2bdc = 1,4-benzenedicarboxylic acid). As-prepared Zn3-ttb-bdc exhibits high water and chemical stability as well as excellent fluorescence property. Due to the -COOH binding sites from H2bdc, Zn3-ttb-bdc shows high sensitivity and a rapid luminescent response to a representative organic micropollutant trinitrophenol (TNP) and inorganic pollutants (Fe3+ and Cr2O72-) in wastewater. The mechanisms of multifunctional detection abilities of Zn3-ttb-bdc toward different types of pollutants are further studied. This work presents the structural design in preparing MOF materials for multifunctional detection performance, thus opening new perspectives for emerging MOF-based sensors as environmental monitors.

Photobiomodulation Promotes Neuronal Axon Regeneration After Oxidative Stress and Induces a Change in Polarization from M1 to M2 in Macrophages via Stimulation of CCL2 in Neurons: Relevance to Spinal Cord Injury.

To study the effect of photobiomodulation (PBM) on axon regeneration and secretion change of dorsal root ganglion (DRG) under oxidative stress after spinal cord injury (SCI), and further explore the effect of changes in DRG secretion caused by PBM on the polarization of macrophages. The PBM-DRG model was constructed to perform PBM on neurons under oxidative stress simulated in vitro. And the irradiation conditions were as follows: wavelength, 810 nm; power density, 2 mW/cm2; irradiation area, 4.5 cm2; and irradiation time, 440 s. Then resulted in an energy of 4 J (2 mW/cm2 × 4.5 cm2 × 440 s). About 100 µM H202 was added to the culture medium to simulate oxidative stress after SCI. An ROS (reactive oxygen species) assay kit was used to measure ROS contend in the DRG. The survival level of the neurons was measured using the CCK-8 method, and the axon regeneration of neurons was observed by using immunofluorescence. The secretion level of CCL2 from DRG was determined by RT-qPCR and ELISA. Further culturing macrophages of DRG-conditioned medium culture, the expression level of iNOS and Arg-1 in macrophages was assessed using Western blot analysis. The expression level of TNF-α and IL-1ß was determined by ELISA. After adding the neutralizing antibody of CCL2 to the DRG neuron-conditioned medium following PBM irradiation to culture macrophages to observe the effects on macrophage polarization and secretion. PBM could reduce ROS levels in neurons, increase neuronal survival under oxidative stress, and promote neuronal axon regeneration. In addition, PBM could also promote CCL2 secretion by DRG under oxidative stress. By constructing a DRG supernatant-M1 macrophage adoptive culture model, we found that the supernatant of DRG after PBM intervention could reduce the expression level of iNOS and the secretion of TNF-α and IL-1ß in M1 macrophages; at the same time, it could also up-regulate the expression of Arg-1, one of the markers of M2 macrophages. Furthermore, these effects could be prevented by the addition of neutralizing antibodies of CCL2. PBM could promote survival and axonal regeneration of DRG under SCI oxidative stress, increase the secretion level of CCL2 by DRG, and this change can reduce the polarization of macrophages to M1, further indicating that PBM could promote spinal cord injury repair.

Polyethylene upcycling to long-chain alkylaromatics by tandem hydrogenolysis/aromatization.

The current scale of plastics production and the accompanying waste disposal problems represent a largely untapped opportunity for chemical upcycling. Tandem catalytic conversion by platinum supported on γ-alumina converts various polyethylene grades in high yields (up to 80 weight percent) to low-molecular-weight liquid/wax products, in the absence of added solvent or molecular hydrogen, with little production of light gases. The major components are valuable long-chain alkylaromatics and alkylnaphthenes (average ~C30, dispersity Ð = 1.1). Coupling exothermic hydrogenolysis with endothermic aromatization renders the overall transformation thermodynamically accessible despite the moderate reaction temperature of 280°C. This approach demonstrates how waste polyolefins can be a viable feedstock for the generation of molecular hydrocarbon products.

Attenuation of the inflammatory response and polarization of macrophages by photobiomodulation.

In spinal cord injury (SCI), inflammation is a major mediator of damage and loss of function and is regulated primarily by the bone marrow-derived macrophages (BMDMs). Photobiomodulation (PBM) or low-level light stimulation is known to have anti-inflammatory effects and has previously been used in the treatment of SCI, although its precise cellular mechanisms remain unclear. In the present study, the effect of PBM at 810 nm on classically activated BMDMs was evaluated to investigate the mechanisms underlying its anti-inflammatory effects. BMDMs were cultured and irradiated (810 nm, 2 mW/cm2) following stimulation with lipopolysaccharide and interferon-γ. CCK-8 assay, 2',7'-dichlorofluorescein diacetate assay, and ELISA and western blot analysis were performed to measure cell viability, reactive oxygen species production, and inflammatory marker production, respectively. PBM irradiation of classically activated macrophages significantly increased the cell viability and inhibited reactive oxygen species generation. PBM suppressed the expression of a marker of classically activated macrophages, inducible nitric oxide synthase; decreased the mRNA expression and secretion of pro-inflammatory cytokines, tumor necrosis factor alpha, and interleukin-1 beta; and increased the secretion of monocyte chemotactic protein 1. Exposure to PBM likewise significantly reduced the expression and phosphorylation of NF-κB p65 in classically activated BMDMs. Taken together, these results suggest that PBM can successfully modulate inflammation and polarization in classically activated BMDMs. The present study provides a theoretical basis to support wider clinical application of PBM in the treatment of SCI.

Photobiomodulation Therapy Inhibit the Activation and Secretory of Astrocytes by Altering Macrophage Polarization.

Spinal cord injury (SCI) stimulates reactive astrogliosis and the infiltration of macrophages, which interact with each other at the injured area. We previously found Photobiomodulation (PBM) significantly decreases the number of M1 macrophages at the injured area of SCI. But the exact nature of the astrocyte response following PBM and relationship with the macrophage have not been explored in detail. In this study, a BALB/c mice model with standardized bilateral spinal cord compression and a macrophage-astrocyte co-culture model were applied to study effects of PBM on astrocytes. Results showed that PBM inhibit the expression of the astrocyte markers glial fibrillary acidic protein (GFAP) and the secretion of chondroitin sulfate proteoglycans (CSPG) in the para-epicenter area, decrease the number of M1 macrophage in vivo. The in vitro experiments indicated M1 macrophages promote the cell viability of astrocytes and the expression of CSPG. However, PBM significantly inhibited the expression of GFAP, decreased activation of astrocyte, and downregulated the expression of CSPG by regulating M1 macrophages. These results demonstrate that PBM may regulate the interaction between macrophages and astrocytes after spinal cord injury, which inhibited the formation of glial scar.

Low-level laser therapy 810-nm up-regulates macrophage secretion of neurotrophic factors via PKA-CREB and promotes neuronal axon regeneration in vitro.

Macrophages play key roles in the secondary injury stage of spinal cord injury (SCI). M1 macrophages occupy the lesion area and secrete high levels of inflammatory factors that hinder lesion repair, and M2 macrophages can secrete neurotrophic factors and promote axonal regeneration. The regulation of macrophage secretion after SCI is critical for injury repair. Low-level laser therapy (810-nm) (LLLT) can boost functional rehabilitation in rats after SCI; however, the mechanisms remain unclear. To explore this issue, we established an in vitro model of low-level laser irradiation of M1 macrophages, and the effects of LLLT on M1 macrophage polarization and neurotrophic factor secretion and the related mechanisms were investigated. The results showed that LLLT irradiation decreased the expression of M1 macrophage-specific markers, and increased the expression of M2 macrophage-specific markers. Through forward and reverse experiments, we verified that LLLT can promote the secretion of various neurotrophic factors by activating the PKA-CREB pathway in macrophages and finally promote the regeneration of axons. Accordingly, LLLT may be an effective therapeutic approach for SCI with clinical application prospects.

Photobiomodulation by diffusing optical fiber on spinal cord: A feasibility study in piglet model.

Previous studies on spinal cord injury (SCI) have confirmed that percutaneous photobiomodulation (PBM) therapy can ameliorate immunoinflammatory responses at sites of injury, accelerate nerve regeneration, suppress glial scar formation and promote the subsequent recovery of locomotor function. The current study was performed to evaluate a large-animal model employing implanted optical fibers to accurately irradiate targeted spinal segments. The method's feasibility and irradiation parameters that do not cause phototoxic reaction were determined, and the methodology of irradiating the spinal cord with near-infrared light was investigated in detail. A diffusing optical fiber was implanted above the T9 spinal cord of Bama miniature pigs and used to transfer near-infrared light (810 nm) onto the spinal cord surface. After daily irradiation with 200, 300, 500 or 1000 mW for 14 days, both sides of the irradiated area of the spinal cord were assessed for temperature changes. The condition of the spinal cord and the position of optical fiber were investigated by magnetic resonance imaging (MRI), and different parameters indicating temperature increases or phototoxicity were measured on the normal spinal cord surface due to light irradiation (ie, heat shock responses, inflammatory reactions and neuronal apoptosis), and the animals' lower-limb neurological function and gait were assessed during the irradiation process. The implanted device was stable inside the freely moving animals, and light energy could be directly projected onto the spinal cord surface. The screening of different irradiation parameters preliminary showed that direct irradiation onto the spinal cord surface at 200 and 300 mW did not significantly increase the temperature, stress responses, inflammatory reactions and neural apoptosis, whereas irradiation at 500 mW slightly increased these parameters, and irradiation at 1000 mW induced a significant temperature increase, heat shock, inflammation and apoptosis responses. HE staining of spinal cord tissue sections did not reveal any significant structural changes of the tissues compared to the control group, and the neurological function and gait of all irradiated animals were normal. In this study, we established an in-vivo optical fiber implantation method, which might be safe and stable and could be used to directly project light energy onto the spinal cord surface. This study might provide a new perspective for clinical applications of PBM in acute SCI.

[The 810 nm low-level laser inhibits the polarization of M1 bone marrow-derived macrophages to promote neuronal axon growth of dorsal root ganglion].

Objective To investigate the effect of low-level laser on the polarization and secretory phenotype of primary cultured M1 bone marrow-derived macrophages (BMDMs) in neuronal axons of dorsal root ganglion (DRG). Methods BMDMs were isolated and cultured, and lipopolysaccharide (LPS) combined with IFN-γ were used to induce M1 phenotype polarization of BMDMs, and then F4/80 and CD16/32 expression was detected by flow cytometry. The mature M1 type BMDMs were randomly divided into low-level laser group and control group. The laser exposure group was subjected to the laser treatments of 0.4J, 4J and 10J, and no laser was used in the control group. After 24 hours of laser exposure, the mRNA level of inducible nitric oxide synthase (iNOS) of M1 type BMDMs was detected by reverse transcription PCR, and the protein level of iNOS was detected by Western blot analysis. The levels of tumor necrosis factor alpha (TNF-α), interleukin-1ß (IL-1ß), brain-derived neurotrophic factor (BDNF) and nerve growth factor (NGF) in the supernatant of cultured cells were tested by ELISA. DRG neurons were cultured with the supernatant fluid of M1 type BMDMs, and immunofluorescence cytochemistry was employed to detect neuronal nuclei (NeuN) and ß-tubulin III expression of DRG neurons for determining the influence on the growth of DRG neuronal axons. Results Compared with the control group, the mRNA level of iNOS in M1 type BMDMs dramatically increased after 24 hours of low-level laser exposure. Among the 3 groups with different energy levels, the decrease of iNOS mRNA level was the most obvious in the group with 4J laser exposure. The protein levels of iNOS in the groups with 0.4J- and 4J- laser exposure were reduced more significantly than that in the control group, and the down-regulation was more prominent in the group with 4J laser exposure than that with 0.4J laser exposure. In addition, the secretion of TNF-α from M1 type BMDMs was reduced more significantly in the groups of 4J- and 10J- laser exposure than that in the control group. With regard to IL-1ß, its secretion was inhibited in all the laser exposure groups compared with the control group, and the suppression was more prominent in the groups of 0.4J- and 4J-laser exposure than that in the group of 10J-laser exposure. Furthermore, 4J-laser exposure significantly potentiated the secretion of BDNF and NGF in M1 type BMDMs compared with the control group. Moreover, co-culture with the supernatants from 4J- and 10J-laser exposure groups could significantly promote the growth of axons of DRG neurons. Conclusion Low-level laser exposure can inhibit the polarization of M1 type BMDM and the secretion of pro-inflammatory factor including TNF-α and IL-1ß. Besides, low-level laser exposure could contribute to the secretion of neurotrophic factors including BDNF and NGF, and promote the growth of DRG axon, and this effect is dose-dependent.

A Molecular Cobalt Hydrogen Evolution Catalyst Showing High Activity and Outstanding Tolerance to CO and O2.

There is a demand to develop molecular catalysts promoting the hydrogen evolution reaction (HER) with a high catalytic rate and a high tolerance to various inhibitors, such as CO and O2 . Herein we report a cobalt catalyst with a penta-dentate macrocyclic ligand (1-Co), which exhibits a fast catalytic rate (TOF=2210 s-1 ) in aqueous pH 7.0 phosphate buffer solution, in which proton transfer from a dihydrogen phosphate anion (H2 PO4 - ) plays a key role in catalytic enhancement. The electrocatalyst exhibits a high tolerance to inhibitors, displaying over 90 % retention of its activity under either CO or air atmosphere. Its high tolerance to CO is concluded to arise from the kinetically labile character of undesirable CO-bound species due to the geometrical frustration posed by the ligand, which prevents an ideal trigonal bipyramid being established.

Rifampin resistance and its fitness cost in Riemerella anatipestifer.

BACKGROUND: Riemerella anatipestifer (R. anatipestifer) is one of the most important poultry pathogens worldwide, with associated infections causing significant economic losses. Rifampin Resistance is an important mechanism of drug resistance. However, there is no information about rpoB mutations conferring rifampin resistance and its fitness cost in Riemerella anatipestifer. RESULTS: Comparative analysis of 18 R.anatipestifer rpoB sequences and the determination of rifampin minimum inhibitory concentrations showed that five point mutations, V382I, H491N, G502K, R494K and S539Y, were related to rifampin resistance. Five overexpression strains were constructed using site-directed mutagenesis to validate these sites. To investigate the origin and fitness costs of the rpoB mutations, 15 types of rpoB mutations were isolated from R. anatipestifer ATCC 11845 by using spontaneous mutation in which R494K was identical to the type of mutation detected in the isolates. The mutation frequency of the rpoB gene was calculated to be 10- 8. A total of 98.8% (247/250) of the obtained mutants were located in cluster I of the rifampin resistance-determining region of the rpoB gene. With the exception of D481Y, I537N and S539F, the rifampin minimum inhibitory concentrations of the remaining mutants were at least 64 µg/mL. The growth performance and competitive experiments of the mutant strains in vitro showed that H491D and 485::TAA exhibit growth delay and severely impaired fitness. Finally, the colonization abilities and sensitivities of the R494K and H491D mutants were investigated. The sensitivity of the two mutants to hydrogen peroxide (H2O2) and sodium nitroprusside (SNP) increased compared to the parental strain. The number of live colonies colonized by the two mutants in the duckling brain and trachea were lower than that of the parental strain within 24 h. CONCLUSIONS: Mutations of rpoB gene in R. anatipestifer mediate rifampin resistance and result in fitness costs. And different single mutations confer different levels of fitness costs. Our study provides, to our knowledge, the first estimates of the fitness cost associated with the R. anatipestifer rifampin resistance in vitro and in vivo.

Electrocatalytic and Photocatalytic Reduction of CO2 to CO by Cobalt(II) Tripodal Complexes: Low Overpotentials, High Efficiency and Selectivity.

The reduction of carbon dioxide (CO2 ) has been considered as an approach to mitigate global warming and to provide renewable carbon-based fuels. Rational design of efficient, selective, and inexpensive catalysts with low overpotentials is urgently desired. In this study, four cobalt(II) tripodal complexes are tested as catalysts for CO2 reduction to CO in a MeCN/H2 O (4:1 v/v) solution. The replacement of pyridyl groups in the ligands with less basic quinolinyl groups greatly reduces the required overpotential for CO2 -to-CO conversion down to 200-380 mV. Benefitting from the low overpotentials, a photocatalyst system for CO2 -to-CO conversion is successfully constructed, with an maximum turnover number (TON) of 10 650±750, a turnover frequency (TOF) of 1150±80 h-1 , and almost 100 % selectivity to CO. These outstanding catalytic performances are further elucidated by DFT calculations.