Charge‐Induced Unzipping of Isolated Proteins to a Defined Secondary Structure

Here we present a combined experimental and theoretical study on the secondary structure of isolated proteins as a function of charge state. In infrared spectra of the proteins ubiquitin and cytochrome c, amide I (C=O stretch) and amide II (N–H bend) bands can be found at positions that are typical for condensed‐phase proteins. For high charge states a new band appears, substantially red‐shifted from the amide II band observed at lower charge states. The observations are interpreted in terms of Coulomb‐driven transitions in secondary structures from mostly helical to extended C₅‐type hydrogen‐bonded structures. Support for this interpretation comes from simple energy considerations as well as from quantum chemical calculations on model peptides. This transition in secondary structure is most likely universal for isolated proteins that occur in mass spectrometric experiments.     

3D-structured carbon-coated MnO/graphene nanocomposites with exceptional electrochemical performance for Li-ion battery anodes

MnO has a high theoretical capacity, moderate discharge plateau, and low polarization when it is used as the anode material in lithium battery. However, the issues that limit its application are its poor conductivity and large volume changes, which can easily result in the collapse of electrode structure during long-term cycling. In the present work, a carbon-coated MnO/graphene 3D-network anode material is synthesized by an electrostatic adsorption of dispersed precipitates precipitation method. The MnO nanoparticles coated by carbon are uniformly distributed on the surface of graphene nanosheets and form a 3D sandwich-like nanostructure. A carbon layer is coated on the surface of MnO nanoparticles, which slows down the volume expansion in the process of lithium intercalation. The graphene nanosheets are cross-linked through carbons in this 3D nanostructure, which provides mechanical support and effective electron conduction pathways during the charge-discharge. The electrochemical tests indicate that the prepared 3D carbon-coated MnO/graphene electrode exhibits an excellent rate capacity of 1247.3 and 713.2 mAh g^?1 at 100 and 1000 mA g^?1, respectively. The capacity is 792.2 mAh g^?1 after long cycle at a current density of 1000 mA g^?1. The specific capacity is higher than that of MnO-based composite lithium anode materials currently reported. The superior rate and cycling performances are attributed to the unique 3D-network structure, which provides an effectively conductive network, buffers volume expansion, and prevents falling and aggregation of MnO in the charge and discharge process of the electrode materials. The 3D-structured carbon-coated MnO/graphene anode material will have an excellent application prospect.

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Graphical abstract Cyclic performance at 1 A g^?1 and SEM images (inset) of the 3D-structured carbon-coated MnO/graphene nanocomposite.

     

PAH metabolism in the earthworm Eisenia fetida – identification of phase II metabolites of phenanthrene and pyrene

Polycyclic aromatic hydrocarbons (PAHs) are soil contaminants. Because of their high lipophilicity, PAHs are associated with the organic matter in the soil. Transformation of PAHs generates polar metabolites and the interaction with organic matter in the soil changes. The polar PAH metabolites are persistent, highly water-soluble and potentially leachable from the soil; the understanding of transformation of PAHs to polar metabolites in the responsible organisms is of great importance. Here, we present a study of transformation of the PAHs pyrene and phenanthrene, by the common earthworm Eisenia fetida. The study showed that E. fetida in hydroponic culture was able to transform PAHs to conjugated phase II metabolites. We detected phenanthrene and pyrene metabolites with single- and multiple-phase II-conjugated groups. Sulphate conjugates were excreted to experiment water, and glucuronide and glucoside conjugates and metabolites with several hydroxylations and multiple conjugations were detected in worm tissue. The results demonstrate that earthworms are able to transform PAHs to water-soluble phase II metabolites, which can be excreted to the surrounding environment.     

旋涡与行进表面水波相互作用的实验研究

采用振动板式造波器在二维水槽中生成近似单色的行进表面水波，采用夹板式涡发生器生成稳定上浮的涡对，在Ｆｒｏｕｄｅ数约为０．５的条件下，得到了水下涡对与不同波长和振幅的行进表面水波相互作用时的干扰图象，以实验方法验证了理论分析和数值计算的结果，并为进一步研究旋涡与行进表面水波的相互作用提供了一种实验研究方法     

Immunomodulatory Properties of Masticadienonic Acid and 3α-Hydroxy Masticadienoic Acid in Dendritic Cells

Dendritic cells are antigen-presenting cells, which identify and process pathogens to subsequently activate specific T lymphocytes. To regulate the immune responses, DCs have to mature by the recognition of TLR ligands, TNFα or IFNγ. These ligands have been used as adjuvants to activate DCs in situ or in vitro, with toxic effects. It has been shown that some molecules affect the immune system, e.g., Masticadienonic acid (MDA) and 3α-hydroxy masticadienoic acid (3α-OH MDA) triterpenes naturally occurring in several medicinal plants, since they activate the nitric oxide synthase in macrophages and induce T lymphocyte proliferation. The DCs maturation induced by MDA or 3a-OH MDA was determined by incubating these cells with MDA or 3α-OH MDA, and their phenotype was afterwards analyzed. The results showed that only 3α-OH MDA was able to induce DCs maturation. When mice with melanoma were inoculated with DCs/3α-OH MDA, a decreased tumor growth rate was observed along with an extended cell death area within tumors compared to mice treated with DCs incubated with MDA. In conclusion, it is proposed that 3α-OH MDA may be an immunostimulant molecule. Conversely, it is proposed that MDA may be a molecule with anti-inflammatory properties.     

Facial Synthesis and Bioevaluation of Well-Defined OEGylated Betulinic Acid-Cyclodextrin Conjugates for Inhibition of Influenza Infection

Betulinic acid (BA) and its derivatives exhibit a variety of biological activities, especially their anti-HIV-1 activity, but generally have only modest inhibitory potency against influenza virus. The entry of influenza virus into host cells can be competitively inhibited by multivalent derivatives targeting hemagglutinin. In this study, a series of hexa-, hepta- and octavalent BA derivatives based on α-, β- and γ-cyclodextrin scaffolds, respectively, with varying lengths of flexible oligo(ethylene glycol) linkers was designed and synthesized using a microwave-assisted copper-catalyzed 1,3-dipolar cycloaddition reaction. The generated BA-cyclodextrin conjugates were tested for their in vitro activity against influenza A/WSN/33 (H1N1) virus and cytotoxicity. Among the tested compounds, 58, 80 and 82 showed slight cytotoxicity to Madin-Darby canine kidney cells with viabilities ranging from 64 to 68% at a high concentration of 100 μM. Four conjugates 51 and 69–71 showed significant inhibitory effects on influenza infection with half maximal inhibitory concentration values of 5.20, 9.82, 7.48 and 7.59 μM, respectively. The structure-activity relationships of multivalent BA-cyclodextrin conjugates were discussed, highlighting that multivalent BA derivatives may be potential antiviral agents against influenza infection.     

Microalgae Biomass as a New Potential Source of Sustainable Green Lubricants

Lubricants are materials able to reduce friction and/or wear of any type of moving surfaces facilitating smooth operations, maintaining reliable machine functions, and reducing risks of failures while contributing to energy savings. At present, most worldwide used lubricants are derived from crude oil. However, production, usage and disposal of these lubricants have significant impact on environment and health. Hence, there is a growing pressure to reduce demand of this sort of lubricants, which has fostered development and use of green lubricants, as vegetable oil-based lubricants (biolubricants). Despite the ecological benefits of producing/using biolubricants, availability of the required raw materials and agricultural land to create a reliable chain supply is still far from being established. Recently, biomass from some microalgae species has attracted attention due to their capacity to produce high-value lipids/oils for potential lubricants production. Thus, this multidisciplinary work reviews the main chemical-physical characteristics of lubricants and the main attempts and progress on microalgae biomass production for developing oils with pertinent lubricating properties. In addition, potential microalgae strains and chemical modifications to their oils to produce lubricants for different industrial applications are identified. Finally, a guide for microalgae oil selection based on its chemical composition for specific lubricant applications is provided.     

Chemoselective Preparation of New Families of Phenolic-Organoselenium Hybrids—A Biological Assessment

Being aware of the enormous biological potential of organoselenium and polyphenolic compounds, we have accomplished the preparation of novel hybrids, combining both pharmacophores in order to obtain new antioxidant and antiproliferative agents. Three different families have been accessed in a straightforward and chemoselective fashion: carbohydrate-containing N-acylisoselenoureas, N-arylisoselenocarbamates and N-arylselenocarbamates. The nature of the organoselenium framework, number and position of phenolic hydroxyl groups and substituents on the aromatic scaffolds afforded valuable structure–activity relationships for the biological assays accomplished: antioxidant properties (antiradical activity, DNA-protective effects, Glutathione peroxidase (GPx) mimicry) and antiproliferative activity. Regarding the antioxidant activity, selenocarbamates 24–27 behaved as excellent mimetics of GPx in the substoichiometric elimination of H₂O₂ as a Reactive Oxygen Species (ROS) model. Isoselenocarbamates and particularly their selenocarbamate isomers exhibited potent antiproliferative activity against non-small lung cell lines (A549, SW1573) in the low micromolar range, with similar potency to that shown by the chemotherapeutic agent cisplatin (cis-diaminodichloroplatin, CDDP) and occasionally with more potency than etoposide (VP-16).     

Cytosolic escape of mitochondrial DNA triggers cGAS-STING-NLRP3 axis-dependent nucleus pulposus cell pyroptosis

Low back pain (LBP) is a major musculoskeletal disorder and the socioeconomic problem with a high prevalence that mainly involves intervertebral disc (IVD) degeneration, characterized by progressive nucleus pulposus (NP) cell death and the development of an inflammatory microenvironment in NP tissue. Excessively accumulated cytosolic DNA acts as a damage-associated molecular pattern (DAMP) that is monitored by the cGAS-STING axis to trigger the immune response in many degenerative diseases. NLRP3 inflammasome-dependent pyroptosis is a type of inflammatory programmed death that promotes a chronic inflammatory response and tissue degeneration. However, the relationship between the cGAS-STING axis and NLRP3 inflammasome-induced pyroptosis in the pathogenesis of IVD degeneration remains unclear. Here, we used magnetic resonance imaging (MRI) and histopathology to demonstrate that cGAS, STING, and NLRP3 are associated with the degree of IVD degeneration. Oxidative stress induced cGAS-STING axis activation and NLRP3 inflammasome-mediated pyroptosis in a STING-dependent manner in human NP cells. Interestingly, the canonical morphological and functional characteristics of mitochondrial permeability transition pore (mPTP) opening with the cytosolic escape of mitochondrial DNA (mtDNA) were observed in human NP cells under oxidative stress. Furthermore, the administration of a specific pharmacological inhibitor of mPTP and self-mtDNA cytosolic leakage effectively reduced NLRP3 inflammasome-mediated pyroptotic NP cell death and microenvironmental inflammation in vitro and degenerative progression in a rat disc needle puncture model. Collectively, these data highlight the critical roles of the cGAS-STING-NLRP3 axis and pyroptosis in the progression of IVD degeneration and provide promising therapeutic approaches for discogenic LBP.Subject terms: Cell death, Diseases