Ultra-Dense Supported Ruthenium Oxide Clusters via Directed Ion Exchange for Efficient Valorization of 5-Hydroxymethylfurfural.

Maximizing the loadings of active centers without aggregation for a supported catalyst is a grand challenge but essential for achieving high gravimetric catalytic activity, especially toward multi-step reactions. The oxidation of 5-hydroxymethylfurfural (HMF), a key biomass-derived platform molecule, into 2,5-furandicarboxylic acid (FDCA), a promising alternative to polyester monomer, is such a multi-step reaction that involves 6 proton and electron transfers. This process often demands strong alkaline environment but also suffers from the alkali-driven polymerization side-reaction. Meanwhile, neutral media ameliorates the polymerization, but lacks efficient catalyst toward deep oxidation. Herein, we devised a strategy of creating ultra-dense supported Ru oxide clusters via directed ion exchange in a Co hydroxyanion (CoHA) support material. Pyrimidine ligands were first incorporated into the CoHA interlayers, and the subsequent evacuation of pyrimidines created porous channels for the directed ion exchange with the built-in anions in CoHA, which allowed the dense and mono-disperse functionalization of RuCl6 2- anions and their resulting Ru oxide clusters. These ultra-dense Ru oxide clusters not only enable high HMF electrooxidation currents under neutral conditions but also create microscopic channels in-between the clusters for the expedited re-adsorption and oxidation of intermediates toward highly oxidized product, such as 5-formyl-2-furoic acid (FFCA) and FDCA. A two-stage HMF oxidation process, consisting of ambient conversion of HMF into FFCA and FFCA oxidation into FDCA under 60 °C, was eventually developed to first achieve a high FDCA yield of 92.1 % under neutral media with significantly reduced polymerization.

Inoculation with thermophiles enhanced the food waste bio-drying and complicated interdomain ecological networks between bacterial and fungal communities.

Bio-drying is a practical approach for treating food waste (FW). However, microbial ecological processes during treatment are essential for improving the dry efficiency, and have not been stressed enough. This study analyzed the microbial community succession and two critical periods of interdomain ecological networks (IDENs) during FW bio-drying inoculated with thermophiles (TB), to determine how TB affects FW bio-drying efficiency. The results showed that TB could rapidly colonize in the FW bio-drying, with the highest relative abundance of 5.13%. Inoculating TB increased the maximum temperature, temperature integrated index and moisture removal rate of FW bio-drying (55.7 °C, 219.5 °C, and 86.11% vs. 52.1 °C, 159.1 °C, and 56.02%), thereby accelerating the FW bio-drying efficiency by altering the succession of microbial communities. The structural equation model and IDEN analysis demonstrated that TB inoculation complicated the IDENs between bacterial and fungal communities by significantly and positively affecting bacterial communities (b = 0.39, p < 0.001) and fungal communities (b = 0.32, p < 0.01), thereby enhancing interdomain interactions between bacteria and fungi. Additionally, inoculation TB significantly increased the relative abundance of keystone taxa, including Clostridium sensu stricto, Ochrobactrum, Phenylobacterium, Microvirga and Candida. In conclusion, the inoculation of TB could effectively improve FW bio-drying, which is a promising technology for rapidly reducing FW with high moisture content and recovering resources from it.

Electrode/Electrolyte Synergy for Concerted Promotion of Electron and Proton Transfers toward Efficient Neutral Water Oxidation.

Neutral water oxidation is a crucial half-reaction for various electrochemical applications requiring pH-benign conditions. However, its sluggish kinetics with limited proton and electron transfer rates greatly impacts the overall energy efficiency. In this work, we created an electrode/electrolyte synergy strategy for simultaneously enhancing the proton and electron transfers at the interface toward highly efficient neutral water oxidation. The charge transfer was accelerated between the iridium oxide and in situ formed nickel oxyhydroxide on the electrode end. The proton transfer was expedited by the compact borate environment that originated from hierarchical fluoride/borate anions on the electrolyte end. These concerted promotions facilitated the proton-coupled electron transfer (PCET) events. Due to the electrode/electrolyte synergy, Ir-O and Ir-OO- intermediates could be directly detected by in situ Raman spectroscopy, and the rate-limiting step of Ir-O oxidation was determined. This synergy strategy can extend the scope of optimizing electrocatalytic activities toward more electrode/electrolyte combinations.

Pyrolysis gas from biomass and plastics over X-Mo@MgO (X = Ni, Fe, Co) catalysts into functional carbon nanocomposite: Gas reforming reaction and proper process mechanisms.

The metal catalysts X-Mo@MgO (X = Ni, Fe, Co) was studied as excellent catalyst for catalytic pyrolysis conversion of biomass and plastics into functional carbon nanocomposite. The proper reaction mechanism of the process was explored through the gas composition, and explored the bactericidal performance of functional carbon nanocomposite. The results showed that the Ni, Fe and Co-based catalysts elevated H2 gas yield reached to 57%, 34% and 44% as the addition of Mo, due to Mo or its oxide species for scission of small molecule compound. The introduction of NiMo@MgO catalyst produced lower CH4, and higher H2 and MWCNTs, which indicated that the formation of MWCNTs is mainly attributed to CH4 dehydrogenation. As a comparison, FeMo@MgO catalyst for CO disproportionation reaction could generate more MWCNTs and lower H2. The functional carbon nanocomposite from FeMo@MgO catalyst were comprehensively evaluated by multiple characterizations. TPO and Raman results confirmed that FeMo@MgO catalyst can provide an excellent carrier to generate MWCNTs with few defects and high graphitization. The functional carbon nanocomposite were initially applied to E.coli extinguishing. The core-shell structure catalyst not only has excellent bactericidal performance, but also has strong resistance to metal leaching.

Hyaluronic acid and albumin based nanoparticles for drug delivery.

Albumin, a multifunctional protein, is widely used to prepare nanocarriers. Hyaluronic acid (HA) is a natural glycosaminoglycan that can specifically bind receptors, such as cluster of differentiation-44. Therefore, HA is commonly used as ligands for the surface modification of versatile nanocarriers. The combined utilization of albumin and HA as nanocarriers shows outstanding superiorities including efficient targeting, reducible particle size, pH and/or hyaluronidase sensitive drug release, combining capacity for various drugs, biocompatibility, non-immunogenicity, biodegradability and high stability. However, to the best of our knowledge, HA and albumin based nanoparticles have not been reviewed for drug delivery so far. This review involves the introduction of the essential information of HA and albumin as well as a brief presentation of the preparation methods of HA and albumin based nanocarriers. Moreover, the application of HA and albumin based nanoparticles as drug delivery carriers in tumors, joints, vitreum and skin tissue is systematically discussed with the potential and prospect in combined therapy and theranostics. In addition, the unique advantages of the HA and albumin based nanoparticles and their contributions to the improvement of drug delivery systems are further expounded in detail.

Preparation and in Vitro Antitumor Study of Two-Dimensional Muscovite Nanosheets.

Inorganic nanosheets are endowed with many two-dimensional (2D) morphological features including ultra-high specific surface area, ultra-thin thickness, easy functionalization, and so on. They push forward an immense influence on effective cancer diagnosis and therapy, overcoming the inherent limitations of traditional treatment methods. However, long-term toxicity and poor biocompatibility are the critical issues for most inorganic nanosheets, which hinder their further oncological applications and clinical translations. Muscovite, also named white mica (WM), an aluminosilicate, is a major component of traditional Chinese medicine, which can be exfoliated into 2D nanosheets and expected to be a potential drug carrier. In this study, WM powder was exfoliated to prepare WM nanosheets (WMNs) through a polyamine intercalation method. In addition, doxorubicin hydrochloride (Dox) was loaded to WMNs via physical adsorption and electrostatic interaction to prepare Dox-loaded WMNs (Dox@WMNs). Then, we studied that Dox@WMNs released Dox in phosphate buffer saline. We also studied the cellular uptake and cytotoxicity of Dox@WMNs in vitro. The results illustrated that Dox@WMNs cumulatively released Dox much faster and more at acidic pH (6.0 and 4.6) compared with that at physiological pH. In addition, WMNs showed selective cytotoxicity. Within a certain concentration range, WMNs were cytotoxic to Hela cells but non-cytotoxic to RAW 264.7 cells. Compared with cytotoxicity at pH 7.4, the cytotoxicity of Dox@WMNs was significantly enhanced at pH 6.4 and 4.6. WMNs mainly promoted the immunostimulatory polarization of RAW 264.7 cells into M1 macrophages.

Biology drives the discovery of bispecific antibodies as innovative therapeutics.

A bispecific antibody (bsAb) is able to bind two different targets or two distinct epitopes on the same target. Broadly speaking, bsAbs can include any single molecule entity containing dual specificities with at least one being antigen-binding antibody domain. Besides additive effect or synergistic effect, the most fascinating applications of bsAbs are to enable novel and often therapeutically important concepts otherwise impossible by using monoclonal antibodies alone or their combination. This so-called obligate bsAbs could open up completely new avenue for developing novel therapeutics. With evolving understanding of structural architecture of various natural or engineered antigen-binding immunoglobulin domains and the connection of different domains of an immunoglobulin molecule, and with greatly improved understanding of molecular mechanisms of many biological processes, the landscape of therapeutic bsAbs has significantly changed in recent years. As of September 2019, over 110 bsAbs are under active clinical development, and near 180 in preclinical development. In this review article, we introduce a system that classifies bsAb formats into 30 categories based on their antigen-binding domains and the presence or absence of Fc domain. We further review the biology applications of approximately 290 bsAbs currently in preclinical and clinical development, with the attempt to illustrate the principle of selecting a bispecific format to meet biology needs and selecting a bispecific molecule as a clinical development candidate by 6 critical criteria. Given the novel mechanisms of many bsAbs, the potential unknown safety risk and risk/benefit should be evaluated carefully during preclinical and clinical development stages. Nevertheless we are optimistic that next decade will witness clinical success of bsAbs or multispecific antibodies employing some novel mechanisms of action and deliver the promise as next wave of antibody-based therapeutics.

Direct Biotransformation of Dioscin into Diosgenin in Rhizome of Dioscorea zingiberensis by Penicillium dioscin.

Diosgenin is an important precursor for synthesis of more than 200 steroidal hormone medicines. Rhizome of Dioscorea zingiberensis C. H. Wright (RDZ) contained the highest content of diosgenin in Dioscorea plant species. Diosgenin is traditionally extracted by acid hydrolysis from RDZ. However, the acid hydrolysis process produces massive wastewater which caused serious environment pollution. In this study, diosgenin extraction by direct biotransformation with Penicillium dioscin was investigated. The spawn cultivation conditions were optimized as: Czapeks liquid culture medium without sugar and agar (1,000 ml) + 6.0 g dioscin/6.0 g DL, 30 °C, 36 h; solid fermentation of RDZ: mycelia/RDZ of 0.05 g/kg, 30 °C, 50 h; the yield of diosgenin was over 90 %. Spawn cultivation was crucial for the direct biotransformation. In the spawn cultivation, amount and ratio of dioscin/DL were the key factors to promote biotransformation activity of P. dioscin. This biotransformation method was environment-friendly, simple and energy saving, and might be a potential substitute for acid hydrolysis in diosgenin extraction industry.

Selenium increases chlorogenic acid, chlorophyll and carotenoids of Lycium chinense leaves.

BACKGROUND: Leaves of Lycium chinense L. are widely used in traditional Chinese medicine and as functional food in China and south-east Asia. Polyphenols are important active compounds in leaves of L. chinense L, but their compositions are still not very clear. Selenium has been reported to increase some components of plants. In this study, the composition of polyphenols of L. chinense leaves were analysed, and the effects of selenium on the polyphenols and other components were studied. RESULTS: The main polyphenols were identified as rutin, chlorogenic acid, quercetin, kaempferol and apigenin-7-O-(6'-O-acetyl) glucose-rhamnose. Chlorogenic acid showed the highest average content of 78.36 g kg⁻¹. Rutin, quercetin and kaempferol were determined at low contents from 3.85 g kg⁻¹ to 7.08 g kg⁻¹. Correlation coefficients between selenium and chlorogenic acid, chlorophyll a, chlorophyll b and carotenoids were: R² = 0.963 (P = 0.002), 0.943 (P = 0.005), 0.957 (P = 0.003) and 0.943 (P = 0.005), respectively. Selenium (0.01-0.05 g kg⁻¹) significantly increased chlorogenic acid, chlorophyll and carotenoids by 200-400% and reduced rutin by 400-900%. CONCLUSION: L. chinense can be an alternative source of chlorogenic acid. Selenium significantly increased chlorogenic acid, chlorophyll a, chlorophyll b and carotenoids, hence increasing the medicinal value of L. chinense leaves. Rutin, quercetin, kaempferol and apigenin-7-O-(6'-O-acetyl) glucose-rhamnose proved to be not significantly influenced by selenium.

Composition and distribution of the main active components in selenium-enriched fruit bodies of Cordyceps militaris link.

Selenium-enriched Cordyceps militaris fruit bodies are industrially cultivated as functional food or medicinal food in China and southeast Asia. However, composition of selenium compounds and distribution of the main bioactive components are still unknown. In the selenium-enriched fruit bodies, the main soluble selenium compounds of low molecular weight were identified as SeMet (selenomethionine), and the main selenium compounds bound in proteins were identified as SeMet and SeCys (methylselenocysteine). Trace minerals as Se (selenium), Zn (zinc), Fe (iron) and the main active components as adenosine, cordycepin and carotenoids were mostly distributed in the terminal of fruit bodies, while P (phosphorus) and K (potassium) were evenly distributed in the fruit bodies. The results indicated that terminal of the fruit bodies should be the better materials for production of advanced functional food. So cultivation of relatively short and thick fruit bodies with bigger terminals deserves further research.

tert-Butyl N-[6-(N,N-dipropyl-carbamo-yl)-1,3-benzothia-zol-2-yl]carbamate.

The title compound C(19)H(27)N(3)O(3)S, crystallizes with two unique mol-ecules in the asymmetric unit. The benzene ring of each benzothia-zole unit carries a dipropyl-carbamoyl substituent in the 6-position and a tert-butyl carbamate unit on each thia-zole ring. In the crystal structure, inter-molecular N-H⋯N and weak C-H⋯O hydrogen bonds form centrosymmetric dimers. Additional C-H⋯O contacts construct a three-dimensional network. A very weak C-H⋯π contact is also present.

Ethyl 2-(tert-butoxy-carbonyl-amino)-1,3-benzothia-zole-6-carboxyl-ate.

In the crystal of the title compound, C(15)H(18)N(2)O(4)S, inversion dimers are formed by inter-molecular N-H⋯N hydrogen bonds and weak C-H⋯O contacts. These dimers stack up along [100] through inversion-related π-π inter-actions between thia-zole rings [centroid-centroid distance = 3.790 (2) Å] and the thia-zole and benzene rings [centroid-centroid distance = 3.845 (2) Å] and C-H⋯π contacts.