Synthesis and characterization of novel functional poly(vinyl alcohol-co-styrene sulfonic acid) copolymers

This paper first time reports the preparation of random anionic copolymers from vinyl acetate (VAc) bearing electro-donating substituent and sodium 4-vinylbenzenesulfonate (SSA) having electro-withdrawing substituent. Copolymers (PVA-co-SSA) of different composition have been successfully prepared by a simple free radical solution polymerization technique. Resulting final copolymer contained neutral hydrophilic as well as ionizable ion exchange sites. Evaluation of spectral data obtained from Fourier transform Infrared spectroscopy, Raman spectroscopy, and ¹H Nuclear magnetic resonance helped in identifying and confirming the chemical structure of copolymers. Characterization of copolymers by gel permeation chromatography revealed high molecular weight with moderate polydispersity index. Analysis of thermal stability and glass transition temperature of copolymers by thermogravimetric analysis and differential scanning calorimetry were found in between corresponding homopolymers. Physicochemical properties of PVA-co-SSA can be beneficial for prospective advanced application in the niche area of smart membrane technology for energy and environment.     

Thermodynamic properties of gaseous cerium phosphate studied by Knudsen effusion mass spectrometry

Gaseous CePO₂ has been identified by Knudsen effusion mass spectrometry during vaporization of CeO₂ and magnesium diphosphate from tungsten double, two‐temperature effusion cell. Structure and molecular parameters of gaseous cerium phosphate under study were determined using quantum chemical calculations. On the basis of equilibrium constants measured for gas‐phase reaction, standard formation enthalpy of CePO₂ was determined to be ?508 ± 41 kJ ? mol^?1 at the temperature 298 K.     

One-step synthesis of porous PtNiCu trimetallic nanoalloy with enhanced electrocatalytic performance toward methanol oxidation

Pt-based alloy nanoporous structures have attracted a lot of attention because of their high activity and stability toward alcohol oxidation reactions. Especially, Pt alloying with Earth-abundant metal can lower the cost of catalyst. Here, we introduce a one-pot approach to synthesize bimetallic PtCu and Ni-doped PtCu nanoalloy with porous structure. The as-synthesized Ni-doped Pt₆₀Ni₃Cu₃₇ nanoalloys exhibit excellent electrocatalytic properties toward methanol oxidation in acidic medium. The mass activity of the as-synthesized Pt₆₀Ni₃Cu₃₇ nanoalloys is 3.6 times and 5.3 times that of Pt₅₅Cu₄₅ nanoalloys and commercial Pt black for methanol oxidation in 0.2?M methanol solution. Besides, the stability of the as-synthesized Pt₆₀Ni₃Cu₃₇ nanoalloys was much better than Pt₅₅Cu₄₅ nanoalloys and commercial Pt black. After 3600?s chronoamperometry test, the remaining values of the Pt₆₀Ni₃Cu₃₇ nanoalloys are 3.7 times and 11.0 times that of Pt₅₅Cu₄₅ nanoalloys and commercial Pt black. And it is the first time to report that small amount of Ni dopants can boost the activity and stability of PtNiCu alloys toward methanol oxidation.     

Nanoparticle‐Mediated Immunogenic Cell Death Enables and Potentiates Cancer Immunotherapy

Cancer immunotherapies that train or stimulate the inherent immunological systems to recognize, attack, and eradicate tumor cells with minimal damage to healthy cells have demonstrated promising clinical responses in recent years. However, most of these immunotherapeutic strategies only benefit a small subset of patients and cause systemic autoimmune side effects in some patients. Immunogenic cell death (ICD)‐inducing modalities not only directly kill cancer cells but also induce antitumor immune responses against a broad spectrum of solid tumors. Such strategies for generating vaccine‐like functions could be used to stimulate a “cold” tumor microenvironment to become an immunogenic, “hot” tumor microenvironment, working in synergy with immunotherapies to increase patient response rates and lead to successful treatment outcomes. This Minireview will focus on nanoparticle‐based treatment modalities that can induce and enhance ICD to potentiate cancer immunotherapy.     

Design,Synthesis, and Phenotypic Profiling of Pyrano‐Furo‐Pyridone Pseudo Natural Products

Natural products (NPs) inspire the design and synthesis of novel biologically relevant chemical matter, for instance through biology‐oriented synthesis (BIOS). However, BIOS is limited by the partial coverage of NP‐like chemical space by the guiding NPs. The design and synthesis of “pseudo NPs” overcomes these limitations by combining NP‐inspired strategies with fragment‐based compound design through de novo combination of NP‐derived fragments to unprecedented compound classes not accessible through biosynthesis. We describe the development and biological evaluation of pyrano‐furo‐pyridone (PFP) pseudo NPs, which combine pyridone‐ and dihydropyran NP fragments in three isomeric arrangements. Cheminformatic analysis indicates that the PFPs reside in an area of NP‐like chemical space not covered by existing NPs but rather by drugs and related compounds. Phenotypic profiling in a target‐agnostic “cell painting” assay revealed that PFPs induce formation of reactive oxygen species and are structurally novel inhibitors of mitochondrial complex I.     

First-Principles Study of Aziridinium Lead Iodide Perovskite for Photovoltaics

The long-term stability remains one of the main challenges for the commercialization of the rapidly developing hybrid organic-inorganic perovskite solar cells. Herein, we investigate the electronic and optical properties of the recently reported hybrid halide perovskite (CH₂)₂NH₂PbI₃ (AZPbI₃), which exhibits a much better stability than the popular halide perovskites CH₃NH₃PbI₃ and HC(NH₂)₂PbI₃, by using density functional theory (DFT). We find that AZPbI₃ possesses a band gap of 1.31 eV, ideal for single-junction solar cells, and its optical absorption is comparable with those of the popular CH₃NH₃PbI₃ and HC(NH₂)₂PbI₃ materials in the whole visible-light region. In addition, the conductivity of AZPbI₃ can be tuned from efficient p-type to n-type, depending on the growth conditions. Besides, the charge-carrier mobilities and lifetimes are unlikely hampered by deep transition energy levels, which have higher formation energies in AZPbI₃ according to our calculations. Overall, we suggest that the perovskite AZPbI₃ is an excellent candidate as a stable high-performance photovoltaic absorber material.     

Ultrathin Silicon Oxide Film-Induced Enhancement of Charge Separation and Transport of Nanostructured Titanium(IV) Oxide Photoelectrode

The development of nanostructured semiconductor electrodes represented by a mesoporous TiO₂ nanocrystalline (mp-TiO₂) film is currently bringing great progresses in photoelectrochemical (PEC) devices for solar-to-electricity and solar-to-chemical conversion. Two serious losses can occur in PEC devices: 1) recombination between the conduction band (CB) electrons and valence band (VB) holes in the bulk and at the surface and 2) back reaction or electron trapping by oxidant in the electrolyte solution during transport to the electron-collecting electrode. Thus, the major challenge in common with the nanostructured semiconductor photoanodes is to achieve efficient charge separation and electron transport. In this study, an ultrathin SiO_x layer was formed on both the external and the internal surface of mp-TiO₂ using an original chemisorption-calcination technique employing 1,3,5,7-tetramethyltetrasiloxane as a starting material. The SiO_x surface modification of the mp-TiO₂ photoanode drastically prolongs the mean lifetime of CB-electrons in TiO₂ because of enhanced charge separation and electron transport by the negative charge applied in aqueous electrolyte solution. We have demonstrated that the performance of a one-compartment H₂O₂-photofuel cell using mp-TiO₂ as the photoanode is greatly boosted by the surface modification with the SiO_x layer. We anticipate that this methodology is widely applicable to nanostructured metal oxide semiconductor electrodes, contributing to the improvement in the performance of PEC devices.     

Ultimate Charge Extraction of Monolayer PbS Quantum Dot for Observation of Multiple Exciton Generation

Multiple exciton generation (MEG) has great potential to improve the Shockley-Queisser (S-Q) efficiency limitation for colloidal quantum dot (CQD) solar cells. However, MEG has rarely been observed in CQD solar cells because of the loss of carriers through the transport mechanism between adjacent QDs. Herein, we demonstrate that excess charge carriers produced via MEG can be efficiently extracted using monolayer PbS QDs. The monolayer PbS QDs solar cells exhibit α=1 in the light intensity dependence of the short-circuit current density J_sc (J_sc∝I^α) and an internal quantum efficiency (IQE) value of 100 % at 2.95 eV because of their very short charge extraction path. In addition, the measured MEG threshold is 2.23 times the bandgap energy (E_g), which is the lowest value in PbS QD solar cells. We believe that this approach can provide a simple method to find suitable CQD materials and design interface engineering for MEG.     

HPLC profiling of phenolics and flavonoids of Adonidia merrillii fruits and their antioxidant and cytotoxic properties

In this study the antioxidant and cytotoxicity activity of the Adonidia merrillii fruits were investigated using different solvent polarities (methanol, ethyl acetate and water). The results showed that the total phenolic and flavonoid contents of the methanolic extract was higher compare with other extract with respective values of 17.80 ± 0.45 mg gallic acid equivalents/g dry weight (DW) and 5.43 ± 0.33 mg rutin equivalents/g DW. Beside that The RP-HPLC analyses indicated the presence of gallic acid, pyrogallol, caffeic acid, vanillic acid, syringic acid, naringin and rutin. In the DPPH, NO2 and ABTS scavenging assays, the methanolic extract exhibited higher antioxidant activity as compared to the ethyl acetate and water extracts. The extracts exhibited moderate to weak cytotoxic activity in the assays using human hepatocytes (Chang liver cells) and NIH/3T3 (fibroblasts cell) cell lines. The findings showed the Adonidia merrillii fruit extracts to possess considerable antioxidant and cytotoxicity properties. The fruit, therefore, is a potential candidate for further work to discover antioxidant and cytotoxic drugs from natural sources.     

Enzymatic inhibitory activity of Ficus deltoidea leaf extract on matrix metalloproteinase-2, 8 and 9

Dysregulation of matrix metalloproteinases (MMPs) activity is known in many pathological conditions with which most of the conditions are related to elevate MMPs activities. Ficus deltoidea (FD) is a plant known for its therapeutic properties. In order to evaluate the therapeutic potential of FD leaf extract, we study the enzymatic inhibition properties of FD leaf extract and its major bioactive compounds (vitexin and isovitexin) on a panel of MMPs (MMP-2, MMP-8 and MMP-9) using experimental and computational approaches. FD leaf extract and its major bioactive compounds showed pronounced inhibition activity towards the MMPs tested. Computational docking analysis revealed that vitexin and isovitexin bind to the active site of the three tested MMPs. We also evaluated the cytotoxicity and cell migration inhibition activity of FD leaf extract in the endothelial EA.hy 926 cell line. Conclusively, this study provided additional information on the potential of FD leaf extract for therapeutical application.