Unraveling the Electrocatalytic Activity in HMF Oxidation to FDCA by Fine-Tuning the Degree of NiOOH Phase Over Ni Nanoparticles Supported on Graphene Oxide.

The development of an efficient electrocatalyst for HMF oxidation to FDCA has been in the early stages. Herein, the NiNPs/GO-Ni-foam is fabricated as an electrocatalyst for FDCA production. However, the electrocatalytic performance of the untreated NiNPs/GO-Ni-foam is observed with moderate Faradaic efficiency (FE) (73.0%) and FDCA yield (80.2%). By electrochemically treating the NiNPs/GO-Ni-foam in an alkaline solution with positive potential at different treatment durations, the degree of NiOOH on metal surfaces is changed. The distinctive electrocatalytic activity obtained when using the different NiOOH degrees allows to understand the crucial impact of NiOOH species in HMF electrooxidation. Enhancing the portion of the NiOOH phase on the electrocatalyst surface improves electrocatalytic activity in terms of FE and FDCA yield up to 94.8±4.8% and 86.9±4.1%, respectively. Interestingly, as long as the NiOOH portion on the electrocatalyst surface is preserved or regenerated, the electrocatalyst performance can be intact even after several catalytic cycles. The theoretical study via density functional theory (DFT) also agrees with the experimental observations and confirms that the NiOOH phase facilitates the electrochemical transformation of HMF to FDCA through the HMFCA pathway, and the potential limiting step of the overall reaction is the oxidation of FFCA to FDCA.

Discovery of Alkyl Triphenylphosphonium Pinostrobin Derivatives as Potent Anti-Breast Cancer Agents.

Pinostrobin demonstrated anticancer properties, but its hydrophobic feature led to a reduction in bioavailability. The mitochondria-targeted approach successfully synthesized eight new alkyl triphenylphosphonium pinostrobin derivatives (1-8) with good yield in this study. Seven compounds (1-3, 5-8) showed greater cytotoxic potency against the human MCF-7 breast cancer cell line than pinostrobin. Molecular docking studies were performed with two important targets in hormone-dependent anticancer strategies, estrogen receptor α (ERα) ligand binding domains, 3ERT (antagonist recognition and antiproliferative function), and 1GWR (agonist recognition and pro-proliferative function). In addition, the MD simulation study of the two most potent compounds (2 and 3) complexed with both ERα forms suggested that compounds 2 and 3 could serve as favourable antagonists. Furthermore, the in silico ADMET prediction indicated that compounds 2 and 3 could be potential drug candidates.

A New abeo-Icetexane-Type Diterpenoid from the Stem Barks of Taxus wallichiana.

From a CH2 Cl2 -soluble fraction of the stem barks of Taxus wallichiana, one new abeo-icetexane-type diterpenoid, taxamairin I (1), was isolated. Its absolute configuration was elucidated based on spectroscopic interpretation and time-dependent density functional theory (TD-DFT) calculation of optical rotation. In addition, the plausible biosynthesis pathway for the formation of the new abeo-icetexane-type diterpenoid was proposed. Taxamairin I (1), at a concentration of 100 µM, did not show cytotoxicity against Hep3B human liver cancer cell lines.

Pt/Ag Solid Solution Alloy Nanoparticles in Miscibility Gaps Synthesized by Cosputtering onto Liquid Polymers.

Pt/Ag solid solution alloy nanoparticles (NPs) with mean size below 3 nm were obtained with composition in miscibility gaps by cosputtering onto liquid polyethylene glycol (PEG, MW = 600). Adjusting the sputtering currents from 10 to 50 mA did not influence the particle sizes obviously but caused a substantial difference in the composition and distributions of Pt/Ag NPs. This is different from sputtered Pt/Au NPs where particle size is correlated with composition. For a pair of sputtering currents, the formed Pt/Ag alloy NPs have a range of compositions. The normal distribution with Pt of 60.2 ± 16.2 at % is observed for the Pt/Ag sample with a nominal Pt content of 55.9 at %, whereas Pt-rich (85.1 ± 14.0 at % Pt) and Ag-rich (19.8 ± 12.2 at % Pt) Pt/Ag samples with nominal Pt contents of 90.9 and 11.9 at % contain more pure Pt and pure Ag NPs, respectively. Different from NPs obtained in PEG, the sputtered NPs on TEM grids had more uniform composition for a longer sputtering time along with a significant increase of particle sizes. This reveals that PEG hindered the combination of NPs and clusters, resulting in small particle sizes even for long time sputtering and broader composition distributions. Thus, the samples obtained in PEG have the compositions mainly determined by the random atom combination in the vacuum chamber and possibly in initial landing of atom/clusters on the PEG surface.

Control of nanoparticles synthesized via vacuum sputter deposition onto liquids: a review.

Sputter deposition onto a low volatile liquid matrix is a recently developed green synthesis method for metal/metal oxide nanoparticles (NPs). In this review, we introduce the synthesis method and highlight its unique features emerging from the combination of the sputter deposition and the ability of the liquid matrix to regulate particle growth. Then, manipulating the synthesis parameters to control the particle size, composition, morphology, and crystal structure of NPs is presented. Subsequently, we evaluate the key experimental factors governing the particle characteristics and the formation of monometallic and alloy NPs to provide overall directions and insights into the preparation of NPs with desired properties. Following that, the current understanding of the growth and formation mechanism of sputtered particles in liquid media, in particular, ionic liquids and liquid polymers, during and after sputtering is emphasized. Finally, we discuss the challenges that remain and share our perspectives on the future prospects of the synthesis method and the obtained NPs.

The coverage of influenza and pneumococcal vaccination among kidney transplant recipients and waiting list patients: A cross-sectional survey in Denmark.

BACKGROUND: To characterize level and predictors of influenza and pneumococcal vaccine uptake among Danish kidney transplant recipients (KTR) and kidney transplant waiting list patients (WLP). METHODS: A cross-sectional survey based on self-reported vaccine uptake including WLP and KTR ≤ 1½ years post transplantation. Descriptive statistics and logistic regression analyses identifying factors associated with influenza vaccine uptake in the latest season were performed. RESULTS: A total of 220 participants were included in the study, 54% KTR and 46% WLP. Self-reported influenza vaccine uptake in the latest season was overall 41.8%. Uptake of influenza vaccine on any prior season apart from the latest season was 53.2% and significantly higher among WLP than KTR (P = .007). Pneumococcal vaccine uptake was only 4% overall. The only factor positively associated with influenza vaccine uptake in the latest season was any prior influenza vaccine uptake (OR 5.79, CI95 2.44-13.76) (P < .001). Recommendations given by other persons (non-physician) were negatively associated with receiving the influenza vaccination in the latest season (OR 0.34, CI95 0.13-0.92) (P = .03). Reasons for not being vaccinated were primarily lack of information, perception of own good health, and fear of adverse reactions. CONCLUSIONS: Influenza and pneumococcal vaccine uptakes were suboptimal among Danish WLP and KTR. Increased awareness about guidelines and physicians´ education are warranted.

Synthesis of Au@Cu2O Core-Shell Nanoparticles with Tunable Shell Thickness and Their Degradation Mechanism in Aqueous Solutions.

Metal@semiconductor core-shell nanoparticles (NPs) are widely used in photocatalysts, sensors, and optical applications owing to their unique metal-semiconductor interface and the integration of the properties from both core and shell materials. Although many efforts have been made toward the precise synthesis of Au@Cu2O core-shell structures, the chemical stability of Au@Cu2O aqueous suspensions, which is of great significance in many related applications, is not mentioned in any published research. Herein we report the synthesis of Au@Cu2O core-shell NPs with small shell thickness from 2 to 40 nm through a wet-chemistry method. The UV-vis absorption properties are found to be tunable with Cu2O thickness in the range of 2-40 nm. Furthermore, the chemical stability of Au@Cu2O core-shell nanoparticle suspensions in water/ethanol mixed solvents is investigated. It is found that water/ethanol mixed solvents with a larger amount of water are more likely to deteriorate the stability of Au@Cu2O NPs by oxidizing Cu2O to CuO. The results from this work may provide useful information for the preparation of metal@Cu2O water-based suspensions that are expected to be used for SERS, photocatalyst, or photothermal applications.

Highly Correlated Size and Composition of Pt/Au Alloy Nanoparticles via Magnetron Sputtering onto Liquid.

Pt/Au alloy nanoparticles (NPs) in a wide composition range have been synthesized by room-temperature simultaneous sputter deposition from two independent magnetron sources onto liquid PEG (MW = 600). The prepared NPs were alloyed with the face-centered cubic (fcc) structure. In addition, the particle sizes, composition, and shape are strongly correlated but can be tailored by an appropriate variation of the sputtering parameters. No individual particle but large agglomerates with partial alloy structure formed at Pt content of less than 16 atom %. Highly dispersed NPs with no agglomeration were observed in PEG when the quantity of Pt is more than 26 atom %. On the other hand, a small amount of Pt could terminate the agglomeration of Au when sputtering on the grids for transmission electron microscope observation. Our experiment and computer simulation carried out by two different methods indicate that the composition-dependent particle size of Pt/Au can be explained by the atomic concentration, formation energy of the cluster, and interaction between different metal atoms and the PEG molecule.

Enhanced Cycling Performance of Rechargeable Zinc-Air Flow Batteries Using Potassium Persulfate as Electrolyte Additive.

Zinc-air batteries (ZABs) offer high specific energy and low-cost production. However, rechargeable ZABs suffer from a limited cycle life. This paper reports that potassium persulfate (KPS) additive in an alkaline electrolyte can effectively enhance the performance and electrochemical characteristics of rechargeable zinc-air flow batteries (ZAFBs). Introducing redox additives into electrolytes is an effective approach to promote battery performance. With the addition of 450 ppm KPS, remarkable improvement in anodic currents corresponding to zinc (Zn) dissolution and limited passivation of the Zn surface is observed, thus indicating its strong effect on the redox reaction of Zn. Besides, the addition of 450 ppm KPS reduces the corrosion rate of Zn, enhances surface reactions and decreases the solution resistance. However, excess KPS (900 and 1350 ppm) has a negative effect on rechargeable ZAFBs, which leads to a shorter cycle life and poor cyclability. The rechargeable ZAFB, using 450 ppm KPS, exhibits a highly stable charge/discharge voltage for 800 cycles. Overall, KPS demonstrates great promise for the enhancement of the charge/discharge performance of rechargeable ZABs.

Binder-Free α-MnO2 Nanowires on Carbon Cloth as Cathode Material for Zinc-ion Batteries.

Recently, rechargeable zinc-ion batteries (ZIBs) have gained a considerable amount of attention due to their high safety, low toxicity, abundance, and low cost. Traditionally, a composite manganese oxide (MnO2) and a conductive carbon having a polymeric binder are used as a positive electrode. In general, a binder is employed to bond all materials together and to prevent detachment and dissolution of the active materials. Herein, the synthesis of α-MnO2 nanowires on carbon cloth via a simple one-step hydrothermal process and its electrochemical performance, as a binder-free cathode in aqueous and nonaqueous-based ZIBs, is duly reported. Morphological and elemental analyses reveal a single crystal α-MnO2 having homogeneous nanowire morphology with preferential growth along {001}. It is significant that analysis of the electrochemical performance of the α-MnO2 nanowires demonstrates more stable capacity and superior cyclability in a dimethyl sulfoxide (DMSO) electrolyte ZIB than in an aqueous electrolyte system. This is because DMSO can prevent irreversible proton insertion as well as unfavorable dendritic zinc deposition. The application of the binder-free α-MnO2 nanowires cathode in DMSO can promote follow-up research on the high cyclability of ZIBs.

MnO2 Heterostructure on Carbon Nanotubes as Cathode Material for Aqueous Zinc-Ion Batteries.

Due to their cost effectiveness, high safety, and eco-friendliness, zinc-ion batteries (ZIBs) are receiving much attention nowadays. In the production of rechargeable ZIBs, the cathode plays an important role. Manganese oxide (MnO2) is considered the most promising and widely investigated intercalation cathode material. Nonetheless, MnO2 cathodes are subjected to challenging issues viz. limited capacity, low rate capability and poor cycling stability. It is seen that the MnO2 heterostructure can enable long-term cycling stability in different types of energy devices. Herein, a versatile chemical method for the preparation of MnO2 heterostructure on multi-walled carbon nanotubes (MNH-CNT) is reported. Besides, the synthesized MNH-CNT is composed of δ-MnO2 and γ-MnO2. A ZIB using the MNH-CNT cathode delivers a high initial discharge capacity of 236 mAh g-1 at 400 mA g-1, 108 mAh g-1 at 1600 mA g-1 and excellent cycling stability. A pseudocapacitive behavior investigation demonstrates fast zinc ion diffusion via a diffusion-controlled process with low capacitive contribution. Overall, the MNH-CNT cathode is seen to exhibit superior electrochemical performance. This work presents new opportunities for improving the discharge capacity and cycling stability of aqueous ZIBs.

Preparation and Growth Mechanism of Pt/Cu Alloy Nanoparticles by Sputter Deposition onto a Liquid Polymer.

We use a green sputtering technique to deposit a Pt/Cu alloy target on liquid polyethylene glycol (PEG) to obtain well-dispersed and stable Pt29Cu71 alloy nanoparticles (NPs). The effects of sputtering current, rotation speed of the stirrer, sputtering time, sputtering period, and temperature of PEG on the particle size are studied systematically. Our key results demonstrate that the aggregation and growth of Pt/Cu alloy NPs occurred at the surface as well as inside the liquid polymer after the particles landed on the liquid surface. According to particle size analysis, a low sputtering current, high rotation speed for the stirrer, short sputtering period, and short sputtering time are found to be favorable for producing small-sized single crystalline alloy NPs. On the other hand, varying the temperature of the liquid PEG does not have any significant impact on the particle size. Thus, our findings shed light on controlling NP growth using the newly developed green sputtering deposition technique.

4-Hydroxypanduratin A and Isopanduratin A Inhibit Tumor Necrosis Factor α-Stimulated Gene Expression and the Nuclear Factor κB-Dependent Signaling Pathway in Human Lung Adenocarcinoma A549 Cells.

Tumor necrosis factor α (TNF-α), a pro-inflammatory cytokine, regulates inflammatory and immune responses by up-regulating gene expression in a manner that is dependent on the transcription factor nuclear factor κB (NF-κB). In the present study, we found that 4-hydroxypanduratin A and isopanduratin A, constituents of the rhizomes of Boesenbergia pandurata, inhibited the TNF-α-stimulated up-regulation of intercellular adhesion molecule-1 (ICAM-1) in human lung adenocarcinoma A549 cells. 4-Hydroxypanduratin A and isopanduratin A also reduced ICAM-1 mRNA expression and NF-κB-responsive luciferase activity in TNF-α-stimulated A549 cells. Moreover, 4-hydroxypanduratin A and isopanduratin A prevented the TNF-α-stimulated translocation of the NF-κB subunit p65 to the nucleus and the phosphorylation and proteasomal degradation of the inhibitor of the NF-κB α protein. The present results revealed that 4-hydroxypanduratin A and isopanduratin A inhibit TNF-α-stimulated gene expression and the NF-κB-dependent signaling pathway in A549 cells.

Sub-2 nm Single-Crystal Pt Nanoparticles via Sputtering onto a Liquid Polymer.

Matrix sputtering with the use of a low vapor pressure liquid as its matrix becomes a green technique to prepare nanoparticles dispersed in liquid. In the present study, we proposed using this method with polyethylene glycol (PEG, molecular weight = 600) as the liquid matrix to produce highly uniform Pt nanoparticles with a small size (below 2.0 nm) and a narrow size distribution. The results indicated that particle sizes were tailorable from 0.9 ± 0.3 to 1.4 ± 0.3 nm by varying the sputtering current (5-50 mA) with negligible particle aggregation that occurred in PEG during sputtering. The slight growth of the particle size observed after sputtering was attributed to the addition of free Pt atoms to the existing Pt nanoparticles. All samples formed stable dispersion in PEG for 5 month storage. This result suggested an advantage of using a liquid matrix to produce and stabilize nanoparticles.

Synthesis of Positively Charged Photoluminescent Bimetallic Au-Ag Nanoclusters by Double-Target Sputtering Method on a Biocompatible Polymer Matrix.

Herein, we report a novel positively charged photoluminescent Au-Ag bimetallic nanocluster synthesized using 11-mercaptoundecyl-N,N,N-trimethylammonium bromide as the capping ligand by means of "green" double-target sputtering method on a biocompatible polymer matrix. The photoluminescent Au-Ag bimetallic cluster showed emission tunability from blue to near infrared (NIR) regions with respect to change in the composition.

Au/Cu Bimetallic Nanoparticles via Double-Target Sputtering onto a Liquid Polymer.

Alloy nanoparticles (NPs) of a bimetal system, Au/Cu, that form intermetallic compounds in a bulk state have been successfully produced using a double-target sputtering technique onto a low-cost and biocompatible liquid polymer (polyethylene glycol, PEG). The formation of an Au/Cu solid solution alloy in individual NPs was revealed by scanning transmission electron microscopy-energy-dispersive X-ray elemental mapping analysis. Altering the sputter currents for Au and Cu targets resulted in a tailored NP composition, but the particle sizes did not significantly vary. We found similar structures, sizes, and optical properties of Au/Cu NPs obtained by double-head sputtering on carbon-coated transmission electron microscopy grids or PEG and by Au/Cu alloy target sputtering. Random alloy formation occurred in matrix sputtering using double-target heads. This method is advantageous for manipulating the alloy composition through highly independent control of sputter parameters for each metal target.

Constituents of the Rhizomes of Boesenbergia pandurata and Their Antiausterity Activities against the PANC-1 Human Pancreatic Cancer Line.

Human pancreatic cancer cell lines have a remarkable tolerance to nutrition starvation, which enables them to survive under a tumor microenvironment. The search for agents that preferentially inhibit the survival of cancer cells under low nutrient conditions represents a novel antiausterity strategy in anticancer drug discovery. In this investigation, a methanol extract of the rhizomes of Boesenbergia pandurata showed potent preferential cytotoxicity against PANC-1 human pancreatic cancer cells under nutrient-deprived conditions, with a PC50 value of 6.6 µg/mL. Phytochemical investigation of this extract led to the isolation of 15 compounds, including eight new cyclohexene chalcones (1-8). The structures of the new compounds were elucidated by NMR spectroscopic data analysis. Among the isolated compounds obtained, isopanduratin A1 (14) and nicolaioidesin C (15) exhibited potent preferential cytotoxicity against PANC-1 human pancreatic cancer cells under nutrition-deprived conditions, with PC50 values of 1.0 and 0.84 µM, respectively.

α-Glucosidase Inhibitory and Cytotoxic Taxane Diterpenoids from the Stem Bark of Taxus wallichiana.

From a CH2Cl2 extract of the bark of Taxus wallichiana, six new taxoids, wallitaxanes A-F (1-6), were isolated, together with 29 known compounds. The structures of the new compounds were elucidated on the basis of spectroscopic data interpretation. Wallitaxane D (4) was identified as an opened oxetane-type taxoid having the first naturally occurring C(H)-20 acetal group, while wallitaxanes E (5) and F (6) are representative of the rare abeo-taxoid class. The isolated compounds were evaluated for their α-glucosidase inhibitory activity and for cytotoxicity against the HeLa human cervical cancer cell line. In the present work, taxanes were found to exhibit α-glucosidase inhibitory activity for the first time, and wallitaxane A (1) showed the most potent effect, with an IC50 value of 3.6 µM. In turn, 7-epi-taxol (16) and 7-epi-10-deacetyltaxol (17) showed IC50 values of 0.05 and 0.085 nM, respectively, against HeLa cells.

Femtosecond laser-induced hard X-ray generation in air from a solution flow of Au nano-sphere suspension using an automatic positioning system.

Femtosecond laser-induced hard X-ray generation in air from a 100-µm-thick solution film of distilled water or Au nano-sphere suspension was carried out by using a newly-developed automatic positioning system with 1-µm precision. By positioning the solution film for the highest X-ray intensity, the optimum position shifted upstream as the laser power increased due to breakdown. Optimized positioning allowed us to control X-ray intensity with high fidelity. X-ray generation from Au nano-sphere suspension and distilled water showed different power scaling. Linear and nonlinear absorption mechanism are analyzed together with numerical modeling of light delivery.

MHz-ultrasound generation by chirped femtosecond laser pulses from gold nano-colloidal suspensions.

Strong absorption of femtosecond laser pulses in Au nano-colloidal suspensions was used to generate coherent ultrasound signals at 1-20 MHz frequency range. The most efficient ultrasound generation was observed at negative chirp values and was proportional to the pulse duration. Maximization of a dimensionless factor A ≡ αc0tp defined as the ratio of pulse duration tp and the time required for sound at speed c0 to cross the optical energy deposition length (an inverse of the absorption coefficient α) given by 1/(αc0). Chirp controlled pulse duration allows effective enhancement of ultrasound generation at higher frequencies (shorter wavelengths) and is promising for a high spatial resolution acoustic imaging.