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105 at 1064 nm. Theoretical calculations have been performed to clarify the correlation between the molecular structure and the optical properties of PVOFS.A bimodal-pore strategy was developed for preparation of the Pt3Co/C catalyst with active Pt3Co nanoparticles located around the mass transfer channels rather than inside them, which leads to ca. 29% higher mass transfer efficiency and a superior single-cell performance under an ultralow Pt loading.Hyperbranched, biodegradable PCL-based polymers are obtained through a random but invasive migration of an in situ generated carbene end group which is unmasked via the thermolysis of its precursor diazirine moiety. These hyperbranched cores are used as macroinitiators for 'grafting-from' polymerisation using controlled radical polymerisation to achieve amphiphilic copolymers which can subsequently be self-assembled into spherical core-shell micelles.Steric hindrance induced by thiophene molecules in predesigned precursors favors the exclusive formation of a three dimensional (3D) π-conjugated cage and quasi-cage like molecules instead of a porphyrinoid macrocycle. Herein we report the synthesis of a tetrapod 3D fully π-conjugated molecular cage using a simple acid catalysed reaction. The X-Ray crystallography analysis confirmed the tetrapod cage structure and intermediates, which resemble three-fourths or half of the cage structures.We propose a conceptual model that describes the in situ formation of androstenedione in agricultural soil from a phytosterol, β-sitosterol, released after crop harvest and soil fertiliser amendment. Based on the recorded agricultural practice at a spring barley field, β-sitosterol and androstenedione concentrations were modelled over the year. PI3K inhibitor While decomposition of crop residues created low soil levels, the application of pig slurry led to an androstenedione soil concentration of 54 μg kg-1. The elevated soil concentration of androstenedione is not due to the introduction of the endocrine disruptor in the fertiliser, but a result of the addition of large concentrations of β-sitosterol as a natural precursor. The limited available data on β-sitosterol and androstenedione concentration in soil prohibited their accurate prediction by our model. However, the potential implication of endocrine-disrupting steroid hormones being formed in situ from currently little considered phytosterols justifies a conceptual description and further research.Pantothenate synthetase from Escherichia coli (PSE. coli) catalyzes the ATP-dependent condensation of (R)-pantoic acid and β-alanine to yield (R)-pantothenic acid (vitamin B5), the biosynthetic precursor to coenzyme A. Herein we show that besides the natural amine substrate β-alanine, the enzyme accepts a wide range of structurally diverse amines including 3-amino-2-fluoropropionic acid, 4-amino-2-hydroxybutyric acid, 4-amino-3-hydroxybutyric acid, and tryptamine for coupling to the native carboxylic acid substrate (R)-pantoic acid to give amide products with up to >99% conversion. The broad amine scope of PSE. coli enabled the efficient synthesis of pharmaceutically-relevant vitamin B5 antimetabolites with excellent isolated yield (up to 89%). This biocatalytic amide synthesis strategy may prove to be useful in the quest for new antimicrobials that target coenzyme A biosynthesis and utilisation.We propose to create nanospheres in aqueous solutions from coordination polymers of Ag+ with a combination of a hydrophilic and a hydrophobic thiol, of diameter ca. 2.7 nm in the case of using cysteine and n-butanethiol. A spectral probe for the formation of the nanospheres is a reversal of the CD signal at 253 nm from negative in the case of cysteine alone to positive when cysteine and n-BuSH are both employed, together with an amplification.Quantifying the isomeric species of metal complexes in solution is difficult. 19F NMR herein was used to determine the abundance of isomeric species and dynamic properties of lanthanide binding tags. The results suggest that 19F is an efficient reporter in assessing and screening paramagnetic tags suitable for protein NMR analysis.With the assistance of Ac in sulfoximine as a protecting group (PG) and MeOH as a de-PG agent, Pd-catalyzed multicomponent reactions were developed to access indene-fused medium-size sulfoximine heterocycles. The reactions proceeded smoothly under exceptionally mild conditions to produce polyheterocyclic sulfoximines with regiospecificity and good functional group tolerance. A double carbopalladation/syn-insertion of triple bond sequences was proposed tothis transformation.The concentration of glycocholic acid (GCA) in urine and blood is an important biomarker for liver cancer. Monitoring of GCA depends to a large extent on the availability of appropriate analytical techniques. In this work, based on the immobilization of GCA-OVA onto the sensor chip surface, a label-free competitive inhibition immunoassay for the determination of GCA with the surface plasmon resonance (SPR) technique was developed. The proposed SPR immunosensor is simple to prepare, recyclable and exhibits excellent sensitivity to GCA (a linear range of 13.3-119.4 ng mL-1 and a limit of detection (LOD) of 2.5 ng mL-1), which was 14 times lower than that of the traditional immunoassay. Excellent recoveries and correlation between these two methods were observed (R2 = 0.995). Hence, it can be proved that the SPR immunosensor could be used to achieve rapid and sensitive quantitative detection of GCA in real urine samples and meet clinical needs.Combined antitumor therapies based on nanomedicines have shown efficacy in various tumor models in recent years, overcoming the disadvantages of inefficiency and undesired toxicity of traditional therapies. Herein, we present a copper sulfide- and doxorubicin-loaded gold nanorods@mesoporous SiO2 multifunctional nanocomposite (AuNR@mSiO2@DOX-CuxS-PEG) to integrate chemotherapy, the photothermal properties of AuNRs, and the photodynamic properties of CuxS into a single nanoplatform based on hydrophobic interaction and electrostatic attraction. Upon near-infrared light irradiation, the AuNR@mSiO2@DOX-CuxS-PEG nanocomposites exhibit a synergistic therapeutic effect and inhibit the in situ tumor growth and lung metastasis in a melanoma model. This occurs because of the high photothermal conversion efficiency, boosted intracellular reactive oxygen species production, and excellent doxorubicin (DOX) release, as well as an induced tumor-specific immune response. The inspired antitumor immunity was confirmed by elevated infiltration of activated T cells in tumor tissues and improved maturation and activation of dendritic cells in tumor-draining lymph nodes. This study highlights the superior antitumor therapeutic effect elicited by a multifunctional nanoplatform for skin with in situ melanoma and lung metastasis inhibition, indicating its satisfactory clinical application prospects.Acetalated dextran (Ac-DEX) is a pH-responsive dextran derivative polymer. Prepared by a simple acetalation reaction, Ac-DEX has tunable acid-triggered release profile. Despite its relatively short research history, Ac-DEX has shown great potential in various therapeutic applications. Furthermore, the recent functionalization of Ac-DEX makes versatile derivatives with additional properties. Herein, we summarize the cutting-edge development of Ac-DEX and related polymers. Specifically, we focus on the chemical synthesis, nano- and micro-particle fabrication techniques, the controlled-release mechanisms, and the rational design Ac-DEX-based of drug delivery systems in various biomedical applications. Finally, we briefly discuss the challenges and future perspectives in the field.The first palladium-catalyzed Ugi-type multicomponent reaction for the synthesis of N-acyl anthranilamides from isocyanides, 2-iodoanilines and carboxylic acids has been developed. This method provides expeditious and highly efficient access to structurally diverse N-acyl anthranilamides from readily available starting materials with good functional group compatibility. link2 The utility of this method has been demonstrated by the late stage functionalization of two commercial drugs Flurbiprofen and Loxoprofen.Copper hydrides are very useful in hydrogenation reactions. We report a stable Stryker-type copper hydride reagent protected by hemilabile phosphines [Cu8H6(dppy)6](OTf)2 (Cu8-H, dppy = diphenylphosphino-2-pyridine). The metal core of this cluster has a bicapped octahedral configuration, and the copper-bound hydrides each triply bridges over a triangular face of the octahedron. This cluster is attractive due to its facile preparation and excellent stability under ambient conditions. The comparable activity and selectivity both in the stoichiometric and catalytic reactions make Cu8-H a promising alternative to Stryker's reagent.Solid phase synthesis of RNA oligonucleotides which are over 100-nt in length remains challenging due to the complexity of purification of the target strand from failure sequences. This work describes a non-chromatographic strategy that will enable routine solid phase synthesis of long RNA strands.We have fabricated Pt-Ca nanoparticles with oxygen reduction reaction catalytic activity via a sodium vapor-induced synthesis method. Prior addition of NaCl to form a eutectic mixture of CaCl2 and NaCl facilitated the formation of intermetallic Pt2Ca nanoparticles. Pt3Mg and Pt5Sr nanoparticles also were suggested to be producible.Commercial sodium citrate is proposed as the self-sacrificial cathode additive for the first time to offset the initial sodium loss. The optimum additive can obviously increase the energy density of the as-constructed hard carbon//Na3V2(PO4)2F3/rGO full-cell by 28.9% without sacrificing its other electrochemical properties, showing promising application prospects in sodium ion batteries.In this work, by using N-methoxybenzamides as efficient acyl nitrene precursors, an iron-catalyzed formal cis-haloamidation of alkyne is reported. Without assistance of additives, the reaction worked well in the presence of 50 mol% FeCl3 or FeBr3, leading to a series of chloro/bromo-containing isoindolin-5-ones with high efficiency and wide reaction scope. In the reaction, the iron-facilitated haloamidation proceeds through a halo anion-participating concerted [3+2] cyclization to release the final products. The key intermediate ferric acyl nitrene A is generated in situ from a formal removal of MeOH.Liquid sampling-atmospheric pressure glow discharge-mass spectrometry (LS-APGD-MS) and inductively coupled plasma-optical emission spectroscopy (ICP-OES) were employed for the quantification of trace metals in cell culture media and their capabilities compared. The LS-APGD is interfaced here to a compact mass spectrometer (Advion CMS) towards the development of an at-bioreactor process monitoring strategy. link3 Both techniques have been previously employed for the quantification of trace metals in samples of various complexities, making them a natural choice for this application. They have also demonstrated comparable analytical figures of merit including limits of detection (LOD), matrix tolerance, etc. While cell culture media is a complex sample, the ICP-OES technique was unaffected by the matrix. However, the LS-APGD-MS suffered from increases in spectral background. Despite this, both techniques achieved appropriate LODs for all metals analyzed in this work (Cu, Fe, Zn, Co, Mn, Ni; LOD less then 100 ng mL-1), except for Mn and Ni via LS-APGD-MS.

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