Near generalized balanced tournament designs with block sizes 4 and 5

A near generalized balanced tournament design, or an NGBTD(k,m) in short, is a (km + 1, k, k − 1)-BIBD defined on a (km +1)-set V. Its blocks can be arranged into an m × (km + 1) array in such a way that (1) the blocks in every column of the array form a partial parallel class partitioning V[x] for some point x, and (2) every element of V is contained in precise k cells of each row. In this paper, we completely solve the existence of NGBTD(4,m) and almost completely solve the existence of NGBTD(5,m) with four exceptions.     

Tunable Oxygen Activation for Catalytic Organic Oxidation: Schottky Junction versus Plasmonic Effects

The charge state of the Pd surface is a critical parameter in terms of the ability of Pd nanocrystals to activate O₂ to generate a species that behaves like singlet O₂ both chemically and physically. Motivated by this finding, we designed a metal–semiconductor hybrid system in which Pd nanocrystals enclosed by {100} facets are deposited on TiO₂ supports. Driven by the Schottky junction, the TiO₂ supports can provide electrons for metal catalysts under illumination by appropriate light. Further examination by ultrafast spectroscopy revealed that the plasmonics of Pd may force a large number of electrons to undergo reverse migration from Pd to the conduction band of TiO₂ under strong illumination, thus lowering the electron density of the Pd surface as a side effect. We were therefore able to rationally tailor the charge state of the metal surface and thus modulate the function of Pd nanocrystals in O₂ activation and organic oxidation reactions by simply altering the intensity of light shed on Pd–TiO₂ hybrid structures.     

Mechanistic Insights into the Interface‐Directed Transformation of Thiols into Disulfides and Molecular Hydrogen by Visible‐Light Irradiation of Quantum Dots

Quantum dots (QDs) offer new and versatile ways to harvest light energy. However, there are few examples involving the utilization of QDs in organic synthesis. Visible‐light irradiation of CdSe QDs was found to result in virtually quantitative coupling of a variety of thiols to give disulfides and H₂ without the need for sacrificial reagents or external oxidants. The addition of small amounts of nickel(II) salts dramatically improved the efficiency and conversion through facilitating the formation of hydrogen atoms, thereby leading to faster regeneration of the ground‐state QDs. Mechanistic studies reveal that the coupling reaction occurs on the QD surfaces rather than in solution and offer a blueprint for how these QDs may be used in other photocatalytic applications. Because no sacrificial agent or oxidant is necessary and the catalyst is reusable, this method may be useful for the formation of disulfide bonds in proteins as well as in other systems sensitive to the presence of oxidants.     

Sorption and desorption of phenanthrene onto iron, copper, and silicon dioxide nanoparticles

The sorption and desorption of phenanthrene by three engineered nanoparticles including nanosize zerovalent iron (NZVI), copper (NZVC), and silicon dioxide (NSiO2) were investigated. The sorption of phenanthrene onto NSiO2 was linear and reversible due to the hydrophilic properties of NSiO2. In comparison, sorption of phenanthrene onto NZVI and NZVC was nonlinear and irreversible, which was potentially due to the existence of significantly heterogeneous surface energy distribution patterns detected by a standard molecular probe technique. Naphthalene exerted significant competitive sorption with phenanthrene for NZVI and NZVC, and the isotherm of phenanthrene changed from being significantly nonlinear to nearly linear when naphthalene was simultaneously absorbed. A surface adsorption mechanism was proposed to explain the observed sorption and competition of phenanthrene on both NZVI and NZVC. In contrast, no competition was observed for sorption onto NSiO2. The sorption of phenanthrene on all three nanoparticles significantly decreased with increasing pH. The sorption irreversibility of phenanthrene on NZVI and NZVC were significantly enhanced with decreasing pH. A pH-dependent hydrophobic effect and dipole interactions between the charged surface (electron acceptors) and phenanthrene with electron-rich pi systems (electron donors) were proposed to explain the observed pH-dependent sorption.     

Bright Free-Radical Emission in Ionic Liquids

It is challenging to achieve stable and efficient radical emissions under ambient conditions. Herein, we present a rational design strategy to protect photoinduced carbonyl free radical emission through electrostatic interaction and spin delocalization effects. The host-guest system is constructed from tricarbonyl-substituted benzene molecules and a series of imidazolium ionic liquids as the guest and host, respectively, whereby the carbonyl anion radical emission can be in situ generated under the light irradiation and further stabilized by electrostatic interaction. More importantly, the anion species and the alkyl chain length of imidazolium ionic liquids show a noticeable effect on luminescence efficiency, with the highest radical emission efficiency is as high as 53.3 % after optimizing the imidazole ionic liquid's structure, which is about four times higher than the polymer-protected radical system. Theoretical calculations confirm the synergistic effect of strong electrostatic interactions and that the spin delocalization effect significantly stabilizes the radical emission. Moreover, such a radical emission system also could be integrated with a fluorescent dye to induce multi-color or even white light emission with reversible temperature-responsive characteristics. The radical emission system can also be used to detect different amine compounds on the basis of the emission changes and photoactivation time.     

Semiconductor SERS on Colourful Substrates with Fabry-Pérot Cavities

Non-metallic materials have emerged as a new family of active substrates for surface-enhanced Raman scattering (SERS), with unique advantages over their metal counterparts. However, owing to their inefficient interaction with the incident wavelength, the Raman enhancement achieved with non-metallic materials is considerably lower with respect to the metallic ones. Herein, we propose colourful semiconductor-based SERS substrates for the first time by utilizing a Fabry-Pérot cavity, which realize a large freedom in manipulating light. Owing to the delicate adjustment of the absorption in terms of both frequency and intensity, resonant absorption can be achieved with a variety of non-metal SERS substrates, with the sensitivity further enhanced by ≈100 times. As a typical example, by introducing a Fabry-Pérot-type substrate fabricated with SiO₂/Si, a rather low detection limit of 10⁻¹⁶ M for the SARS-CoV-2S protein is achieved on SnS₂. This study provides a realistic strategy for increasing SERS sensitivity when semiconductors are employed as SERS substrates.     

Synthesis and Characterization of 2-[(3-Aminophenyl)sulfonyl] ethanol Hydrogen Sulfate

2-[(3-Aminophenyl)sulfonyl] ethanol hydrogen sulfate (APSES) is an important intermediate for reactive dyes.It can be used to synthesize KN type reactive dyes, which have broad colour spectra,good water solubility, excellent adaptability for different dye technique,etc. Synthesis of APSES were currently developed by Kato Kuniok et al^[1] and Sanki^[2].Kato had attempted to synthesize of APSES by reaction of sodium benzenesulfinate as raw material with ethylene oxide to obtain 2-phenylsulfonyl ethanol(PSE). The PSE could further be nitrated and hydrogenated to obtain 2-[(3-aminophenyl)sulfonyl]ethanol (APSE). Finally,APSE was reacted with oleum to obtain 2-[(3-aminophenyl) sulfonyl] ethanol hydrogen sulfate (APSES). Sanki had discoved a new synthetic method for the PSE. The PSE was prepared by first reaction of thiophenol as raw material with chloroethanol, and then by oxidation with hydrogen peroxide.The above mentioned two methods are not easily be adopted in industries at home. The shortage and cost of the thiophenol and sodium benzenesulfinate are mainly limited. We modificated a new synthetic pathway for APSES by five steps. The experimental procedures are shown the following.     

Synthesis and Properties of Double Calix[4]arene Derivatives Linked by Schiff-base in the Lower Rim

Calixarenesareregardedasthethirdgenerationofh0stmoleculesbecauseoftheirinclusionabilitytocati0ns,anionsandneutralmoleculesI'2.Duringthepastdecademosteff0rtshavebeentakenonthefunctionalizati0n0fcalixareness0thattheycanbeappliedn0tonlyastheionoph0resintheextractionprocess','andassensitivematerialsforionelectrodes"',butalsoastheenZymemimicscatalyzingthecleavageofphosphatediesters"'.Inordertoenablethemtoincludeandrecognizelargerchemicalspecies,manyappr0acheshavebeenusedtoc0nstructoIigo-calixarene…     

Highly efficient heterogeneous procedure for the synthesis of fructone fragrancy

A novel heterogeneous strong acid catalyst was synthesized through the copolymerization of p-toluenesulfonic acid and paraformaldehyde and utilized for the synthesis of fructone. The results showed that the catalyst was very efficient for the reaction with the yield over 95%. The advantages of extremely high density of acidity, high thermal and chemical stability, low cost for the simple synthetic procedure, and reusability made the catalyst one of the best choices for the reaction.     

Bioelectrochemical response of a choline biosensor fabricated by using polyaniline

On the basis of the isoelectric point of an enzyme and the doping principle of conducting polymers, choline oxidase was doped in a polyaniline film to form a biosensor. The amperometric detection of choline is based on the oxidation of the H₂O₂ enzymatically produced on the choline biosensor. The response current of the biosensor as a function of temperature was determined from 3 to 40°C. An apparent activation energy of 22.8 kJ·mol⁻¹ was obtained. The biosensor had a wide linear response range from 5 × 10⁻⁷ to 1 × 10⁻⁴ M choline with a correlation coefficient of 0.9999 and a detection limit of 0.2 μM, and had a high sensitivity of 61.9 mA·M⁻¹·cm⁻² at 0.50 V and at pH 8.0. The apparent Michaelis constant and the optimum pH for the immobilized enzyme are 1.4 mM choline and 8.4, respectively, which are very close to those of choline oxidase in solution. The effect of selected organic compounds on the response of the choline biosensor was studied.