To the issue of temperature-dependent behavior of standard molar volumes of components in the binary system (water + tetrahydrofuran) at ambient pressure

This report presents a comparative analysis of temperature-dependent data on density of both dilute aqueous solutions of tetrahydrofuran (THF) and dilute solutions of water in THF, as well as standard molar volumes of water or THF as a solute. For this purpose, new results on studying the volume-related properties of THF in a water-rich region at temperatures from (278.15 to 318.15) K, with a step of 5 K, and at the ambient pressure have been derived densimetrically. In discussion, some comments on previously published investigations, being related to temperature-dependent changes in the solution density and standard molar volumes of components of the system (water + THF), have been made.     

Low molecular weight organogelators derived from threefold symmetric tricarbamates

A group of new low molecular weight organogelators based on threefold symmetric tricarbamate were synthesized and characterized. The tricarbamates with long alkyl chains were able to gelate a wide range of polar and nonpolar organic solvents such as acetonitrile and cyclohexane, generally at concentrations lower than 20 g/L. The best organogel formation was obtained using a threefold symmetric tricarbamate in n-dodecane, in which a sufficiently transparent gel was formed at the critical gelation concentration 1 g/L. Intermolecular hydrogen bonding by the tricarbamate in a nonpolar solvent benzene-d₆ was indicated by ¹H NMR spectra. Its maximum UV absorption was 11 nm higher in chloroform than in n-dodecane, and this red shift indicated increased conjugation between the benzene core and the carbamate substituents, which confirmed a change in its conformation from nonpolar to polar solvent. The self-assembling behavior of the tricarbamate in dilute solutions was investigated by TEM. Fiber-like networks were observed in a large range of solution concentrations.     

Organocatalytic chemoselective monoacylation of 1,n-linear disulfonamides

Predominant monoacylation of 1,n-linear disulfonamides took place in the presence of pyrrolidinopyridine-type organocatalysts when the chain length of the linear disulfonamides was n = 3, 4, or 5 (monoacylate/diacylate = up to 44). The chemoselectivity of the competitive acylation between N,N′-ditosyl-1,5-pentanediamine (n = 5) and N,N′-ditosyl-1,3-propanediamine (n = 3) was found to be 36, favoring the former substrate. Different chain length by only one carbon atom was discriminated in the competitive acylation between N,N′-ditosyl-1,5-pentanediamine (n = 5) and of N,N′-ditosyl-1,4-butanediamine (n = 4) with the relative acylation rate of 16 in the presence of the organocatalyst.     

Novel phosphorescent neutral iridium(III) complex with the steric hindrance for highly efficient red organic light-emitting diodes

A novel and highly efficient thiophenquinolone-based red iridium(III) complex bearing a bulky fluorophenyl moiety is designed and synthesized. The complex shows intensive red phosphorescence (596 nm with shoulder at 642 nm), high photoluminescence efficiency (0.62) and broad full width at half maximum (81 nm). The bulky fluorophenyl moiety introduced into the complex could improve the efficiency of electroluminescence with the maximum current efficiency, power efficiency and the external quantum efficiency up to 29.0 cd/A, 30.4 lm/W and 17.6% due to the effective steric hindrance in solid states.     

A novel fluorescent probe with a large Stokes shift for real-time imaging mitochondria in different living cell lines

Fluorescent dyes with large Stokes shift play a key role in avoiding self-quenching and scattered light of dyes in the process of biological imaging. In this work, a novel mitochondria-targetable fluorescent dye (PI-C2) with large Stokes shift (e. g. Maximum value is 219 nm in DMSO) have been developed. Compared to the commercial mitochondria probes MTR and MTG (Less than 30 nm in various solution), the newly constructed PI-C2 has a much larger Stokes shift in various solutions (169–219 nm in various solutions). Furthermore, the probe can successfully be applied for sensing mitochondria, and exhibited excellent photostability in different living cell lines. The novel fluorescent platform with the large Stokes may be extended to construct powerful fluorescent probes with large Stokes shift for detecting a wide variety of biomolecules in mitochondria.     

Super-resolution morphological dissemination of intercalating dye in single DNA molecules via binding activated localization microscopy

Super-localization of intercalating dye YOYO-1 in single λ-DNA at super-resolution by binding activation localization microscopy (BALM).     

Highly sensitive fluorescent sensor targeting CuCl2 based on thiophene attached anthracene compound (TA)

A novel thiophene attached anthracene (TA) based fluorescent compound was designed and synthesized. The TA showed a high quantum yield (Qy = 0.34) in regard to fluorescence. We applied this TA compound to detect specific metal compound and found that it could identify CuCl₂ from other metals through dramatic fluorescence change at λ_max = 460 nm. It showed strong quenching fluorescence property with CuCl₂ while with other metal compounds it exhibited strong blue fluorescence emission. UV/Vis absorption spectroscopy clearly demonstrated that the quenching property of TA at λ_max = 460 nm was due to overlapping of the fluorescence peak of TA at λ_max = 460 nm and the absorption band of CuCl₂ (from 190 nm to 525 nm). Binding constant (K′), which was 0.0895 mM^?2, indicated a complexation ratio between TA and CuCl₂ as 1:2 and this interaction induced quenching property.     

Highly selective fluorescence turn-on determination of fluoride ions via chromogenic aggregation of a silyloxy-functionalized salicylaldehyde azine

A novel fluorescent chemsensor TBS-protected salicylaldehyde azine (TSAA) for fluoride ion was developed based on aggregation-induced emission (AIE). The probe TSAA was prepared by the reaction of salicylaldehyde azine (SAA) with tert-butyldimethylsilyl chloride (TBS-Cl) via an unusual synthetic methodology and shows only non-emission. Upon treatment with fluoride in aqueous MeCN solution, the TBS protective group of probe TSAA was removed readily and the fluorescence of the probe was switched on, which resulted in a new fluorescence peak around 543 nm. The fluorescent intensity at 543 nm increases linearly with fluoride ion concentration in the range 1–50 μmol L^?1. This proposed probe shows excellent selectivity toward fluoride ion over other common anions and cations.     

Ovalbumin-stabilized gold nanoclusters with ascorbic acid as reducing agent for detection of serum copper

Ovalbumin-stabilized gold nanoclusters(OVA@AuNCs) were prepared with ascorbic acid as a reducing agent. This strategy could realize the synthesis of water-soluble OVA@AuNCs within 20 min. The asprepared fluorescent probe showed a red fluorescence emission at 630 nm. Moreover, the properties of the OVA@AuNCs were characterized by transmission electron microscope, dynamic light scattering,ultraviolet-visible spectroscopy, fluorescent spectroscopy. Based on the surface electron density decrease-induced fluorescence quenching mechanism, the OVA@AuNCs provided high sensitivity and selectivity for sensing copper ions. A good linear relationship was obtained between the fluorescence intensity of OVA@AuNCs and the concentration of copper ions in the range of 5.0-100.0 μmol/L(R~2=0.999) with a detection limit of 640 nmol/L Furthermore, the rat serum copper contents were determined by using the OVA@AuNCs based assay, indicating great potential of fluorescent probes for application in biological and clinical analysis.     

In-line Raman spectroscopy and advanced process control for the extraction of anethole and fenchone from fennel (Foeniculum vulgare L. MILL.)

Plants are a desirable source for molecules of all kinds and for every purpose. Besides traditional techniques for extraction, plants are challenging for modern process engineering due to great variations because of their natural origin. One way to ensure high quality and low costs, as well as highly resource-efficient extraction, is in-line monitoring and process control. This study demonstrates the use of in-line Raman spectroscopy for monitoring the extraction of anethole and fenchone from fennel seed as a typical example. A partial least square calibration model with high accuracy was created. (Anethole: R² = 0.99, root mean square error of calibration (RMSEC) = 0.01256 g/L, root mean square error of validation (RMSEV) = 0.02608 g/L, and calibration range up to 2 g/L. Fenchone: R² = 0.98, RMSEC = 0.01188 g/L, RMSEV = 0.01945 g/L, and calibration up to 0.75 g/L.) These data are directly linked to a physicochemical process model to control the extraction process in real time and to perform predictive simulations while processing. The added value of this approach for modern phytoextraction is highlighted and exemplified as a major step toward sustainable Green Extraction processes.     

Synthesis and red electroluminescence of a dimesityl-functionalized bistetracene

The single crystal analysis of the as-prepared 8,16-dimesityltetraceno[2,1,12,11-opqra]tetracene (DMTA) suggests that the parent bistetracene backbone is almost in a plane without any intermolecular p-stacking interaction. The fabricated devices based on DMTA as an emitter exhibit a maximum brightness of 632 cd/m² at 14.7 V with the CIE coordinate of (0.623, 0.349).     

Photocatalytic hydrogen production from acidic aqueous solution in BODIPY-cobaloxime-ascorbic acid homogeneous system

For the first time, iodinated BODIPY dyes with phenylamine or 8-hydroxylquinoline moiety at the meso-position on the BODIPY core were tested for the light-driven production of H₂ from the acidic aqueous solutions.     

Enantioselective enzymatic resolution of racemic alcohols by lipases in green organic solvents

The effects of two eco-friendly solvents, 2-methyltetrahydrofuran (MeTHF) and cyclopentyl methyl ether (CPME), on the enzyme activity and enantioselectivity of Novozym 435, Candida rugosa lipase (CRL), Porcine pancreas lipase (PPL), Lipase AK, Lipase PS, and Lipozyme, a series of commercial lipases, in the enantioselective transesterfications of racemic menthol, racemic sulcatol and racemic α-cyclogeraniol were studied. Vinyl acetate was chosen as the acyl donor and the reactions were carried out at water activity 0.06. The activity of lipases in CPME was similar to that observed in other largely employed organic solvents [toluene and tert-butyl methyl ether (MTBE)], and was slightly lower in MeTHF. However, for most of the lipases tested, the enantioselectivity was higher in the eco-friendly solvents. Lipase AK exhibited a high enantioselectivity (E = 232) for the resolution of racemic menthol but the reaction rate was low. Lipase formulation (the enzyme was frozen and lyophilized in potassium phosphate buffer without and with 5% (w/v) of sucrose, d-mannitol, or methoxy poly(ethylene glycol)) was tested with this lipase in order to improve its activity, which increased up to 4.5 times, compared to the untreated enzyme. CALB was found to be a useful biocatalyst for the resolution of racemic sulcatol, where high activity and enantioselectivity were obtained (E ≥ 1000). For the resolution of the racemic primary alcohol α-cyclogeraniol, most of the lipases tested were active but not enantioselective, except lipase PS which displayed a moderate enantioselectivity (E = 19). The effect of the presence of a low percentage of two ionic liquids (ILs) 1-Butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([BMIM][TFSI]) (5% (v/v)) and 1-Butyl-3-methylimidazoliumtetrafluoroborate ([BMIM][BF4]) (1% (v/v)) in the medium was also investigated. Only in the case of CRL the ILs slightly increased the enantioselectivity from E = 91 to E = 103 and E = 120 for [BMIM][TFSI] and [BMIM][BF4], respectively. However, in all cases ILs caused a decrease of enzyme activity.     

Synthesis,spectroscopic, structural and thermal characterizations of [(C7H6NO4)2TeBr6·4H2O]

Tellurium (IV) complexes with pyridine-2,6-dicarboxylate ligand were synthesized by slow evaporation from aqueous solutions yielding a new compound: [(C₇H₆NO₄)₂TeBr₆·4H₂O]. The structure of this compound was solved and refined by single-crystal X-ray diffraction. The compound is centrosymmetric P2₁/c (N°: 14) with the parameters a = 8.875(5) Å, b = 15.174(5) Å, c = 10.199(5) Å, β = 94.271° (5) and Z = 2. The structure consists of isolated H₂O, isolated [TeBr₆]^2? octahedral anions and (pyridine-2,6-dicarboxylate) [C₇H₆NO₄]⁺ cations. The stability of the structure was ensured by ionic and hydrogen bonding contacts (N–H?Br and O–H?Br) and Van-Der Walls interaction. The thermal decomposition of the compound was studied by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The FTIR and Raman spectroscopy at different temperatures confirm the existence of vibrational modes that correspond to the organic, inorganic and water molecular groups. Additionally, the UV–Vis diffuse reflectance spectrum was recorded in order to investigate the band gap nature. The measurements show that this compound exhibits a semiconducting behavior with an optical band gap of 2.66 eV.     

Intercalation of melamine into layered zirconium phosphates and their adsorption properties of formaldehyde in gas and solution phase

The intercalations of melamine into α- and γ-zirconium phosphates (α- and γ-ZrP) were investigated. Melamine-intercalated α-ZrP afforded two phases with different interlayer distances (d = 1.30 and 1.55 nm). The phase with d = 1.30 nm was obtained as the mixture with original α-ZrP at 30 min reaction by batch method, whereas the single phase with d = 1.55 nm was obtained by decantation method in saturated melamine aqueous solution. Contrary to this, for γ-ZrP a phase with d = 1.78 nm was obtained by both batch and decantation methods in saturated melamine aqueous solution. And new phase with d = 1.48 nm was formed in batch method at low pH or lower concentration of melamine aqueous solution. In these phases the arrangement of melamine changed from a monolayer structure to a bilayer structure with the increase of interlayer distance. Furthermore, melamine-intercalated α- and γ-ZrP adsorbed formaldehyde gas and formaldehyde in formalin solution by interacting with melamine molecule in the interlayer region. In melamine-intercalated γ-ZrP with d = 1.48 nm, the expansion of interlayer distance to around 1.6 nm was observed after the adsorption of formaldehyde gas and formaldehyde in formalin solution. The adsorption of formaldehyde in formalin solution was accompanied with the release of melamine in the interlayer region with increasing the concentration of formaldehyde at 65 °C.     

A selective hydration of nitriles catalysed by a Pd(OAc)2-based system in water

In situ formation of a [Pd(OAc)₂bipy] (bipy = 2,2′-bipyridyl) complex in water selectively catalyses the hydration of a wide range of organonitriles at 70 °C. Catalyst loadings of 5 mol% afford primary amide products in excellent yields in the absence of hydration-promoting additives such as oximes and hydroxylamines.     

An ESIPT-based fluorescent probe for sensitive and selective detection of Cys/Hcy over GSH with a red emission and a large Stokes shift

An ESIPT-based fluorescent probe (Probe 1) using acrylate as recognition group for the selective and sensitive detection of cysteine/homocysteine (Cys/Hcy) has been developed. In the presence of Cys/Hcy, this probe was transformed into 1,3-bis(bispyridin-2ylimino)isoindolin-4-ol (dye 4) which displayed red fluorescence with a large Stokes shift (217 nm) when excited. The detection limits are as low as 5.4 nM and 7.0 nM for Cys and Hcy respectively (based on S/N = 3). Importantly, this probe has been successfully demonstrated for the detection of intracellular Cys/Hcy in living cells.     

Tunable amplified spontaneous emissions by dimensional-controlled microcrystal synthesis

One-dimensional (1D) microwires and 2D microdisks of DMF-HPPO have been selectively prepared by controlling the solution polarity. Tunable amplified spontaneous emissions are achieved and 1D microwire demonstrates sharp splitting photoluminescence peaks around 618 nm, while 2D microdisk shows a red-shifted emission central at 650 nm.     

Synthesis of a reduction-sensitive Bletilla striata polysaccharide amphiphilic copolymer

A reduction-sensitive stearic acid modified-Bletilla striata polysaccharide amphiphilic copolymer is synthesized. The copolymer enabled to spontaneously form micelles which display faster docetaxel release rates under reduction condition and enhanced anticancer activity in vitro after incorporating docetaxel into micelles.     

Novel dual inhibitors against FP-2 and PfDHFR as potential antimalarial agents: Design,synthesis and biological evaluation

A series of novel 2,4-diaminopyrimidine-modified compounds was designed and synthesized. Compound 14 showed micromolar dual inhibitory effect on both FP-2 and PfDHFR, and potential inhibition to the proliferation of P. falciparum 3D7 strain and chloroquine-resistant P. falciparum Dd2 strain.