Development of chemometric-assisted supercritical fluid extraction of effective and natural tyrosinase inhibitor from Syzygium aqueum leaves.

Tyrosinase is a key enzyme in enzymatic browning, causing quality losses in food through the oxidation process. Thus, the discovery of an effective and natural tyrosinase inhibitor via green technology is of great interest to the global food market due to food security and climate change issues. In this study, Syzygium aqueum (S. aqueum) leaves, which are known to be rich in phenolic compounds (PC), were chosen as a natural source of tyrosinase inhibitor, and the effect of the sustainable, supercritical fluid extraction (SFE) process was evaluated. Response surface methodology-assisted supercritical fluid extraction (RSM-assisted SFE) was utilized to optimize the PCs extracted from S. aqueum. The highest amount of PC was obtained at the optimum conditions (55 °C, 3350 psi, and 70 min). The IC50 (661.815 µg/mL) of the optimized extract was evaluated, and its antioxidant activity (96.8 %) was determined. Gas chromatography-mass spectrometry (GC-MS) results reveal that 2',6'-dihydroxy-4'-methoxychalcone (2,6-D4MC) (82.65 %) was the major PC in S. aqueum. Chemometric analysis indicated that 2,6-D4MC has similar chemical properties to the tyrosinase inhibitor control (kaempferol). The toxicity and physiochemical properties of the novel 2,6-D4MC from S. aqueum revealed that the 2,6-D4MC is safer than kaempferol as predicted via absorption, distribution, metabolism, and excretion (ADME) evaluation. Enzyme kinetic analysis shows that the type of inhibition of the optimized extract is non-competitive inhibition with Km = 1.55 mM and Vmax = 0.017 µM/s. High-performance liquid chromatography (HPLC) analysis shows the effectiveness of S. aqueum as a tyrosinase inhibitor. The mechanistic insight of the tyrosinase inhibition using 2,6-D4MC was successfully calculated using density functional theory (DFT) and molecular docking approaches. The findings could have a significant impact on food security development by devising a sustainable and effective tyrosinase inhibitor from waste by-products that is aligned with the United Nation's SDG 2, zero hunger.

Recent advances in halal food authentication: Challenges and strategies.

Increasing public awareness of food quality and safety has prompted a rapid increase in food authentication of halal food, which covers the production method, technical processing, identification of undeclared components, and species substitution in halal food products. This urges for extensive research into analytical methods to obtain accurate and reliable results for monitoring and controlling the authenticity of halal food. Nonetheless, authentication of halal food is often challenging because of the complex nature of food and the increasing number of food adulterants that cause detection difficulties. This review provides a comprehensive and impartial overview of recent studies on the analytical techniques used in the analysis of halal food authenticity (from 1980 to the present, but there has been no significant trend in the choice of techniques for authentication of halal food during this period). Additionally, this review highlights the classification of different methodologies based on validity measures that provide valuable information for future developments in advanced technology. In addition, methodological developments, and novel emerging techniques as well as their implementations have been explored in the evaluation of halal food authentication. This includes food categories that require halal authentication, illustrating the advantages and disadvantages as well as shortcomings during the use of all approaches in the halal food industry.

Correction: White light employing luminescent engineered large (mega) Stokes shift molecules: a review.

[This corrects the article DOI: 10.1039/D1RA00129A.].

White light employing luminescent engineered large (mega) Stokes shift molecules: a review.

Large (mega) Stokes shift molecules have shown great potential in white light emission for optoelectronic applications, such as flat panel display technology, light-emitting diodes, photosensitizers, molecular probes, cellular and bioimaging, and other applications. This review aims to summarize recent developments of white light generation that incorporate a large Stokes shift component, key approaches to designing large Stokes shift molecules, perspectives on future opportunities, and remaining challenges confronting this emerging research field. After a brief introduction of feasible pathways in generating white light, exemplifications of large Stokes shift molecules as white light candidates from organic and inorganic-based materials are illustrated. Various possible ways to design such molecules have been revealed by integrating the photophysical mechanisms that are essential to produce red-shifted emission upon photoexcitation, such as excited state intramolecular proton transfer (ESIPT), intramolecular charge transfer (ICT), excited state geometrical relaxation or structural deformation, aggregation-induced emission (AIE) alongside the different formations of aggregates, interplay between monomer and excimer emission, host-guest interaction, and lastly metal to ligand charge transfer (MLCT) via harvesting triplet state. Furthermore, previously reported fluorescent materials are described and categorized based on luminescence behaviors on account of the Stokes shifts value. This review will serve as a rationalized introduction and reference for researchers who are interested in exploring large or mega Stokes shift molecules, and will motivate new strategies along with instigation of persistent efforts in this prominent subject area with great avenues.

Unraveling the surface properties of PMMA/azobenzene blends as coating films with photoreversible surface polarity.

Various reports demonstrated that azobenzene derivatives are the chromophore of choice in photoresponsive surfaces showing reversible surface polarity. Hitherto the surface study of coating films based on polymer/azobenzene blends using contact angle measurements remained unexplored. To provide insight into the surface polarity of polymer/dye blend films, poly(methyl methacrylate) (PMMA) blends containing photoresponsive 4-hydroxy-4'-methylazobenzene (AZO1) and 4,4'-dimethylazobenzene (AZO2) as coating films on clear glass substrates are investigated in this work. Contact angle measurements were carried out to unravel the role of substituents in the surface polarity and the orientation of chromophores in the coating matrices before and after UV light (λ max = 365 nm) irradiation. Changes in water contact angles measured on the PMMA/azobenzene coating films indicated that the surface polarity is reversible as the chromophores underwent reversible trans-cis isomerisation. It has been revealed that the repeated trans-cis isomerisation led to the random reorientation and arrangement of chromophores in PMMA/AZO1 coating films. Then, to indicate the possibility of the disruption of interfacial interactions due to the repeated trans-cis isomerisation processes, as a proof of concept experiment, it is shown that the commercial acrylic-based pressure-sensitive sticker which adhered strongly to the PMMA/AZO1(13) coating film is peeled off from the coating surface after being subjected to a cycle of UV light irradiation for 12 hours, followed by dark conditions for another 12 hours within 14 days. The proof of concept study will lead to more development of smart photoresponsive coating films using simple polymer/dye blends.

Accelerated nucleophilic substitution reactions of dansyl chloride with aniline under ambient conditions via dual-tip reactive paper spray.

Paper spray ionization (PSI) mass spectrometry (MS) is an emerging tool for ambient reaction monitoring via microdroplet reaction acceleration. PSI-MS was used to accelerate and monitor the time course of the reaction of dansyl chloride with aniline, in acetonitrile, to produce dansyl aniline. Three distinct PSI arrangements were explored in this study representing alternative approaches for sample loading and interaction; conventional single tip as well as two novel setups, a dual-tip and a co-axial arrangement were designed so as to limit any on-paper interaction between reagents. The effect on product abundance was investigated using these different paper configurations as it relates to the time course and distance of microdroplet travel. It was observed that product yield increases at a given distance and then decreases thereafter for all PSI configurations. The fluorescent property of the product (dansyl aniline) was used to visually inspect the reaction progress on the paper substrate during the spraying process. Amongst the variety of sample loading methods the novel dual-tip arrangement showed an increased product yield and microdroplet density, whilst avoiding any on-paper interaction between the reagents.

Furo[3,2-c]coumarin-derived Fe3+ Selective Fluorescence Sensor: Synthesis, Fluorescence Study and Application to Water Analysis.

Furocoumarin (furo[3,2-c]coumarin) derivatives have been synthesized from single step, high yielding (82-92%) chemistry involving a 4-hydroxycoumarin 4 + 1 cycloaddition reaction. They are characterized by FTIR, 1H-NMR, and, for the first time, a comprehensive UV-Vis and fluorescence spectroscopy study has been carried out to determine if these compounds can serve as useful sensors. Based on the fluorescence data, the most promising furocoumarin derivative (2-(cyclohexylamino)-3-phenyl-4H-furo[3,2-c]chromen-4-one, FH), exhibits strong fluorescence (ФF = 0.48) with long fluorescence lifetime (5.6 ns) and large Stokes' shift, suggesting FH could be used as a novel fluorescent chemosensor. FH exhibits a highly selective, sensitive and instant turn-off fluorescence response to Fe3+ over other metal ions which was attributed to a charge transfer mechanism. Selectivity was demonstrated against 13 other competing metal ions (Na+, K+, Mg2+, Ca2+, Mn2+, Fe2+, Al3+, Ni2+, Cu2+, Zn2+, Co2+, Pb2+ and Ru3+) and aqueous compatibility was demonstrated in 10% MeOH-H2O solution. The FH sensor coordinates Fe3+ in a 1:2 stoichiometry with a binding constant, Ka = 5.25 × 103 M-1. This novel sensor has a limit of detection of 1.93 µM, below that of the US environmental protection agency guidelines (5.37 µM), with a linear dynamic range of ~28 (~2-30 µM) and an R2 value of 0.9975. As an exemplar application we demonstrate the potential of this sensor for the rapid measurement of Fe3+ in mineral and tap water samples demonstrating the real-world application of FH as a "turn off" fluorescence sensor.

Reflexin A, a new indole alkaloid from Rauvolfia reflexa induces apoptosis against colon cancer cells.

One new indole alkaloid, reflexin A (1), and two known indoles, macusine B (2) and vinorine (3), were isolated from the bark of Rauvolfia reflexa. Their structures were elucidated by 1D and 2D NMR, UV, IR, and MS spectroscopic analyses. Compound 1 displayed anticancer activity against HCT-116 colon cancer cells with an IC50 value of 30.24 ± 0.75 µM. The results implied that the newly isolated 1 induced apoptosis in HCT-116 cells, suggesting its possible role as an anticancer agent. In vivo acute toxicity study was performed on compound 1 to evaluate its safety profile.

White Light Emission from a Simple Mixture of Fluorescent Organic Compounds.

Three fluorescent organic compounds-furocoumarin (FC), dansyl aniline (DA), and 7-hydroxycoumarin-3-carboxylic acid (CC)-are mixed to produce almost pure white light emission (WLE). This novel mixture is immobilised in silica aerogel and applied as a coating to a UV LED to demonstrate its applicability as a low-cost, organic coating for WLE via simultaneous emission. In ethanol solution and when immobilised in silica aerogel, the mixture exhibits a Commission Internationale d'Eclairage (CIE) chromaticity index of (0.27, 0.33). It was observed that a broadband and simultaneous emission involving coumarin carboxylic acid, furocoumarin and dansyl aniline played a vital role in obtaining a CIE index close to that of pure white light.

Antioxidant Properties and Gastroprotective Effects of 2-(Ethylthio)Benzohydrazones on Ethanol-Induced Acute Gastric Mucosal Lesions in Rats.

A series of new 2-(ethylthio)benzohydrazone derivatives (1-6) were prepared and characterised by IR, 1H NMR, and 13C NMR spectroscopy and mass spectrometry. The newly prepared compounds were screened for their in vitro antioxidant activities using free radical scavenging 2,2-diphenyl-1-picrylhydrazyl (DPPH) and ferric reducing antioxidant power (FRAP) assays. Among them, most powerful antioxidant, compound 1 has been selected in order to illustrate anti-ulcer effect on ethanol-induced gastric mucosal lesions in rats. Four groups of Sprague Dawley rats were respectively treated with 10% Tween 20 as ulcer control group, 20 mg/kg omeprazole as reference group, 50 mg/kg and 100 mg/kg compound 1 as experimental animals. Macroscopically, ulcer control group showed extensive hemorrhagic lesions of gastric mucosa compared with omeprazole or compound 1. Rats pre-treated with compound 1 showed increased in gastric pH and gastric mucus. Histologically, ulcer control group showed severe damage to gastric mucosa with edema and leucocytes infiltration of submucosal layer. In immunohistochemical analysis, rats which were pre-treated with compound 1 showed up-regulation of HSP70 and down-regulation of Bax proteins. In conclusion, the gastroprotective effect of compound 1 may be due to its antioxidant activity, and/or due to up-regulation of HSP70 and down-regulation of Bax protein in stained tissue section.

Solvent and pH Effects of Coumarin-Terminated Monolayer on Silver Particles.

A coumarin-terminated self-assembled monolayer on silver particles (C-SAM) from the reduction of silver ions in the presence of compound 3 was successfully prepared by utilizing phase transfer method, and analyzed by FTIR, SEM-EDS, UV-Visible and a particle sizer. The fluorescence behavior of coumarin termini was carried out in ethanol and chloroform with emission wavelength determined at 386 nm, suggesting an interaction between the carbonyl group and the solvent media. The dispersion was then investigated in acidic and basic conditions, showing a direct proportional correlation between the emission and the pH of the aqueous. These results were consistent for interpreting hydrogen bonds, particularly between the carbonyl group with either proton of the alcohol (C=O----H-O-R) or positive species in acidic conditions (C=O----H(+)). The interactions were possible only when the coumarin terminal rearranged in the monolayer and the carbonyl exerted towards the solvent media, while the rest of the molecules were separated from the solvents.

Crystal structure of a new monoclinic polymorph of N-(4-methyl-phen-yl)-3-nitro-pyridin-2-amine.

The title compound, C12H11N3O2, is a second monoclinic polymorph (P21, with Z' = 4) of the previously reported monoclinic (P21/c, with Z' = 2) form [Akhmad Aznan et al. (2010 ▶). Acta Cryst. E66, o2400]. Four independent mol-ecules comprise the asymmetric unit, which have the common features of a syn disposition of the pyridine N atom and the toluene ring, and an intra-molecular amine-nitro N-H⋯O hydrogen bond. The differences between mol-ecules relate to the dihedral angles between the rings which range from 2.92 (19) to 26.24 (19)°. The geometry-optimized structure [B3LYP level of theory and 6-311 g+(d,p) basis set] has the same features except that the entire mol-ecule is planar. In the crystal, the three-dimensional architecture is consolidated by a combination of C-H⋯O, C-H⋯π, nitro-N-O⋯π and π-π inter-actions [inter-centroid distances = 3.649 (2)-3.916 (2) Å].

Crystal structures of 1,4-di-aza-bicyclo-[2.2.2]octan-1-ium 4-nitro-benzoate dihydrate and 1,4-di-aza-bicyclo-[2.2.2]octane-1,4-diium bis-(4-nitro-benzoate): the influence of solvent upon the stoichiometry of the formed salt.

The 1:1 co-crystallization of 1,4-di-aza-bicyclo-[2.2.2]octane (DABCO) with 4-nitro-benzoic acid in ethanol-water (3/1) gave the salt dihydrate C6H13N2 (+)·C7H4NO4 (-)·2H2O, (1), whereas from methanol, the salt C6H14N2 (2+)·2C7H4NO4 (-), (2), was isolated. In (1), the cation and anion are linked by a strong N-H⋯O hydrogen bond, and the carboxyl-ate anion is close to planar [dihedral angle between terminal residues = 6.83 (9)°]. In (2), a three-ion aggregate is assembled by two N-H⋯O hydrogen bonds, and the carboxyl-ate anions are again close to planar [dihedral angles between terminal residues = 1.7 (3) and 5.9 (3)°]. Through the inter-vention of solvent water mol-ecules, which self-assemble into helical supra-molecular chains along the b axis, the three-dimensional architecture in (1) is stabilized by water-DABCO O-H⋯N and water-carboxyl-ate O-H⋯O hydrogen bonds, with additional stability afforded by C-H⋯O inter-actions. The global crystal structure comprises alternating layers of water mol-ecules and ion pairs stacked along the c axis. In the crystal of (2), the three-ion aggregates are assembled into a three-dimensional architecture by a large number of methyl-ene-carboxyl-ate/nitro C-H⋯O inter-actions as well as π-π contacts between inversion-related benzene rings [inter-centroid distances = 3.5644 (16) and 3.6527 (16) Å]. The cations and anions assemble into alternating layers along the c axis.

New thiosemicarbazides and 1,2,4-triazolethiones derived from 2-(ethylsulfanyl) benzohydrazide as potent antioxidants.

New thiosemicarbazide derivatives 2-6 were synthesised by reacting 2-(ethylsulfanyl)benzohydrazide with various aryl isothiocyanates. The cyclisation of compounds 2-6 under reflux conditions in a basic medium (aqueous NaOH, 4 N) yielded compounds 7-11 that contain a 1,2,4-triazole ring. All of the synthesised compounds were screened for their antioxidant activities. Compounds 2, 3, and 7 showed better radical scavenging in a 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay, with IC50 values of 1.08, 0.22, and 0.74 µg/mL, respectively, compared to gallic acid (IC50, 1.2 µg/mL). Compound 3 also showed superior results in a ferric reducing antioxidant power (FRAP) assay (3054 µM/100 g) compared to those of ascorbic acid (1207 µM/100 g).

1-Methyl-3-phenyl-imidazolidine-2-thione.

The asymmetric unit of the title cyclic thio-urea derivative, C10H12N2S, comprises two mol-ecules, each of which has a twist about the CH2-CH2 bond within the five-membered ring. The major difference between the independent mol-ecules is manifested in the relative orientations of the five- and six-membered rings [dihedral angles between the least-squares planes = 28.03 (11) and 41.54 (11)°]. A network of C-H⋯π inter-actions consolidates the three-dimensional crystal packing.

Synthesis and antibacterial evaluation of some novel imidazole and benzimidazole sulfonamides.

Several new substituted sulfonamide compounds were synthesized and their structures were confirmed by ¹H-NMR, ¹³C-NMR, FT-IR, and mass spectroscopy. The antibacterial activities of the synthesized compounds were screened against standard strains of six Gram positive and four Gram negative bacteria using the microbroth dilution assay. Most of the compounds studied showed promising activities against both types of bacteria.

Lumusidines A-D and villalstonidine F, macroline-macroline and macroline-pleiocarpamine bisindole alkaloids from Alstonia macrophylla.

Lumusidines A-D, bisindole alkaloids of the macroline-macroline type, and one of the macroline-pleiocarpamine type, villalstonidine F, were isolated from the stem-bark extract of Alstonia macrophylla (Apocynaceae). The structures and absolute configurations of these alkaloids were established using NMR, MS, and X-ray diffraction analyses.

N,N'-{[Ethane-1,2-diylbis(-oxy)]bis-(ethane-2,1-di-yl)}bis-(4-methyl-benzene-sulfonamide).

The asymmetric unit of the title compound, C(20)H(28)N(2)O(6)S(2), contains one half-mol-ecule, related to the other half by a twofold rotation axis. The two aromatic rings of the mol-ecule make a dihedral angle of 50.91 (7)°. The O-CH(2)-CH(2)-O and N-CH(2)-CH(2)-O fragments both adopt gauche conformations, with torsion angles of 76.0 (4) and 70.4 (3)°, respectively. In the crystal, adjacent mol-ecules are linked through N-H⋯O hydrogen bonds into chains along the a-axis direction. The chains are further connected via C-H⋯O inter-actions into a two-dimensional supra-molecular network in the ac plane.

tert-Butyl 2-(1H-benzimidazol-1-yl)acetate.

In the title compound, C(13)H(16)N(2)O(2), the planes of the benzimidazole ring system and the acetate O-C=O fragment make a dihedral angle of 84.5 (3)°. In the crystal, mol-ecules are connected through C-H⋯N hydrogen bonds to form infinite chains in the [-110] direction.

tert-Butyl 2-(1H-imidazol-1-yl)acetate.

In the title compound, C(9)H(14)N(2)O(2), the imidazole ring and the acetate O-C=O plane make a dihedral angle of 80.54 (12)°. In the crystal, mol-ecules are connected via pairs of C-H⋯O hydrogen bonds, forming centrosymmetric dimers.