Determination of photoluminescence quantum yields in dilute solution using non-monochromatic excitation light.

The photoluminescence (PL) quantum yields (QYs) of fluorophores in dilute solutions can be determined fluorimetrically according to the comparative method employing standards of known PLQY. This method has recently been demonstrated to become more robust when the absorption of the excitation light and the PL emission are measured simultaneously using a transmitted light detector integrated in the fluorimeter. Herein, aided by fiber-coupled spectroscopic equipment and computerized data processing, we elaborate on this method by measuring the full corrected intensity spectrum of the excitation light transmitted through the sample. This further releases constraints on the monochromatic character of the excitation light and enables the use of broad-band excitation sources such as light-emitting diodes (LEDs). Furthermore, the protocol includes measurements at increasing dye concentration, rigorously verifying the required proportionality between absorbed and emitted light intensities. The PLQYs of solutions of fluorophores determined using the new method are in close agreement with published values.

Tomentosin Induces Telomere Shortening and Caspase-Dependant Apoptosis in Cervical Cancer Cells.

Tomentosin, a natural sesquiterpene lactone purified from of Inula viscosa L., was investigated for its anti-proliferative, telomere shortening, and apoptotic effects on human cervical cancer HeLa and SiHa cell lines. Tomentosin was found to inhibit the growth of SiHa and HeLa cell lines in dose and time-dependent manner (IC50 values of 7.10 ± 0.78 µM and 5.87 ± 0.36 µM, respectively after 96 h of treatment). As evidenced by TTAGGG telomere length assay, tomentosin target specifically the telomeric overhang lengthening. This was confirmed by the evaluation of the cytotoxic effects of tomentosin in the foetal fibroblast Wi38 and JW10 cells which were derived from Wi38 and express hTERT, the telomerase catalytic subunit. We found that JW10 cells are 4.7-fold more sensitive to tomentosin which argues for telomere as its specific target. Furthermore, we found that tomentosin mediate this cytotoxic effect by inducing apoptosis and cell cycle arrest at G2/M phase. Morphological features of treated cells, as evidenced by Hoechst 33324 staining, revealed that the cytotoxic effect was due to induction of apoptosis. This was accompanied by pro-caspase-3 cleavage, an increase in caspase-3 activity and a cleavage of poly (ADP-ribose) polymerase (PARP). Moreover, tomentosin induced a decrease in mitochondrial membrane potential (ΔΨm) and an increase in reactive oxygen species (ROS), accompanied by a decrease in Bcl-2 expression. This indicates that tomentosin-induced apoptosis may involve a mitochondria-mediated signaling pathway. This study provides the first evidence that tomentosin targets telomere machinery and induces apoptosis in cervical cancer cells. The molecular mechanism underlying tomentosin-induced apoptosis may involve a mitochondria-mediated signaling pathway. J. Cell. Biochem. 118: 1689-1698, 2017. © 2016 Wiley Periodicals, Inc.

Inula Viscosa Extracts Induces Telomere Shortening and Apoptosis in Cancer Cells and Overcome Drug Resistance.

Telomerase is activated in human papillomavirus (HPV) positive cervical cancer and targeting telomeres offers a novel anticancer therapeutic strategy. In this study, the telomere targeting properties, the cytotoxic as well as the pro-apoptotic effects of hexane (IV-HE) and dichloromethane (IV-DF) fractions from Inula viscosa L. extracts were investigated on human cervical HeLa and SiHa cancer cells. Our data demonstrate that IV-HE and IV-DF extracts were able to inhibit cell growth in HeLa and SiHa cells in a dose-dependent manner and studied resistant cell lines exhibited a resistance factor less than 2 when treated with the extracts. IV-HE and IV-DF extracts were able to inhibit telomerase activity and to induce telomere shortening as shown by telomeric repeat amplification protocol and TTAGGG telomere length assay, respectively. The sensitivity of fibroblasts to the extracts was increased when telomerase was expressed. Finally, IV-HE and IV-DF were able to induce apoptosis as evidenced by an increase in annexin-V labeling and caspase-3 activity. This study provides the first evidence that the IV-HE and IV-DF extracts from Inula viscosa L. target telomeres induce apoptosis and overcome drug resistance in tumor cells. Future studies will focus on the identification of the molecules involved in the anticancer activity.

A Simple Chiral Cu(II) Complex as an Effective Phase-Transfer Catalyst for the Enantioselective Alkylation of Dissymmetric Glycinate Ketimines.

Catalytic asymmetric benzylation of a dissymmetric tert-butylglycinate ketimine, incorporating 1-naphthyl and phenyl groups as the Schiff base substituents, under phase-transfer conditions was investigated. It was interesting to note that the sense of asymmetric induction of the alkylation of Z-imine stereoisomer is opposite to that of the corresponding E stereoisomer with a similar degree of enantioselectivity. More interestingly, the chiral Cu(II) complex of the Schiff base derived from (R)-2-phenylglycinol and 2-hydroxy-1-naphthaldehyde was found to catalyze the same reaction under solid-liquid conditions with comparable enantioselectivity (up to 60% ee) with respect to known cinchona alkaloid catalysts. The solvent/base-system parameter was shown to control the optimal catalytic activity.

Characterization of bottom ash from two hospital waste incinerators in Rabat, Morocco.

The uncontrolled disposal of bottom ash generated by the incineration units of hazardous and infected wastes in developed countries are the main cause of significant damage, such as contamination of the soil, as well as surface and underground waters, which may put both the environment and public health at risk. In Morocco, little information is available on the chemical properties of the resulting ashes. In this study, 16 hospital waste ash samples were collected from the incinerators of the two main hospitals in Rabat: Ibn Sina and Cheikh Zayd. A series of tests was conducted, including particle size distribution, mineralogical and chemical composition, and heavy metal leaching behaviour. The results showed that the samples were composed mainly of P2O5 (18%), SiO2 (17%), Na2O (16%), CaO (14%) and SO3 (10%). Moreover, chemical analysis clearly demonstrated that medical waste (MW) contains large amounts of waste generated by domestic activities in the hospital, with a lack of sorting system in the monitoring of MW. Furthermore, the ashes contained high concentrations of heavy metals such as zinc, lead, chromium and nickel with a vast range of 0.5-25071 mg/kg. Leaching tests showed that the extracted amounts of all the heavy metals were lower, with concentrations < 2.85 mg/kg. Comparison of the corresponding heavy metal concentrations with the limit values set by the Council Decision 2003/33/EC allowed us to conclude that bottom ashes meet the waste acceptance criteria regarding these heavy metals.

3'-(4-Meth-oxy-phen-yl)-4'-phenyl-3H,4'H-spiro-[1-benzothio-phene-2,5'-isoxazol]-3-one.

In the title compound, C(23)H(17)NO(3)S, the thio-phene and isoxazole rings each have an envelope conformation with the spiro C atom linking them forming the flap of the envelope in each case. The dihedral angle between the mean planes of the benzothio-phene ring and isoxazole rings is 81.35 (7)°. In the crystal, an inter-molecular C-H⋯O hydrogen bond links the mol-ecules into a chain running parallel to the a axis.

(2RS,4'RS)-3'-(3-Chloro-4-meth-oxy-phen-yl)-4'-phenyl-4'H-spiro-[indene-2,5'-isoxazol]-1(3H)-one ethanol monosolvate.

The title compound, C(23)H(17)ClN(2)O(3)·C(2)H(6)O, is the stoichiometric 1:1 ethanol solvate of a racemic reaction product, which forms a conglomerate. The refined Flack parameter of 0.36 (3) indicates racemic twinning. In the structure, mol-ecules are linked into zigzag chains by a series of inter-molecular N-H⋯O and O-H⋯O hydrogen bonds.

Ethyl 2-amino-4-phenyl-4H-1-benzo-thieno[3,2-b]pyran-3-carboxyl-ate.

The title heterocyclic compound, C(20)H(17)NO(3)S, was synthesized by condensation of ethyl cyano-acetate with (Z)-2-benzyl-idenebenzo[b]thio-phen-3(2H)-one in the presence of a basic catalyst in ethanol. The phenyl and ester groups make dihedral angles of 77.67 (6) and 8.52 (6)°, respectively, with the benzothienopyran ring system [maximum r.m.s. deviation = 0.1177 (13) Å]. In the crystal, centrosymmetric dimers are formed through pairs of N-H⋯O hydrogen bonds between the amine and ester groups. Inter-molecular C-H⋯N hydrogen bonds and C-H⋯π inter-actions involving the thio-phene ring are also observed.

Stipa tenacissima L.: A New Promising Source of Bioactive Compounds with Antioxidant and Anticancer Potentials.

BACKGROUND: Stipa tenacissima L. (S. tenacissima), called Esparto grass, is a cultivated species used for industrial purposes, including textile production. This species has never been studied for its medical potential before, nor has it been used in traditional medicines. It is thus fitting that the present study aimed to investigate the pharmacological potential of S. tenacissima. To achieve this goal, this work was conducted to study the chemical composition, antioxidant properties, and antiproliferative effects of S. tenacissima against cancerous cell lines, including the human colorectal adenocarcinoma cell line (HT-29) and human breast adenocarcinoma cell line (MDA-MB-231). Fractionation and characterization of S. tenacissima extract showed the presence of promising bioactive fractions. The fractions obtained from S. tenacissima extract exhibited interesting antioxidant properties, with IC50 values ranging from 1.26 to 1.85 mg/mL. All fractions, such as F1, F2, F3, and F4, induced an important antiproliferative effect on the cancer cell lines MDA-MB-231, scoring IC50 values ranging from 63.58 ± 3.14 to 99.880 ± 0.061 µg/mL. These fractions (F1, F2, F3, and F4) also exhibited a potent antiproliferative effect versus HT-29 cell lines, with IC50 values ranging from 71.50 ± 4.97 to 87.500 ± 1.799 µg/mL. Therefore, S. tenacissima could constitute a new natural source of bioactive compounds that can be used for therapeutic purposes to fight cancer and free radical damage.

Entrapment of organic fluorophores in calcium phosphate nanoparticles with slow release.

Two organic fluorophores, fluorescein (F) and rhodamine B (Rd), were entrapped in calcium phosphate nanoparticles. The as-obtained nanoparticles can be used for biological release applications. For this aim, calcium phosphate nanoparticles were synthesized using the precipitation method. Structural analysis of these nanoparticles was performed using XRD, FTIR, and Raman spectroscopy, confirming that the synthesized nanoparticles were hydroxyapatite. TEM and SEM analyses demonstrated that these nanoparticles had a size of 20 nm and a well-defined morphology. F and Rd (about 0.5 wt.%) were entrapped in these nanoparticles and their release, as a function of time, was studied via UV-Vis spectroscopy. The obtained results showed that the release of both fluorophores was progressive over time. The trapping efficiencies of the fluorophores were 67.15% and 90.76% for F and Rd, respectively.

Immobilisation of bacteria onto magnetic nanoparticles for the decolorisation and degradation of azo dyes.

Azo dyes are widely used in industries and their release in the environment contributes to the pollution of effluents. The authors aim to develop a new eco-friendly water treatment method for the degradation of azo dyes based on in situ magnetic separation and immobilisation of bacterial cells. The immobilisation was achieved using superparamagnetic Fe3O4 nanoparticles and offers the possibility of reusing bacteria by magnetic separation for several degradation cycles. The iron-oxide nanoparticles were synthesised by reverse co-precipitation. The Gram-positive bacteria Bacillus subtilis were immobilised using iron-oxide nanoparticles by adsorption and then separated with an external magnetic field. Transmission electron microscopy observation showed that the particles' diameter was ∼20 nm with a narrow size distribution. Moreover, the iron-oxide nanoparticles were adsorbed onto the surface in order to coat the cells. B. subtilis has proved its ability to decolorise and degrade several azo dyes at different values of pH, with the highest decolorisation rate for Congo red. Furthermore, immobilised cells have a degradation activity similar to that of free cells. The system provided a degradation rate up to 80% and could be reused for seven batch cycles.

Antioxidant and Antiproliferative Activities of Bioactive Compounds Contained in Rosmarinus officinalis Used in the Mediterranean Diet.

BACKGROUND: Rosmarinus officinalis (R. officinalis) is a medicinal plant called rosemary, largely used in the Mediterranean diet for many decades ago. OBJECTIVE: The aim of the present study was to investigate the polyphenolic content, the antioxidant activity, and the antiproliferative effect against human prostate cancer cell lines (LNCaP) of carnosol and carnosic acid as bioactive compounds contained in R. officinalis growing in Morocco. MATERIALS AND METHODS: Polyphenolic content of R. officinalis ethanolic extract was studied using colorimetric assay. Carnosol and carnosic acid contained in R. officinalis extract were quantified using high-performance liquid chromatography (HPLC). The antiproliferative effect of the studied extracts on LNCaP was evaluated by WST-1 bioassay, and the antioxidant activity was assessed using DPPH assay. RESULTS: The extracts of R. officinalis showed an important polyphenolic content ranging from 74.15 µg·GAE/mg to 146.63 µg·GAE/mg. The percentage of carnosol and carnosic acid in rosemary crops ranges from 11.7 to 17.3% and 1.09% to 3%, respectively. The extracts of R. officinalis exhibited a promoting antioxidant activity with IC50 ranging from 0.236 mg/mL to 0.176 mg/mL. Regarding the antiproliferative effect, the WST-1 assay revealed that all the tested extracts reduced notably the cell viability with IC50 values ranging from 14.15 to 15. 04 µg/mL. CONCLUSION: In the current work, carnosol and carnosic acid exhibit antioxidant and antiproliferative activities in a concentration-dependent manner.

Production of cellulose nanocrystals from vine shoots and their use for the development of nanocomposite materials.

In the present work, cellulose nanocrystals (CNC) were produced from vine shoots waste using chemical treatments followed by acid hydrolysis process. FTIR analysis confirmed that the non-cellulosic components were progressively removed during the chemical treatments, and the final obtained materials are composed of pure cellulose. AFM and TEM observations showed that the extracted CNC possess a needle-like shape with an average length of 456 nm and an average diameter of 14 nm, giving rise to an average aspect ratio of about 32. The as-extracted CNC exhibit a cellulose I structure with high crystallinity index (82%), as determined by XRD characterization. Importantly, the resulted CNC provide a higher thermal stability in comparison with CNC extracted from other resources, using the same extraction process. The isolated CNC's surface charge density was evaluated by XPS analysis and resulted in ~2.0 sulfate groups per 100 anhydroglucose units. In order to identify the reinforcing ability of the new extracted CNC, Carboxymethyl cellulose nanocomposite films were prepared with various CNC contents (1, 3, 5, 8 wt%) and their mechanical properties were investigated by uniaxial tensile test. The results showed that the as-extracted CNC displayed a higher reinforcing ability for nanocomposite materials.

A NADPH substitute for selective photo-initiation of reductive bioprocesses via two-photon induced electron transfer.

A NADPH substitute where the nicotinamide moiety is replaced by a chromophoric unit having much larger two-photon absorption cross-section and able to transfer electrons to flavins only upon excitation is described as an effective two-photon nanotrigger for selective photo-activation of electron transfer in bioreductive processes.

Activation of bismuth(III) derivatives in ionic liquids: novel and recyclable catalytic systems for Friedel-Crafts acylation of aromatic compounds.

The activity of four bismuth(III) derivatives when employed as Friedel-Crafts catalysts for the acylation of aromatics was found to increase dramatically when dissolved in ionic liquids. Solutions of bismuth oxide or triflate in [emim][NTf(2)] and [bmim][NTf(2)] are the most efficient catalytic systems, with catalyst loading as low as 1% leading to clean, high-yielding acylation of a variety of benzene derivatives. These improved Friedel-Crafts catalytic systems can also be efficiently recycled as opposed to traditional systems. [reaction: see text]

Superoxide-stable ionic liquids: new and efficient media for electrosynthesis of functional siloxanes.

The electrogeneration of diorganylsilanones from difunctional precursors Y(CH(2))(3)(Me)SiX(2) and Ph(2)SiX(2)(Y = NH(2), CF(3), CN; X = Cl, OEt, OMe), performed in the presence of hexamethyldisiloxane or hexamethylcyclotrisiloxane (D(3)) in the ionic liquids [C(5)H(5)NC(8)F(18)].NTf(2), [C(5)H(5)NC(18)H(38)].NTf(2) and Me(3)BuN.NTf(2), which reveal high solubility of oxygen and are inert toward superoxide anion, allows functionalized siloxanes to be produced selectively in good isolated yields.

Criteria to design green enzymatic processes in ionic liquid/supercritical carbon dioxide systems.

Five different ionic liquids (ILs) based on quaternary ammonium cations, with functional side chains ((3-hydroxypropyl)-trimethyl-, (3-cyanopropyl)-trimethyl-, butyl-trimethyl-, (5-cyanopentyl)-trimethyl- and hexyl-trimethyl-) associated with the same anion (bis(trifluoromethane)sulfonyl amide)), were synthesized, and their suitability for Candida antarctica lipase B (CALB)-catalyzed ester synthesis in IL/supercritical carbon dioxide (scCO(2)) biphasic systems was assayed. Catalytic efficiency of the system has been analyzed as a function of both enzyme properties and mass-transfer phenomena criteria. First, the suitability of these ILs as enzymic reaction media was tested for the kinetic resolution of rac-phenylethanol. All ILs were found to be suitable media for enzyme catalysis, the best catalytic parameter (5.3 U/mg specific activity, 94.9% selectivity) being obtained for the (5-cyanopentyl)-trimethylammonium. Second, enzyme stability in all of the ILs was studied at 50 degrees C over a period of 50 days, and data were analyzed by a two-step kinetic deactivation model. All of the ILs were shown to act as stabilizing agents with respect to hexane, producing an increase in the free energy of deactivation (to 25 kJ/mol protein) and an improvement in the half-life time of the enzyme (2000-fold), which agrees with the observed increased hydrophobicity of the cation alkyl side chain (measured by Hansen's solubility parameter, delta). By using two different CALB-IL systems with different hydrophobicity in the cation, continuous processes to synthesize six different short chain alkyl esters (butyl acetate, butyl propionate, butyl butyrate, hexyl propionate, hexyl butyrate, and octyl propionate) in scCO(2) at 10 MPa and 50 degrees C were carried out. Both rate-limiting parameters (synthetic activity and scCO(2)-ILs mass-transfer phenomena) were related with the delta-parameter of the ILs-alkyl chain and reagents.

Reaction rates as a function of scale within ionic liquids: microscale in droplet microreactors versus macroscale reactions in the case of the Grieco three-component condensation reaction.

Task-specific ionic liquids (TSILs) and more specifically binary task-specific ionic liquids (BTSILs), a unique subclass, have been shown to be excellent supports for solution-phase chemistry. The negligible volatility of ionic liquids enables their use as stable droplet microreactors in atmospheric environments without oil protection or confinement. These droplets can be moved, merged and mixed by electrowetting on a chip. Solution-phase synthesis can be performed on these open digital microfluidic labs-on-a-chip as illustrated by a study of the Grieco three-component reaction in [tmba][NTf(2)]-droplet (tmba=N-trimethyl-N-butylammonium NTf(2)=bis(trifluoromethylsulfonyl)imide) microreactors. A detailed study of matrices and scale effects on conversion and kinetic rates of this three-component condensation is presented in this paper. Reactions have been shown to be slower in droplets than in batches in the absence of additional mixing. Also, a significant influence of the ionic-liquid matrix has been observed. Finally, an increase of droplet's temperature resulted in a kinetics enhancement so as to reach macroscale reaction rates, probably because of a much better mixing of reaction's components involving a Marangoni's effect.

Synchronous photoinitiation of endothelial NO synthase activity by a nanotrigger targeted at its NADPH site.

We designed a new nanotrigger to synchronize and monitor an enzymatic activity interacting specifically with the conserved NADPH binding site. The nanotrigger (NT) combines a docking moiety targeting the NADPH site and a chromophore moiety responsive to light excitation for efficient electron transfer to the protein. Specific binding of the nanotrigger to the reductase domain of the endothelial nitric oxide synthase (eNOSred) was demonstrated by competition between NADPH and the nanotrigger on the reduction of eNOSred flavin. A micromolar Ki was estimated. We had monitored initiation of eNOSred activity by ultrafast transient spectroscopy. The transient absorption spectrum recorded at 250 ps fits the expected sum of the reduced and oxidized species, independently obtained by other chemical methods, in agreement with a photoinduced electron transfer from the excited nanotrigger to the flavin moiety of eNOSred. The rate of electron transfer from the excited state of the nanotrigger (NT*) to the protein is estimated to be k(ET) = (7 +/- 2) x 10(9) s(-1) using the decay of oxidized eNOSred-bound nanotrigger compared against prereduced eNOSred or glucose 6-P dehydrogenase as controls. This fast electron transfer bypasses the slow hydride transfer to initiate NOS catalysis as shown by ultrafast kinetics using the eNOSred mutated in the regulatory F1160 residue. The selective targeting of the nanotrigger to NADPH sites should allow controlled initiation of the enzymatic activity of numerous proteins containing an NADPH site.