Cytotoxic and apoptotic effects of Hypericum androsaemum on prostate adenocarcinoma (PC-3) and hepatocellular carcinoma (Hep G2) cell lines with identification of secondary metabolites by LC-HRMS

The study aims to determine the secondary metabolites of Hypericum androsaemum L. extracts by liquid chromatography-high resolution mass spectrometry (LC-HRMS), and investigate the antioxidant and cytotoxic activities of the plant. Cytotoxic activity was evaluated by MTT assay, and apoptosis induction abilities on human prostate adenocarcinoma (PC-3), and hepatocellular carcinoma (Hep G2) cell lines. Accordingly, major secondary metabolites were found as hederagenin (762 ± 70.10 μg/g) in the leaves dichloromethane (LD), herniarin (167 ± 1.50 μg/g) in fruit dichloromethane (FD), (-)-epicatechin (6538 ± 235.36 μg/g) in the leaves methanol (LM), (-)-epigallocatechin gallate (758 ± 20.46 μg/g) in the fruit methanol (FM), and caffeic acid (370 ± 8.88 μg/g) in the fruit water (FW), and (3313 ± 79.51 μg/g) in the leaves water (LW) extracts. LM exerted strong antioxidant activity in DPPH free (IC₅₀ 10.94 ± 0.08 μg/mL), and ABTS cation radicals scavenging (IC₅₀ 9.09 ± 0.05 μg/mL) activities. FM exhibited cytotoxic activity with IC₅₀ values of 73.23 ± 3.06 µg/mL and 31.64 ± 2.75 µg/mL on PC-3 and Hep G2 cell lines, respectively. Being the richest extract in terms of quillaic acid (630 ± 18.9 μg/g), which is a well-known cytotoxic triterpenoid with proven apoptosis induction ability on different cells, FM extract showed apoptosis induction activity with 64.75% on PC-3 cells at 50 μg/mL concentration. The study provides promising results about the potential of Hypericum androsaemum on cancer prevention.     

Enhancement of dispersion stability of inorganic additives via poly(sodium-4-styrenesulfonate) treatment geared to hydrogel applications

This study reports the preparation of poly(sodium-4-styrene sulfonate) (PSS) treated bentonite and clinoptilolite to prevent the agglomeration and sedimentation of these inorganic fillers during the preparation of hydrogel. For this purpose PSS treated fillers were prepared by using various techniques (dip and dry, hydrothermal, one-step ball milling and ultrasonication methods). The most suitable technique for preparing these PSS treated inorganic fillers (abbreviated as BP-dip and CP-dip) was the dip and dry method. BP-dip and CP-dip based polyvinyl alcohol/polyvinylpyrrolidone (PVA/PVP) composite hydrogels were prepared using the freeze/thawing method after the addition of one of BP-dip and CP-dip inorganic fillers in various amounts. The swelling properties, stability behaviors and Rhodamine B (RhB) adsorption of the composite hydrogels were studied. It was found that the swelling degrees of CP-dip and BP-dip based composite hydrogels with 25 mg of filler were higher than that of all other samples. The kinetic mechanism of RhB adsorption process and the related characteristic kinetic parameters were investigated by Pseudo kinetic models. The adsorption kinetics results for RhB adsorption were found best fitted with pseudo-second-order kinetics model. The maximum RhB adsorption capacity was determined to be for PVA/PVP-CP-dip25, which was 3.3 times higher than that of the unfilled PVA/PVP hydrogel.     

Grafting on crosslinked polymer beads by ATRP from polymer supported N-chlorosulfonamides

Grafting of methyl methacrylate (MMA) and ethyl acrylate (EA) monomers from immobilized N-chlorosulfonamide (NCSA) groups on crosslinked polystyrene-based beads have been achieved by copper mediated atom transfer radical polymerisation (ATRP) methodology. The initiation takes place via NCSA groups on the polymer, created by chlorination of crosslinked polystyrene sulfonamides. Using CuBr and hexacishexyl triethylenetetramine ligand for MMA and EA grafting showed a first order kinetics for each monomers.Polymers with 3.18 mmol g⁻¹ of NCSA groups have a progressive mass increase in accordance with increasing MMA graft polymerisation up to 380.0% grafting obtained after 6 h.By the method presented, grafting of MMA and EA have been successfully achieved with negligible amounts of free polymer formation (6.2%) in the solution. Hence grafting by ATRP through polymer supported NCSA is superior to the common radical grafting methods which are yielding free polymers simultaneously.The method provides an efficient procedure in preparing core-shell type of polymers, with retention of the bead shapes.     

Isoflavonoid Glycosides from the Rhizomes of Iris germanica

Five new di‐ and triglycosides, irigenin 7‐[O‐β‐D ‐glucopyranosyl‐(1→6)‐β‐D ‐glucopyranoside] ( 1 ), 6‐hydroxygenistein 4′‐[O‐β‐D ‐glucopyranosyl‐(1→6)‐β‐D ‐glucopyranoside] ( 2 ), nigricin 4′‐[O‐β‐D ‐glucopyanosyl‐(1→6)‐β‐D ‐glucopyranoside] ( 3 ), nigricin 4′‐[O‐β‐D ‐glucopyanosyl‐(1→2)‐O‐[α‐L ‐rhamnopyranosyl‐(1→6)]‐β‐D ‐glucopyranoside] ( 4 ), and 7‐{4′‐{[2″‐O‐(4′′′′‐acetyl‐2′′′′‐methoxyphenyl)‐β‐D ‐glucopyranosyl]oxy}‐3′‐(β‐D ‐glucopyranosyloxy)phenyl]‐9‐methoxy‐8H‐1,3‐dioxolo[4,5‐g]‐[1 benzopyran‐8‐one‐] ( 5 ), along with a known compound, nigricin 4′‐(β‐D ‐glucopyranoside) ( 6 ), were isolated from the rhizomes of Iris germanica. The structures of these compounds were established by spectroscopic methods, including 2D NMR spectroscopic techniques.     

Norditerpenoid Alkaloids from the Aerial Parts of Aconitum cochleare Woroschin

From the aerial parts of Aconitum cochleare Woroschin, two new norditerpenoid alkaloids named aconitilearine ( 1 ) and N‐deethylmethyllycaconitine ( 2 ) were isolated along with the eight known norditerpenoid alkaloids 3 – 10 . The structures for the new compounds were established on the basis of ¹H, ¹³C, DEPT, homonuclear ¹H,¹H‐COSY, NOESY, HSQC, and HMBC NMR studies.     

On-line stacking techniques for the nonaqueous capillary electrophoretic determination of acrylamide in processed food

In the present study, field amplified sample stacking (FASS) techniques in the nonaqueous capillary electrophoresis method (NACE) were introduced for the on-line concentration of the acrylamide to improve acrylamide detection at 210 nm by diode-array detection. Acetonitrile (ACN) as a nonaqueous solvent permits acrylamide to be protonated through the change of its acid-base chemistry, allowing capillary electrophoretic separation of this compound. Choosing 30 mmol L(-1) HClO(4), 20 mmol L(-1) NaClO(4), 218 mmol L(-1) CH(3)COOH in ACN as the separation electrolyte and employing sample stacking methods, the LOD value of acrylamide was decreased to 2.6 ng mL(-1) with electrokinetic injection and 4.4 ng mL(-1) with hydrodynamic injection. Optimized stacking conditions were applied to the determination of acrylamide in several foodstuffs. The method is simple, rapid, inexpensive, and widely applicable for the determination of acrylamide in food samples.     

Synergetic Effect of Sodium Borohydride Addition in Ammonia Borane Hydrolysis Reaction Mechanism and Kinetics

Synergetic effect of sodium borohydride (NaBH4) addition to ammonia borane (NH3BH3) hydrolysis reaction had been studied and iron-borate (FeB) was used to catalyze the reaction. Hydrogen generation performance of the hydrolysis reactions was compared for three different operating conditions: (1) in the presence of NaBH₄ with FeB catalyst, (2) with FeB without NaBH₄ addition and (3) in the presence of NaBH₄ without FeB. It was found that addition of NaBH₄ to the NH₃BH₃ hydrolysis reaction catalyzed by FeB resulted in the synergetic effect (synergetic factor (SF) > 0) and improved the hydrogen generation performance. Kinetic analysis showed that NaBH4 addition decreases the activation energy (E_a) from 52.11 ± 0.85 to 27.19 ± 0.44 kJ/mol. Simulation of hydrolysis kinetics curves indicated that addition of NaBH₄ (the mole fraction of NaBH₄ added to NH₃BH₃ is (1)) changed the three-dimensional diffusion mechanism to the one-dimensional one and brought on better hydrolysis properties in terms of higher hydrogen generation rate and lower induction time.     

Atom transfer radical polymerization through N‐chlorosulfonamides

Controlled polymerizations of vinyl monomers such as methyl methacrylate and styrene are achieved using N‐chloro,N‐propyl‐p‐toluenesulfonamide (NCPT) together with a cuprous bromide/hexahexyl triethylenetetramine (CuBr/H‐TETA) complex. Although N‐halosulfonamides are known to decompose radically to give free chlorine, NCPT alone (without a cuprous complex) does not initiate any polymerization even in prolonged reaction times. Instead these add to the double bonds to give 2‐chloroethylsulfonamides. In the present polymerization system a good chlorine donator (NCPT) is combined with an organic soluble complex (CuBr/H‐TETA) to perform atom transfer radical polymerizations (ATRPs) in homogenous conditions. The linear proportionality of the molecular weights to the conversions and straight lines observed in ln(M₀/M) (where M₀ and M are the monomer contents at the beginning and at any time, respectively) versus time plots indicate typical controlled polymerization characteristics. The use of freshly prepared NCPT is advisable due to its slow and spontaneous decomposition when standing at room temperatures. Because of their easy preparation, N‐chlorosulfonamides can be used and are preferred instead of special halogen compounds commonly used in copper mediated ATRP. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2691–2695, 2001     

Chemical guiding of magnetic nanoparticles in dispersed media containing poly-(methylmethacrylate-co-vinylpyrrolidone)

The differential reactivity of methylmethacrylate (MMA) and vinylpyrrolidone (VP) in free radical copolymerization, with stirring in methanol, renders an emulsified two phase system. The dispersed and continuous liquid phases contain copolymers rich in MMA and VP, respectively. When Fe(3)O(4) magnetic nanoparticles (mNPs) stabilized with tetramethylammonium hydroxide are added to this emulsion, the mNPs are located in the continuous phase. Very small chemical changes in the methacrylic or vinylic chains are able to guide the mNP toward the interface or to the inside of the dispersed phase since quite a selective functionalization of each phase may be achieved separately. Thus, a small addition of methacrylic acid as comonomer (0.5% molar) guides all of the mNPs to the interface while a 0.5% molar of sulfopropyl methacrylate induces the migration of all mNPs to the dispersed phase. When 0.5% molar of a VP derivative bearing sulfonate functionality is added, the mNPs are found both in the interface and in the continuous phase. The addition of water allows solid MMA-based microspheres to be obtained incorporating the mNPs selectively either at the surface or in the core.     

A short proof of the generalized Bonnet theorem

In three‐dimensional Euclidean space E³, the Bonnet theorem says that a curve on a ruled surface in three‐dimensional Euclidean space, having two of the following properties, has also a third one, namely, it can be a geodesic, that it can be the striction line, and that it cuts the generators under constant angle. In this work, in n dimensional Euclidean space Eⁿ, a short proof of the theorem generalized for (k + 1) dimensional ruled surfaces by Hagen in 4 is given. Copyright © 2013 John Wiley & Sons, Ltd.