Using an electrical potential to reversibly switch surfaces between two states for dynamically controlling cell adhesion

Smart surfaces presenting both antifouling molecules with a charged functional group at their distal end, and molecules that are terminated by RGD peptides for cell adhesion, were fabricated and characterized (see picture). By applying potentials of +300 or -300?mV, the surfaces could be dynamically switched to make the peptide accessible or inaccessible to cells.     

Phenolics and flavonoids compounds, phenylanine ammonia lyase and antioxidant activity responses to elevated CO₂ in Labisia pumila (Myrisinaceae)

A split plot 3 × 3 experiment was designed to examine the impact of three concentrations of CO? (400, 800 and 1,200 μmol·mol?1) on the phenolic and flavonoid compound profiles, phenylalanine ammonia lyase (PAL) and antioxidant activity in three varieties of Labisia pumila Benth. (var. alata, pumila and lanceolata) after 15 weeks of exposure. HPLC analysis revealed a strong influence of increased CO? concentration on the modification of phenolic and flavonoid profiles, whose intensity depended on the interaction between CO? levels and L. pumila varieties. Gallic acid and quercetin were the most abundant phenolics and flavonoids commonly present in all the varieties. With elevated CO? (1,200 μmol·mol?1) exposure, gallic acid increased tremendously, especially in var. alata and pumila (101-111%), whilst a large quercetin increase was noted in var. lanceolata (260%), followed closely by alata (201%). Kaempferol, although detected under ambient CO? conditions, was undetected in all varieties after exposure. Instead, caffeic acid was enhanced tremendously in var. alata (338~1,100%) and pumila (298~433%). Meanwhile, pyragallol and rutin were only seen in var. alata (810 μg·g?1 DW) and pumila (25 μg·g?1 DW), respectively, under ambient conditions; but the former compound went undetected in all varieties while rutin continued to increase by 262% after CO? enrichment. Interestingly, naringenin that was present in all varieties under ambient conditions went undetected under enrichment, except for var. pumila where it was enhanced by 1,100%. PAL activity, DPPH and FRAP also increased with increasing CO? levels implying the possible improvement of health-promoting quality of Malaysian L. pumila under high CO? enrichment conditions.     

Impact of elevated carbon dioxide on primary, secondary metabolites and antioxidant responses of Eleais guineensis Jacq. (oil palm) seedlings

A split plot 3 by 3 experiment was designed to investigate the relationships among production of primary metabolites (soluble sugar and starch), secondary metabolites (total flavonoids, TF; total phenolics, TP), phenylalanine lyase (PAL) activity (EC 4.3.1.5), protein and antioxidant activity (FRAP) of three progenies of oil palm seedlings, namely Deli AVROS, Deli Yangambi and Deli URT, under three levels of CO? enrichment (400, 800 and 1,200 μmol·mol?1) for 15 weeks of exposure. During the study, the treatment effects were solely contributed by CO? enrichment levels; no progenies and interaction effects were observed. As CO? levels increased from 400 to 1,200 μmol·mol?1, the production of carbohydrate increased steadily, especially for starch more than soluble sugar. The production of total flavonoids and phenolics contents, were the highest under 1,200 and lowest at 400 μmol·mol?1. It was found that PAL activity was peaked under 1,200 μmol·mol?1 followed by 800 μmol·mol?1 and 400 μmol·mol?1. However, soluble protein was highest under 400 μmol·mol?1 and lowest under 1,200 μmol·mol?1. The sucrose/starch ratio, i.e., the indication of sucrose phosphate synthase actvity (EC 2.4.1.14) was found to be lowest as CO? concentration increased from 400 > 800 > 1,200 μmol·mol?1. The antioxidant activity, as determined by the ferric reducing/antioxidant potential (FRAP) activity, increased with increasing CO? levels, and was significantly lower than vitamin C and α-tocopherol but higher than butylated hydroxytoluene (BHT). Correlation analysis revealed that nitrogen has a significant negative correlation with carbohydrate, secondary metabolites and FRAP activity indicating up-regulation of production of carbohydrate, secondary metabolites and antioxidant activity of oil palm seedling under elevated CO? was due to reduction in nitrogen content in oil palm seedling expose to high CO? levels.     

Large deviation analysis for layered percolation problems on the complete graph

We analyze the large deviation properties for the (multitype) version of percolation on the complete graph – the simplest substitutive generalization of the Erd&0151;s‐Rènyi random graph that was treated in article by Bollobás et al. (Random Structures Algorithms 31 (2007), 3–122). Here the vertices of the graph are divided into a fixed finite number of sets (called layers) the probability of {u,v} being in our edge set depends on the respective layers of u and v. We determine the exponential rate function for the probability that a giant component occupies a fixed fraction of the graph, while all other components are small. We also determine the exponential rate function for the probability that a particular exploration process on the random graph will discover a certain fraction of vertices in each layer, without encountering a giant component.© 2011 Wiley Periodicals, Inc. Random Struct. Alg., 40, 460–492, 2012     

Λ‐{1,4,7,10‐Tetrakis­[(S)‐2‐hydroxy­propyl‐κO]‐1,4,7,10‐tetra­aza­cyclo­do­decane‐κ4N}cadmium(II) bis(2,4,6‐tri­nitro­phenolate) aceto­nitrile solvate

Crystallization of [Cd(S‐thpc12)](ClO₄)₂·H₂O {S‐thpc12 is 1,4,7,10‐tetrakis­[(S)‐2‐hydroxy­propyl]‐1,4,7,10‐tetra­aza­cyclo­do­decane} in the presence of two equivalents of sodium picrate monohydrate (sodium 2,4,6‐tri­nitro­phenolate monohydrate) diastereoselectively produces a neutral receptor complex, viz. the title compound, Λ‐[Cd(C₂₀H₄₄N₄O₄)](C₆H₂N₃O₇)₂·CH₃CN. In this complex, two picrate anions hydrogen bond, via their phenolate moieties, to the pendant hydroxyl groups of the receptor which, together with the four N atoms, themselves bond to Cd^II in an approximately cubic arrangement. One picrate anion hydrogen bonds to all four hydroxyl groups, one of which also acts as the sole hydrogen‐bond donor to the second picrate anion.     

Multiple phases in the system MgF2---Nb2O5 an electron microscope study of intergrowths, defects, and disordered crystals

Mixtures of MgF₂·xNb₂O₅ with x = 7 and 14 have, on annealing at high temperatures yielded a wide variety of block structures in which MgF₂ has replaced MeO₂ (Me = Ti⁴⁺, Nb⁴⁺). With F⁻ stabilizing the formation of large blocks, numerous defect structures have been characterized by direct lattice resolution electron microscopy. Features thus observed include planar faults, intergrowths, segregated domain structures, and disordered crystals. Chemical implications of these features are discussed.     

Copper Microelectrode as Liquid Chromatography Detector for Herbicide Glyphosate

Electrochemical behavior of herbicide glyphosate at copper microelectrode was investigated in alkaline and buffer solutions, and two mechanisms seemed to take place for glyphosate: i) complexation reaction at lower potential in alkaline and buffer solutions and ii) catalysis process at higher potential in alkaline solution. It was demonstrated that the copper microelectrode can be used as coulometric detector for glyphosate in HPLC, using the complexation reaction in buffer solution. Under optimized conditions, the detection limit for glyphosate was 5.9×10^?7 mol L^?1. The present method was successfully applied to the determination of glyphosate in tomato juice with a recovery of 88%.     

The synthesis of prostaglandin E1 and related substances

The authors describe in detail the conversion of 4 isometric exo-substituted bicyclo (3.1.0) hexanones 1a, 1b, 2a and 2b (R=CH3) to 4 prostaglandins of the E series, including crystalline dl-prostaglandin E1 (PGE1). Oxidative solvolysis of the keto esters 1a and 2a and of the desired keto acids 1a and 2a (R=H) according to the method of Just and Simonovitch resulted in a good yield of the mixture of vic-glycols of unrearranged carbon skeleton. The presence of dl-PGE1, or dl-8-iso PGE1 or their methyl esters was not detected in either case. Analysis of the unalkylated ketones 5a and 5b under the same and other conditions yielded unrearranged vic-glycols 6 as essentially the only product. A reaction sequence produced dl-8-isoprostaglandin E1, the 15-epimers of these prostaglandins, and dl-PGA1 and dl-PGB1 methyl esters.     

Tuning Photoinduced Electron Transfer Efficiency of Fluorogenic BODIPY‐α‐Tocopherol Analogues

Fluorogenic analogues of α‐tocopherol developed by our group have been instrumental in monitoring reactive oxygen species (ROS) within lipid membranes. Prepared as two‐segment trap‐reporter (chromanol‐BODIPY) probes, photoinduced electron transfer (PeT) was utilized to provide these probes with an off/on switch mechanism warranting the necessary sensitivity. Herein, we rationalize within the context of Marcus theory of electron transfer how substituents on the BODIPY core and linker length joining the trap and reporter segments, tune PeT efficiency. DFT and electrochemical studies were used to estimate the thermodynamic driving force of PeT in our constructs. By tuning the redox potential over a 400 mV range, we observed over an order of magnitude increase in PeT efficiency. Increasing the linker length between the chromanol and BODIPY by 2.8 angstroms, in turn, decreased PeT efficiency 2.7‐fold. Our results illustrate how substituent and linker choice enable “darkening” the off state of fluorogenic probes based on BODIPY fluorophores, by favoring PeT over radiative emission from the singlet excited state manifold. Ultimately, our work brings light to the sensitivity ceiling one may achieve in developing fluorogenic antioxidant analogues of α‐tocopherol. The work provides general guidelines applicable to those developing fluorogenic probes based on PeT.