Biosensors based on gold nanoelectrode ensembles and screen printed electrodes

Gold nanowires were synthesized within polycarbonate membranes according to an electroless deposition method, obtaining nanoelectrode ensembles (NEEs) with special electrochemical features. NEEs were coupled with home-produced carbon graphite screen printed electrodes and the electrochemical properties of the original nanoelectrode ensemble on screen printed substrate (NEE/SPS) assembly has been tested for sensors application. Glucose oxidase has been used as model enzyme in order to verify the feasibility of disposable gold NEE/SPS biosensors. Finally, different immobilisation and electrochemical deposition techniques based on either self assembled monolayers of cysteamine (CYS) or amino-propyl-triethoxysilane (APTES) and conductive polyaniline (PANI) molecular wires were used. Spatial patterning of the enzyme on the polycarbonate surface and of PANI wires on gold nanoelectrodes was obtained. Possible direct electron transfer between the enzyme and the PANI modified gold nanoelectrodes has been evaluated.     

Homogeneous Catalytic Hydrogenation of Amides to Amines

Hydrogenation of amides in the presence of [Ru(acac)₃] (acacH=2,4‐pentanedione), triphos [1,1,1‐tris‐ (diphenylphosphinomethyl)ethane] and methanesulfonic acid (MSA) produces secondary and tertiary amines with selectivities as high as 93 % provided that there is at least one aromatic ring on N. The system is also active for the synthesis of primary amines. In an attempt to probe the role of MSA and the mechanism of the reaction, a range of methanesulfonato complexes has been prepared from [Ru(acac)₃], triphos and MSA, or from reactions of [RuX(OAc)(triphos)] (X=H or OAc) or [RuH₂(CO)(triphos)] with MSA. Crystallographically characterised complexes include: [Ru(OAc‐κ¹O)₂(H₂O)(triphos)], [Ru(OAc‐κ²O,O′)(CH₃SO₃‐κ¹O)(triphos)], [Ru(CH₃SO₃‐κ¹O)₂(H₂O)(triphos)] and [Ru₂(μ‐CH₃SO₃)₃(triphos)₂][CH₃SO₃], whereas other complexes, such as [Ru(OAc‐κ¹O)(OAc‐κ²O,O′)(triphos)], [Ru(CH₃SO₃‐κ¹O)(CH₃SO₃‐κ²O,O′)(triphos)], H[Ru(CH₃SO₃‐κ¹O)₃(triphos)], [RuH(CH₃SO₃‐κ¹O)(CO)(triphos)] and [RuH(CH₃SO₃‐κ²O,O′)(triphos)] have been characterised spectroscopically. The interactions between these various complexes and their relevance to the catalytic reactions are discussed.     

Concerted Asynchronous Hula‐Twist Photoisomerization in the S65T/H148D Mutant of Green Fluorescent Protein

Fluorescence emission of wild‐type green fluorescent protein (GFP) is lost in the S65T mutant, but partly recovered in the S65T/H148D double mutant. These experimental findings are rationalized by a combined quantum mechanics/molecular mechanics (QM/MM) study at the QM(CASPT2//CASSCF)/AMBER level. A barrierless excited‐state proton transfer, which is exclusively driven by the Asp148 residue introduced in the double mutant, is responsible for the ultrafast formation of the anionic fluorescent state, which can be deactivated through a concerted asynchronous hula‐twist photoisomerization. This causes the lower fluorescence quantum yield in S65T/H148D compared to wild‐type GFP. Hydrogen out‐of‐plane motion plays an important role in the deactivation of the S65T/H148D fluorescent state.     

The rheological properties of hydrogenated castor oil crystals

The present study focuses on the rheological performance of a surfactant-rich aqueous suspension containing hydrogenated castor oil (HCO) crystals. HCO can be typically crystallized in five distinct shapes: spherically shaped, irregularly shaped, star-shaped (also called rosettes), short needles, and thick or thin fibers. The effect of the differences in shape on the rheological performance is studied, and the rheological properties are compared to the behavior of other triacylglycerol’s (TAG) suspensions. A suspension of TAG crystals usually behaves as a colloidal gel wherein a colloidal gel is defined as a network of flocs, with each floc being an aggregate of smaller subunits. All of these surfactant-rich aqueous suspensions of HCO crystals behaved according to a colloidal gel in the transient regime, independent of the studied crystal shapes, except the long thin fibers at a concentration above 0.1 wt% HCO transitioning from a heterogeneous fractal rod network to a homogeneous rod network, shifting from a colloidal gel to a glass.     

Photodynamic Activity on Biofilm in Endotracheal Tubes of Patients Admitted to an Intensive Care Unit

Ventilator-associated pneumonia (VAP) is an infection that arises after endotracheal intubation affecting patients under intensive care. The presence of the endotracheal tube (ETT) is a risk factor since it is colonized by multispecies biofilm. Antimicrobial photodynamic therapy (aPDT) could be a strategy to decontaminate ETTs. We verify if methylene blue (MB) associated with external illumination of the ETT could be an alternative to destroy biofilm. We performed an in vitro and ex vivo study. In vitro study was performed with P. aeruginosa biofilm grew over ETT for 7 days. After treatment, the surviving cells were cultured for 3 days and the biofilm was analyzed by crystal violet absorbance. Ex vivo study employed ETT obtained from extubated patients. aPDT was performed with MB (100 µm ) and red LED (λ = 640±20 nm). We quantified the biofilm thickness and used scanning electron microscopy and fluorescence technique to verify morphological and functional changes after aPDT. Our results showed that bacteria remain susceptible to aPDT after sequential treatments. We also attested that aPDT can reduce biofilm thickness, disrupt biofilm attachment from ETT surface and kill microbial cells. These data suggest that aPDT should be investigated to decrease VAP incidence via ETT decontamination.     

Competition between Liquid-liquid De-mixing,Crystallization, and Glass Transition in Solutions of PLA of Different Stereochemistry and DEET

Liquid-liquid(L-L)de-mixing and vitrification of solutions of either crystallizable poly(L-lactic acid)(PLLA)or non-crystallizable poly(D/L-lactic acid)(PDLLA)with 50 m%N,N-diethyl-3-methylbenzamide(DEET)were analyzed by calorimetry and cloud-point measurements,which allows drawing conclusions about the effect of polymer stereochemistry on the phase behavior.Regardless of the PLA stereochemistry,vitrification of the solutions on fast cooling,hindering crystallization of PLLA,occurred below-20℃ and suppressed prior L-L de-mixing.The experimental results prove that crystallization in samples containing crystallizable PLLA,observed at around 55℃ on slow cooling,is not preceded by L-L de-mixing.     

Circular colorings of weighted graphs

Suppose that G is a finite simple graph and w is a weight function which assigns to each vertex of G a nonnegative real number. Let C be a circle of length t. A t-circular coloring of (G, w) is a mapping Δ of the vertices of G to arcs of C such that Δ(x)∩Δ(y) = 0 if (x, y) ∈ E(G) and Δ(x) has length w(x). The circular-chromatic number of (G, w) is the least t for which there is a t-circular coloring of (G, w). This paper discusses basic properties of circular chromatic number of a weighted graph and relations between this parameter and other graph parameters. We are particularly interested in graphs G for which the circular-chromatic number of (G, w) is equal to the fractional clique weight of (G, w) for arbitrary weight function w. We call such graphs star-superperfect. We prove that odd cycles and their complements are star-superperfect. We then prove a theorem about the circular chromatic number of lexicographic product of graphs which provides a tool of constructing new star-superperfect graphs from old ones. © 1996 John Wiley & Sons, Inc.