A cortisol nanocomposite-based electrochemical sensor for enantioselective recognition of mandelic acid

An electrochemical chiral sensor was designed based on graphene (GR) as a catalyst for signal enhancement. Hydrocortisone has been immobilized as a chiral selector on GR to discriminate electrochemical signals of mandelic acid (MA) enantiomers. A two-step electrodeposition strategy was used to fabricate hydrocortisone-loaded overoxidized polypyrrole film (HC-OPPy) on graphene-modified glassy carbon electrode, which was successfully utilized as a working electrode for direct monitoring of MA enantiomers based on an inhibitory sensing mechanism. The stepwise modification of the surface was confirmed by cyclic voltammetry, impedance spectroscopy, and scanning electron microscopy. Because of the different interactions of enantiomers with the chiral electroactive platform, voltammetric signals with different intensities were observed for S-MA and R-MA at 1.36 and 1.40 V (vs. Ag/AgCl), respectively. The introduced design for the chiral sensor, with exploiting the chemometrics tools such as partial least squares, principle component regression, and genetic algorithm, was able to discriminate highly overlapping signals of MA enantiomers in their mixtures. The hydrocortisone-based sensor showed a linear response towards MA enantiomers within a concentration range of 1.0–25 mM with a detection limit of 0.25 mM (S/N = 3). The sensor not only extends the enantioselective sensing of MA enantiomers but also stimulates new opportunities for investigating stereo-selective behavior of hydrocortisone. The recognition mechanism was also investigated using docking analysis and DFT calculations.

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Evaluation of measurement uncertainty in the determination of jasmonic acid in <Emphasis Type="Italic">Lemna minor</Emphasis> L. by liquid chromatography with fluorescence detection

The uncertainty was estimated for the determination of jasmonic acid (JA) content in Lemna minor L. plant extracts using a reverse-phase liquid chromatography with fluorescence detection. JA was extracted from plant material, followed by solid-phase extraction procedures, derivatisation and quantification. In the estimation of uncertainty, the sampling, sample processing and chromatographic determination that may significantly influence the uncertainty of analytical data were considered. The results show that the method recovery and sample homogeneity are the two main contributors to uncertainty. The method has a relative expanded uncertainty (coverage factor k = 2) of about 17% at the JA content of approximately 100 ng/g.     

A perspective on non-enzymatic electrochemical nanosensors for direct detection of pesticides

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Extending Time Profile of Morphine‐Induced Analgesia Using a Chitosan‐Based Molecular Imprinted Polymer Nanogel

Chitosan‐based molecular imprinted polymer (CS‐MIP) nanogel is prepared in the presence of morphine template, fully characterized and used as a new vehicle to extend duration of morphine analgesic effect in Naval Medical Research Institute mice. The CS‐MIP nanogel with ≈25 nm size range exhibits 98% loading efficiency, and in vitro release studies show an initial burst followed by an extended slow release of morphine. In order to study the feasibility of CS‐MIP nanogel as morphine carrier, 20 mice are divided into two groups randomly and received subcutaneous injection of morphine‐loaded CS‐MIP and morphine (10 mg kg^?1) dissolved in physiologic saline. Those received injection of morphine‐loaded CS‐MIP show slower and long lasting release of morphine with 193 min effective time of 50% (ET50) analgesia compared to 120 min ET50 in mice received morphine dissolved in physiologic saline. These results suggest that CS‐MIP nanogel can be a possible strategy as morphine carrier for controlled release and extension of its analgesic efficacy.

     

D-Gulonolactone as a synthon for L-noviose: first preparation of 4-O-demethyl-L-noviofuranose and related derivatives

[reaction: see text] A new synthesis of L-noviose (11), a sugar moiety of novobiocin, is presented. D-Gulonolactone was initially converted in a few steps to the key ester derivative 7 [1-O-benzyl methyl 2,3-O-(1-methylethylidene)-alpha-L-lyxofuranosiduronate]. An appropriate selection of protecting groups enabled transformation of 7 under mild reaction conditions to 4-O-demethyl-L-noviofuranose 9a and related 9b-c. Derivatives 9 were further converted either to L-lyxopyranoses (10a and 10b) or to methyl L-lyxofuranoside 12.     

Induction of tumor necrosis factor-alpha by UVB: a role for reactive oxygen intermediates and eicosanoids

UVB irradiation induces nuclear factor-kappaB (NF-kappaB) activation, tumor necrosis factor-alpha (TNF-alpha) expression and reactive oxygen intermediates (ROI) in keratinocytes. We investigated whether ROI play a role in UVB-induced TNF-alpha mRNA expression. The antioxidants N-acetyl cysteine, NAC, epigallocathin gallate, EGCG, butylated hydroxyanisole (BHA) and vitamin C could reduce UVB-induced TNF-alpha mRNA levels to various degrees; vitamin E (alpha-tocopherol) had no effect. BHA was the most potent inhibitor. The oxidant tertiary butylated hydroperoxide could effectively induce TNF-alpha mRNA expression. Nordihydroguaiaretic acid (NDGA) and MK-886, inhibitors of lipoxygenase (LOX), and indometacin and quinacrine, inhibitors of cyclooxygenase (COX) and phospholipase A2, respectively, could also reduce UVB-induced TNF-alpha mRNA expression. Inhibition by NDGA was in concordance with the results for BHA. NDGA, indometacin, quinacrine and BHA could also effectively inhibit the inhibitor of NF-kappaB degradation, thereby maintaining NF-kappaB inactivity. In conclusion, we show that ROI are implicated in the induction of TNF-alpha mRNA by UVB and that not all antioxidants are equally effective inhibitors. COX products and more importantly LOX products, which themselves are products of an oxidative metabolism, are the main ROI implicated in this induction of TNF-alpha expression by UVB probably via activation of NF-kappaB.     

Type and conductor of simplicial affine semigroups

We provide a generalization of pseudo-Frobenius numbers of numerical semigroups to the context of the simplicial affine semigroups. In this way, we characterize the Cohen-Macaulay type of the simplicial affine semigroup ring $\mathbb{K}[S]$. We define the type of S, $\mathrm{type}(S)$, in terms of some Apéry sets of S and show that it coincides with the Cohen-Macaulay type of the semigroup ring, when $\mathbb{K}[S]$ is Cohen-Macaulay. If $\mathbb{K}[S]$ is a d-dimensional Cohen-Macaulay ring of embedding dimension at most $d+2$, then $\mathrm{type}(S)\le 2$. Otherwise, $\mathrm{type}(S)$ might be arbitrary large and it has no upper bound in terms of the embedding dimension. Finally, we present a generating set for the conductor of S as an ideal of its normalization.     

Rings consisting entirely of certain elements

We completely determine when a ring consists entirely of weak idempotents, units and nilpotents. We prove that such ring is exactly isomorphic to one of the following: a Boolean ring; Z₃ ⊕ Z₃; Z₃ ⊕ B where B is a Boolean ring; local ring with nil Jacobson radical; M₂(Z₂) or M₂(Z₃); or the ring of a Morita context with zero pairings where the underlying rings are Z₂ or Z₃.     

The two-machine open shop problem: To fit or not to fit, that is the question

We consider the open shop scheduling problem with two machines. Each job consists of two operations, and it is prescribed that the first (second) operation has to be executed by the first (second) machine. The order in which the two operations are scheduled is not fixed, but their execution intervals cannot overlap. We are interested in the question whether, for two given values D₁ and D₂, there exists a feasible schedule such that the first and second machine process all jobs during the intervals [0,D₁] and [0,D₂], respectively.We formulate four simple conditions on D₁ and D₂, which can be verified in linear time. These conditions are necessary and sufficient for the existence of a feasible schedule. The proof of sufficiency is algorithmical, and yields a feasible schedule in linear time. Furthermore, we show that there are at most two non-dominated points (D₁,D₂) for which there exists a feasible schedule.     

2D numerical simulation of submerged hydraulic jumps

Hydraulic jumps are usually used to dissipate energy in hydraulic engineering. In this paper, the turbulent submerged hydraulic jumps are simulated by solving the unsteady Reynolds averaged Navier–Stokes equations along with the continuity equation and the standard k–? equations for turbulence modeling. The Lagrangian moving grid method is employed for the simulation of the free surface. In the developed model, kinematic free-surface boundary condition is solved simultaneously with the momentum and continuity equations, so that the water elevation can be obtained along with velocity and pressure fields as part of the solution. Computational results are presented for Froude numbers ranging from 3.2 to 8.2 and submergence factors ranging from 0.24 to 0.85. Comparisons with experimental measurements show that numerical model can simulate the velocity field, variation of free surface, maximum velocity, Reynolds shear and normal stresses at various stations with reasonable accuracy.