Temperature-sensitive polypeptide brushes-coated mesoporous silica nanoparticles for dual-responsive drug release

A multifunctional nanohybrid based on mesoporous silica nanoparticle and biocompatible polypeptide was fabricated for targeted and dual-responsive therapy of tumor cells.     

Screen-printed electrochemical sensors for label-free potentiometric and impedimetric detection of human serum albumin

Herein, two electrochemical methods based on potentiometric and impedimetric transductions were presented for albumin targeting, employing screen-printed platforms (SPEs) to make easy and cost-effective sensors with good detection merits. The SPEs incorporated ion-to-electron multi-walled carbon nanotubes (MWCNTs) transducer. Sensors were constructed using either tridodecyl methyl-ammonium chloride (TDMACl) (sensor I) or aliquate 336S (sensor II) in plasticized polymeric matrices of carboxylated poly (vinyl chloride) (PVC-COOH). Analytical performances of the sensors were evaluated using the above-mentioned electrochemical techniques. For potentiometric assay, constructed sensors responded to albumin with −81.7 ± 1.7 (r² = 0.9986) and −146.2 ± 2.3 mV/decade (r² = 0.9991) slopes over the linearity range 1.5 μM–1.5 mM with 0.8 and 1.0 μM detection limits for respective TDMAC- and aliquate-based sensors. Interference study showed apparent selectivity for both sensors. Impedimetric assays were performed at pH = 7.5 in 10 mM PBS buffer solution with a 0.02 M [Fe(CN)₆]^−3/−4 redox-active electrolyte. Sensors achieved detection limits of 4.3 × 10⁻⁸ and 1.8 × 10⁻⁷ M over the linear ranges of 5.2×10⁻⁸–1.0×10⁻⁴ M and 1.4×10⁻⁶–1.4×10⁻³ M, with 0.09 ± 0.004 and 0.168 ± 0.009 log Ω/decade slopes for sensors based on TDMAC and aliquate, respectively. These sensors are characterized with simple construction, high sensitivity and selectivity, fast response time, single-use, and cost-effectiveness. The methods were successfully applied to albumin assessment in different biological fluids.     

Pressure‐Induced Conversion of a Paramagnetic FeCo Complex into a Molecular Magnetic Switch with Tuneable Hysteresis

A key challenge in the design of magnetic molecular switches is to obtain bistability at room temperature. Here, we show that application of moderate pressure makes it possible to convert a paramagnetic Fe^III₂Co^II₂ square complex into a molecular switch exhibiting a full dia‐ to paramagnetic transition: Fe^IICo^III ? Fe^IIICo^II. Moreover, the complex follows a rare behavior: the higher the pressure, the broader the magnetic hysteresis. Thus, the application of an adequate pressure allows inducing a magnetic bistability at room temperature with predictable hysteresis width. The structural studies at different pressures suggest that the pressure‐enhanced bistability is due to the strengthening of intermolecular interactions upon pressure increase. An original microscopic Ising‐like model including pressure effects is developed to simulate this unprecedented behavior. Overall, this study shows that FeCo complexes could be very sensitive piezo switches with potential use as sensors.     

Global weak solutions to a ferrofluid flow model

We are concerned with the global solvability of the differential system introduced by Shliomis to describe the flow of a colloidal suspension of magnetized nanoparticles in a nonconducting liquid, under the action of an external magnetic field. The system is a combination of the Navier–Stokes equations, the magnetization equation, and the magnetostatic equations. We prove, by using a method of regularization, the existence of global‐in‐time weak solutions with finite energy to an initial boundary‐value problem and establish the long‐time behaviour of such solutions. The main difficulty is due to the singularity of the gradient magnetic force and the torque. Copyright © 2007 John Wiley & Sons, Ltd.     

A new disposable biosensor platform: carbon nanotube/poly(o-toluidine) nanocomposite for direct biosensing of urea

The development of new techniques for rapid and continuous monitoring of urea in biomedical and clinical analysis is very important. Thus, conductive polymer-supported carbon nanotube as an effective electrochemical biosensing platform for direct detection of urea in blood samples was designed. For the assay optimization, several conductive polymers were synthesized and tested as electrode modifiers; among the tested polymers, poly-o-toluidine (PoT) showed the highest electrochemical signals. However, after the enzyme immobilization, direct bioelectrochemical signals were not obtained when the PoT was used alone. Due to the lower electrocatalytic feature of PoT, integration of carbon nanotube, to form a composite with the PoT, was exploited to enable the direct electron transfer. Successfully, using the hybrid, the catalytic activity of the immobilized urease enzyme was retained. Consequently, a sensitive and specific chronoamperometric signals were achieved after the bioassay optimization. Eventually, a standard calibration curve for urea determination was obtained. A linear range was found from 0.1 to 11 mM with the limit of detection of 0.03 mM. Successfully, several blood samples were analyzed and urea level was correlated with the reference analytical method.

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Graphical abstract Scheme 1: Schematic representation of screen-printed electrode-modified urease biosensors. Three-layer functionalized surface (multi-walled carbon nanotube/poly(o-toluidine) nanocomposite, with glutaraldehyde (cross-linker and urease-immobilized enzyme), was designed for urea biosensors.

     

Nonexponential relaxation of the metastable state of the spin-crossover system [Fe(L)2](ClO4)2.H2O [L = 2,6-Bis(pyrazol-1-ylmethyl)pyridine

The relaxation of the metastable state of the spin-crossover compound [Fe(L)(2)](ClO(4))(2).H(2)O, with L = 2,6-bis(pyrazol-1-ylmethyl)pyridine, populated by the LIESST (light induced excited spin state trapping) effect, has been investigated by magnetic measurements. The time dependence of the relaxation curve at several temperatures, starting from different initial states, is in the shape of stretched exponentials, and the thermal variation of the photostationary state under constant photoexcitation is progressive and reversible. These features are satisfactorily modeled by considering noninteracting two-level systems with a distribution of activation energies. A suggested origin for the distribution is the conformational flexibility of the nonplanar heterocyclic ligands. The effect of the intensity distribution during the LIESST process is also accounted for in a simple way.     

Collisionally-induced dissociation of purine antiviral agents: mechanisms of ion formation using gas phase hydrogen/deuterium exchange and electrospray ionization tandem mass spectrometry

ESI and CID mass spectra were obtained for two purine nucleoside antiviral agents (acycloguanosine and vidarabine) and one purine nucleotide (vidarabine monophosphate) and the corresponding compounds in which the labile hydrogens were replaced by deuterium gas phase exchange. The number of labile hydrogens, x, was determined from a comparison of ESI spectra obtained with N(2) and with ND(3) as the nebulizer gas. CID mass spectra were obtained for [M+H](+) and [M -H](-) ions and the exchanged analogs, [M(Dx)+D](+) and [M(Dx)-D](-), produced by ESI using a Sciex API-IIIplus mass spectrometer. Compositions of product ions and mechanisms of decomposition were determined by comparison of the CID mass spectra of the undeuterated and deuterated species. Protonated purine antiviral agents dissociate through rearrangement decompositions of base-protonated [M+H](+) ions by cleavage of the glycosidic bonds to give the protonated bases with a sugar moiety as the neutral fragment. Cleavage of the same bonds with charge retention on the sugar moiety gives low abundance ions, due to the low proton affinity of the sugar moiety compared to that of purine base. CID of protonated purine bases [B+H](+) occurs through two major pathways: (1) elimination of NH(3) (ND(3)) and (2) loss of NH(2)CN (ND(2)CN). Minor pathways include elimination of HNCO (DNCO), loss of CO, and loss of HCN (DCN). Deprotonated acycloguanosine and vidarabine exhibit the deprotonated base [B-H](-) as a major fragment from glycosidic bond cleavage and charge delocalization on the base. Deprotonated vidarabine monophosphate, however, shows predominantly phosphate related product ions. CID of deprotonated guanine shows two principal pathways: (1) elimination of NH(3) (ND(3)) and (2) loss of NH(2)CN (ND(2)CN). Minor pathways include elimination of HNCO (DNCO), loss of CO, and loss of HCN (DCN). The dissociation reactions of deprotonated adenine, however, proceed by elimination of HCN and (2) elimination of NCHNH (NCHND). The mass spectra of the antiviral agents studied in this paper may be useful in predicting reaction pathways in other heteroaromatic ring decompositions of nucleosides and nucleotides.     

Theoretical study of laser light generation and color image formation: FA1:Cs+ and FA2:Li+ centers at the low coordination (100) and (110) surfaces of AgCl and AgBr

The F_A1:Cs⁺ and F_A2:Li⁺ color centers at the low coordination (100) and (110) surfaces of AgCl and AgBr play important roles in laser light generation and color image formation. Double‐well potentials at these surfaces are investigated by using ab initio calculations. Quantum clusters were embedded in the simulated Coulomb fields that closely approximate the Madelung fields of the host surfaces, and ions that are the nearest neighbors to the F_A ? defect site are allowed to relax to equilibrium. The calculated Stokes shifts suggest that laser light generation is sensitive to the simultaneous effects of the vibrational coupling mode, the impurity cation, the coordination number of the surface ion, the lattice anion, and the choice of the basis set centered on the anion vacancy. An attempt has been made to explain these effects in terms of Madelung potential, electron affinity, and optical–optical conversion efficiency. All relaxed excited states of the defect‐containing surfaces are deep below the lower edges of the conduction bands of the ground‐state defect‐free surfaces, suggesting that the F_A(I):Cs⁺ and F_A(II):Li⁺ centers are suitable laser defects. The dependence of orientational destruction, recording sensitivity, and exciton (energy) transfer on the empty cation; the coordination number of the surface ion; and the lattice anion is clarified. The Glasner–Tompkins empirical rule was generalized to include the impurity cation and the coordination number of the surface ion. As far as color image formation is concerned, the supersensitizer was found to increase the sensitizing capabilities of two primary dyes in the excited states by increasing the relative yield of quantum efficiency. The (110) surfaces of AgBr and AgCl were more sensitive than the corresponding (100) surfaces, and AgBr thin film was found to be more sensitive than that of AgCl. On the basis of quasi‐Fermi levels, the difference in the sensitizing capabilities between the examined dyes in the excited states is determined. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005