Substrates with discretely immobilized silver nanoparticles for ultrasensitive detection of anions in water using surface-enhanced Raman scattering

Positively charged silver nanoparticles, Ag [+], obtained by UV-assisted reduction of silver nitrate using branched poly(ethyleneimine) (BPEI) and 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES) solutions as reducing agents, were immobilized on glass surfaces to produce substrates active in surface-enhanced Raman scattering (SERS). Negatively charged silver nanoparticles, Ag [-], synthesized via a modified citrate reduction method, were also investigated for comparison. At a sparse surface coverage of 30 nanoparticles/microm(2), substrates with immobilized Ag [+] showed increasing SERS sensitivity to a variety of anions in water in the order SO(4)(2-) < CN(-) < SCN(-) approximately ClO(4)(-), with corresponding binding constants of 10(5), 3.3 x 10(5), and 10(7) (for both SCN- and ClO(4)(-)) M(-1), respectively. This order followed the Hofmeister series of anion binding in water. Significantly, substrates with Ag [+] allowed limit of detection values of 8.0 x 10(-8) M (8 ppb) and 2.7 x 10(-7) M (7 ppb) for environmentally relevant perchlorate (ClO(4)(-)) and cyanide (CN(-)) anions, respectively. In contrast, substrates with immobilized Ag [-], even upon subsequent modification by a monolayer of BPEI for positive surface charge of the nanoparticles, showed a drastically lower sensitivity to these anions. The high sensitivity of substrates with Ag [+] for anion detection can be attributed to the presence of two types of functional groups, amino and amide, on the nanoparticle surface resulting from UV-assisted fragmentation of BPEI chains. Both amino and amide provide strong binding of anions with Ag [+] nanoparticles due to the synergistic effect through a combination of electrostatic, hydrogen bonding, and dispersive interactions.     

Synthesis and characterization of a methacrylate polymer with side chain ketone and its derivatives

A new type of methacrylate monomer,2-(4-benzoylphenoxy)-2-oxoethyl methylacrylate(BOEMA) was synthesized.The radical homopolymerization of BOEMA was performed at 65℃in a 1,4-dioxane solution with benzoyl peroxide as an initiator.The oxime and thiosemicarbazone derivatives of poly[2-(4-benzoylphenoxy)-2-oxoethyl methylacrylate]poly(BOEMA) were prepared with hydroxylamine hydrochloride,and thiosemicarbazone hydrochloride, respectively.The monomer and its homopolymer were characterized with Fourier transform infrared and NMR techniques. The thermal stabilities of poly(BOEMA) and its derivatives were investigated with thermogravimetric analysis and differential scanning calorimetry.The ultraviolet stability of the polymers was compared.The antibacterial and antifungal effects of the monomer and the polymer and its derivatives were also investigated on various bacteria and fungi.The activation energies of the thermal degradation of the polymers were calculated with the Ozawa and Kissinger methods.     

Multivalent Recognition of Concanavalin A by {Mo132} Glyconanocapsules—Toward Biomimetic Hybrid Multilayers

Herein, we consider Müller’s spherical, porous, anionic, molybdenum oxide based capsule, (NH₄)₄₂‐ [{(Mo^VI)Mo^VI₅O₂₁(H₂O)₆}₁₂{Mo^V₂O₄(CH₃COO)}₃₀]?10 CH₃COONH₄? 300 H₂O≡(NH₄)₄₂? 1 a ?crystal ingredients≡ 1 , {Mo₁₃₂}, as an effective sugar‐decorated nanoplatform for multivalent lectin recognition. The ion‐exchange of NH₄⁺ ions of 1 with cationic‐sugars, D ‐mannose‐ammonium chloride ( 2 ) or D ‐glucose‐ammonium chloride ( 3 ) results in the formation of glyconanocapsules (NH₄)_42?n 2 _n? 1 a and (NH₄)_42?m 3 _m? 1 a . The Mannose (NH₄)_42?n 2 _n? 1 a capsules bind selectively Concanavalin A (Con A) in aqueous solution, giving an association avidity constant of ${K{{{\rm multi}\hfill \atop {\rm a}\hfill}}}$ =4.6×10⁴ M ^?1 and an enhancement factor of β=K${{{{\rm multi}\hfill \atop {\rm a}\hfill}}}$ /K${{{{\rm mono}\hfill \atop {\rm ass}\hfill}}}$ =21.9, reminiscent of the formation of “glycoside clusters” on the external surface of glyconanocapsule. The glyconanocapsules (NH₄)_42?n 2 _n? 1 a and (NH₄)_42?m 3 _m? 1 a self‐assemble in “hybrid multilayers” by successive layer‐by‐layer deposition of (NH₄)_42?n 2 _n? 1 a or (NH₄)_42?m 3 _m? 1 a and Con A. These architectures, reminiscent of versatile mimics of artificial tissues, can be easily prepared and quantified by using quartz crystal microgravimetry (QCM). The “biomimetic hybrid multilayers” described here are stable under a continual water flow and they may serve as artificial networks for a greater depth of understanding of various biological mechanisms, which can directly benefit the fields of chemical separations, sensors or storage‐delivery devices.     

Stationary State Entanglement of Two Atoms Inside an Optical Cavity under Noise

In this paper, the entanglement properties of a system of two atoms inside an optical cavity in a stochastic interaction with field are studied by the Jaynes-Cummings Model. The phase telegraph noise is considered as a noise term and an exact solution to the model is obtained. The solution reveals the resulting decoherence effects of the noise on the entanglement properties of the system. It shows that under the noise the individual atoms do not entangle with the cavity field. However, a strong atom-atom entanglement is observed in a stationary state. It is seen that a relatively strong noise is cooperative in the construction of the steady state atom-atom entanglement.     

Nonlinear Responses of a Magnetoelastic Beam in a Step-Pulsed Magnetic Field

A theoretical study is carried out on the dynamics of a magnetoelastic beam being in a step-pulsed magnetic field. For this aim, the magnetic potential and elastic energies are determined for the beam and partial differential equations are established according to Hamilton's principle. It is proven that the magnetoelastic beam can give a variety of complex behavior in the case of step-pulsed field excitations. An intermediate regime of two-well chaos is observed. Theoretical findings were found to be in a good agreement with the experimental results for the specific system parameters. On leave from Institute of Physics, University of Bayreuth, 65440 Bayreuth, Germany An erratum to this article is available at .     

Rheological behavior of concentrated suspensions as affected by the dynamics of the mixing process

The rheological characterizations of concentrated suspensions are generally carried out assuming “well-mixed” suspensions. However, the variation of the concentration distributions of the ingredients of the formulation, i.e., the “goodness of mixing”, the size and shape distributions of the particle clusters and the rheological behavior of the suspension all depend on the thermo-mechanical history that the suspension is exposed to during the mixing process. Here, various experimental tools are used for the characterization of the degree of mixedness (concentration distributions) of various ingredients along with the characterization of rheological material functions, wall slip behavior and the maximum packing fraction of a graphite/elastomer suspension. The degree of mixedness values of the ingredients of the suspensions processed using batch and continuous processes and under differing operating conditions were characterized quantitatively using wide-angle X-ray diffraction and thermo gravimetric analysis and were elucidated under the light of the electrical properties of the suspension as affected by the mixing process. Upon achieving better homogeneity of the graphite particles and the binder and decreases in the size and breadth of the size distributions of particle clusters (as inferred from electrical measurements and maximum packing fraction values), the elasticity (storage modulus) and the shear viscosity (magnitude of the complex viscosity from small-amplitude oscillatory shear and shear viscosity from steady torsional and capillary rheometry) of the suspension decreased significantly and the wall slip velocity values increased. These findings demonstrate the intimate relationships that exist between the rheological behavior of concentrated suspensions and the thermo-mechanical history that they are exposed to during the processing stage and suggest that the preparation conditions for suspensions should be carefully selected and well documented to achieve reproducible characterization of rheological material functions.     

Global behavior of homogeneous random neural systems

We define a simple form of homogeneous neural network model whose characteristics are expressed in terms of probabilistic assumptions. The networks considered operate in an asynchronous manner and receive the influence of the environment in the form of external stimulations. The operation of the network is described by means of a Markovian process whose steady-statesolution yields several global measures of the network's activity. Three different types of external stimulations are investigated, which represent possible input mechanisms. The analytical results obtained concern the macroscopic viewpoint and provide a quick insight into the structure of the network's behavior.     

Molecular structure and vibrational spectra of [2-Oxo-2-(4-acetyl) phenyl amino] ethylene methacrylate by density functional theory and ab initio Hartree–Fock calculations

The molecular geometry and vibrational frequencies of the [2-Oxo-2-(4-acetyl) phenyl amino] ethylene methacrylate (APEMA) were examined theoretically using the Hartree–Fock and Density function method (B3LYP) with 6-31G(d) basis set. The calculated geometrical parameters of the investigated molecule were compared with experimental data. Both the calculated structural parameters and vibrational frequencies are in good agreement with the available experimental data.     

Structure elucidation of cresylviolet perchlorate in polyvinylbutyral by the joint application of IR, FTIR, Raman, UV and visible spectroscopy

Infrared, Fourier transform infrared, Raman, UV absorption and emission spectra of cresylviolet perchlorate (CV) in polyvinylbutyral (PVB) were recorded in the region 1250-4000 cm(-1) at room temperature and assignments have been made for the observed absorption emission and Raman scattered lines.