Immobilizing a Fluorescent Dye Offers Potential to Investigate the Glass/Resin Interface

Silane coupling agents are commonly applied to glass fibers to promote fiber/resin adhesion and enhance durability in composite parts. In this study, a coupling agent multilayer on glass was doped with trace levels of the dimethylaminonitrostilbene (DMANS) fluorophore. The fluorophore was immobilized on the glass surface by tethering the molecule to a triethoxy silane coupling agent, creating the DMANS/silane coupling agent molecule (DMSCA). DMSCA was then diluted with commonly used coupling agents and grafted to a glass microscope coverslip to create a model composite interface. A 53-nm blue shift in fluorescence from the immobilized DMSCA can be followed during cure of an epoxy resin overlayer, giving this technique potential to monitor the properties of the fiber/resin interface during composite processing. Contact angle measurements on these coupling agent layers were similar in the presence or absence of the DMSCA molecule, suggesting that trace levels of the fluorescent probe did not affect the structure of the layer. The immobilized DMSCA molecule behaved similarly to the DMANS precursor in solution. Both showed longer wavelength fluorescence in more polar environments. Copyright 2000 Academic Press.     

(Z)-3-p-tolylsulfinylacrylonitrile as a chiral dienophile: diels-alder reactions with furan and acyclic dienes

The behavior of (Z)-3-p-tolylsulfinylacrylonitrile (1) as a chiral dienophile has been evaluated from its reactions with furan and acyclic dienes. Electrostatic interactions of the cyano group with the sulfinyl one restrict the conformational mobility around the C-S bond, thus controlling the pi-facial selectivity, which is almost complete in all cases, the approach of the diene from the less-hindered face of the dienophile (that bearing the lone electron pair) in the predominant rotamer being the favored one. The regioselectivity is also completely controlled by the cyano group. Additionally, the reactivity of compound 1 as well as its endo-selectivity are both higher than those observed for the corresponding (Z)-3-sulfinylacrylates, thus proving the potential of sulfinylnitriles as chiral dienophiles.     

Solid-Phase Synthesis of a Monofunctional trans-a(2)Pt(II) Complex Tethered to a Single-Stranded Oligonucleotide

Cross-linking ability is possible with the oligonucleotide-tethered, monofunctional trans-Pt(II) complex shown. It was synthesized by a novel solid-phase approach comprising conjugation of immobilized tetrathymidylic acid with a trans-a(2)Pt(II) building unit, ammonolysis, and transformation of the resulting complex (R=1-N-cyclohexylmethylthyminate) into the chloro derivative (R=Cl). a=NH(2)CH(3), T=thymine.     

An outdoor smog chamber and modeling study of toluene–NOx photooxidation

An experimental investigation of the gas-phase photooxidation of toluene–NO_x–air mixtures at part-per-million concentrations has been carried out in a 65-m³, outdoor smog chamber to assess our understanding of the atmospheric chemistry of toluene. In addition, six CO? NO_x–air irradiations were conducted to characterize the chamber with regard to any wall radical sources. Measured parameters in the toluene–NO_x experiments included O₃, NO, NO₂, HNO₃, peroxyacetyl nitrate (PAN), CO, toluene, benzaldehyde, o-cresol, m-nitrotoluene, peroxybenzoyl nitrate (PBZN), temperature, relative humidity, aerosol size distributions, and particulate organic carbon. Predictions of the reaction mechanism of Leone and Seinfeld [7] are found to be in good agreement with the data under a variety of initial conditions. Additional simulations are used to investigate various mechanistic pathways in areas where our understanding of toluene chemistry is still incomplete.     

Control of stochastic distributed-parameter systems

A scheme is proposed for the feedback control of distributed-parameter systems with unknown boundary and volume disturbances and observation errors. The scheme consists of employing a nonlinear filter in the control loop such that the controller uses the optimal estimates of the state of the system. A theoretical comparison of feedback proportional control of a styrene polymerization reactor with and without filtering is presented. It is indicated how an approximate filter can be constructed, greatly reducing the amount of computing required.Notation a(t) l-vector noisy dynamic input to system - A(t, a) l-vector function - A frequency factor for first-order rate law (5.68×10⁶ sec^–1) - b distance to the centerline between two coil banks in the reactor (4.7 cm) - B k-vector function defining the control action - c(, ) concentration of styrene monomer, molel ^–1 - C _p heat capacity (0.43 cal · g^–1 · K^–1) - C _ij constants in approximate filter, Eqs. (49)–(52) - E activation energy (20330 cal · mole^–1) - expectation operator - f(t,...) n-vector function - g ₀,g ₁(t,...) n-vector functions - h(t, u) m-vector function relating observations to states - H(t) function defined in Eq. (36) - k dimensionality of control vectorv(x, t) - k _i constants in approximate filter, Eqs. (49)–(52) - K dimensionless proportional gain - l dimensionality of dynamic inputa(t) - m dimensionality of observation vectory(t) - n dimensionality of state vectoru(x, t) - P ^(vv)(x, s, t) n×n matrix governed by Eq. (9) - P ^(va)(x, t) n×l matrix governed by Eq. (10) - P ^(aa)(t) l×l matrix governed by Eq. (11) - q _i (t) diagonal elements ofm×m matrixQ(x, s, t) - Q(x, s, t) m×m weighting matrix - R universal gas constant (1.987 cal · mole^–1 · K^–1) - R(x, s, t) n×n weighting matrix - R _i (t) n×n weighting matrix - s dimensionless spatial variable - S(x, s, t) matrix defined in Eq. (11) - t dimensionless time variable - T(, ) temperature, K - u(x, t) n-dimensional state vector - u _c (t) wall temperature - u _d desired value ofu ₁(1,t) - u _c * reference control value ofu _c - u _c ^max maximum value ofu _c - u _c ^min minimum value of _c - v(x, t) k-dimensional control vector - W(t) l×l weighting matrix - x dimensionless spatial variable - y(t) m-dimensional observation vector - _i constants in approximate filter, Eqs. (49)–(52) - dimensionless parameter defined in Eq. (29) - H heat of reaction (17500 cal · mole^–1) - dimensionless activation energy, defined in Eq. (29) - (x) Dirac delta function - (x, t) m-dimensional observation noise - thermal conductivity (0.43×10^–3 cal · cm^–1 · sec^–1 · K^–1) - density (1 g · cm^–3) - time, sec - dimensionless parameter defined in Eq. (29) - spatial variable, cm - * reference value - ^ estimated value