Methods and approaches for determination and enantioseparation of (RS)‐propranolol

Propranolol, a β‐adrenergic receptor antagonist, is a chiral compound that is marketed as a racemate, but only the (S)‐(?)‐enantiomer is responsible for the β‐adrenoceptor blocking activity. Different chromatographic methods have been applied for separation and determination of enantiomers of (RS)‐propranolol. In this article a review is presented on different liquid chromatographic methods used for enantioseparation of (RS)‐propranolol, using both HPLC and TLC. In addition, some aspects of enantioseparation under achiral phases of liquid chromatography have been briefly mentioned.     

Determination of monensin, narasin, and salinomycin in mineral premixes, supplements, and animal feeds by liquid chromatography and post-column derivatization: collaborative study

A liquid chromatographic (LC) method for the analysis of monensin, narasin, and salinomycin in mineral premixes, supplements, and complete animal feeds at medicating and trace levels was collaboratively studied. The method uses methanol-water (90 + 10) extraction with mechanical shaking for 1 h, filtration, and dilution if necessary. Determination of the 3 ionophores is by reversed-phase LC using post-column derivatization with vanillin and detection at 520 nm. Suspect positive trace-level products and medicated feeds containing unexpected ionophores are confirmed by hexane extraction or post-column derivatization with dimethylaminobenzaldehyde (DMAB). Twenty-five test samples of medicated feeds, supplements, and mineral and drug premixes, and 9 test samples for trace-level analysis were sent to 11 collaborators in Bulgaria, Czech Republic, Portugal, France, The Netherlands, United States, and Canada. Acceptable results were received from 10 laboratories. For the medicated complete feeds, supplements, and mineral premixes, RSDr values (within-laboratory repeatability) ranged from 2.5 to 5.2%, RSDR values (among-laboratory reproducibility) ranged from 2.7 to 6.8%, and HorRat values ranged from 0.31 to 1.30. For the drug premixes, the result variability was excessive and HorRat values ranged from 2.27 to 14.1. For the trace-level test samples, all laboratories correctly identified the analytes and did not report any false positives. RSDr values ranged from 1.3 to 9.5%, RSDR values ranged from 5.2 to 13.1%, and HorRat values ranged from 0.4 to 0.97.     

Molecularly Imprinted Nanospheres by Nonaqueous Emulsion Polymerization

The preparation of nanosized, molecularly imprinted polymer particles by nonaqueous emulsion polymerization is presented. Monodisperse cross‐linked polymer nanospheres with a diameter of around 100 nm were synthesized using a standard monomer mixture of methacrylic acid and ethylene dimethacrylate, containing (±)‐propranolol as a template. The rebinding efficiency of the resulting particles was determined by batch rebinding tests and isothermal titration calorimetry (ITC). The results indicate that the proposed imprinting process under nonaqueous conditions lead to particles with an enhanced capacity of template rebinding compared to both nonimprinted ones and to particles obtained by more conventional emulsion polymerization in water.

     

Analytical Solution for Radial Deformations of Functionally Graded Isotropic and Incompressible Second-Order Elastic Hollow Spheres

We analytically analyze radial expansion/contraction of a hollow sphere composed of a second-order elastic, isotropic, incompressible and inhomogeneous material to delineate differences and similarities between solutions of the first- and the second-order problems. The two elastic moduli are assumed to be either affine or power-law functions of the radial coordinate R in the undeformed reference configuration. For the affine variation of the shear modulus μ, the hoop stress for the linear elastic (or the first-order) problem at the point R=(R _ou R _in (R _ou +R _in )/2)^1/3 is independent of the slope of the μ vs. R line. Here R _in and R _ou equal, respectively, the inner and the outer radius of the sphere in the reference configuration. For μ(R)∝R ⁿ , for the linear problem, the hoop stress is constant in the sphere for n=1. However, no such results are found for the second-order (i.e., materially nonlinear) problem. Whereas for the first-order problem the shear modulus influences only the radial displacement and not the stresses, for the second-order problem the two elastic constants affect both the radial displacement and the stresses. In a very thick homogeneous hollow sphere subjected only to pressure on the outer surface, the hoop stress at a point on the inner surface depends upon values of the two elastic moduli. Thus conclusions drawn from the analysis of the first-order problem do not hold for the second-order problem. Closed form solutions for the displacement and stresses for the first-order and the second-order problems provided herein can be used to verify solutions of the problem obtained by using numerical methods.     

Exact Solutions and Material Tailoring for Functionally Graded Hollow Circular Cylinders

We employ the Airy stress function to derive analytical solutions for plane strain static deformations of a functionally graded (FG) hollow circular cylinder with Young’s modulus E and Poisson’s ratio v taken to be functions of the radius r. For E ₁ and v ₁ power law functions of r, and for E ₁ an exponential but v ₁ an affine function of r, we derive explicit expressions for stresses and displacements. Here E ₁ and v ₁ are effective Young’s modulus and Poisson’s ratio appearing in the stress-strain relations. It is found that when exponents of the power law variations of E ₁ and v ₁ are equal then stresses in the cylinder are independent of v ₁; however, displacements depend upon v ₁. We have investigated deformations of a FG hollow cylinder with the outer surface loaded by pressure that varies with the angular position of a point, of a thin cylinder with pressure on the inner surface varying with the angular position, and of a cut circular cylinder with equal and opposite tangential tractions applied at the cut surfaces. When v ₁ varies logarithmically through-the-thickness of a hollow cylinder, then the maximum radial stress, the maximum hoop stress and the maximum radial displacements are noticeably affected by values of v ₁. Conversely, we find how E ₁ and v ₁ ought to vary with r in order to achieve desired distributions of a linear combination of the radial and the hoop stresses. It is found that for the hoop stress to be constant in the cylinder, E ₁ and v ₁ must be affine functions of r. For the in-plane shear stress to be uniform through the cylinder thickness, E ₁ and v ₁ must be functions of r ². Exact solutions and optimal design parameters presented herein should serve as benchmarks for comparing approximate solutions derived through numerical algorithms.     

Exact solutions for radial deformations of a functionally graded isotropic and incompressible second-order elastic cylinder

We find closed-form solutions for axisymmetric plane strain deformations of a functionally graded circular cylinder comprised of an isotropic and incompressible second-order elastic material with moduli varying only in the radial direction. Cylinder's inner and outer surfaces are loaded by hydrostatic pressures. These solutions are specialized to cases where only one of the two surfaces is loaded. It is found that for a linear through-the-thickness variation of the elastic moduli, the hoop stress for the first-order solution (or in a cylinder comprised of a linear elastic material) is a constant but that for the second-order solution varies through the thickness. The radial displacement, the radial stress and the hoop stress do not depend upon the second-order elastic constant but the hydrostatic pressure and hence the axial stress depends upon it. When the two elastic moduli vary as the radius raised to the power two or four, the radial and the hoop stresses in an infinite space with a pressurized cylindrical cavity equal the pressure in the cavity. For an affine variation of the elastic moduli, the hoop stress in an internally loaded cylinder made of a linear elastic isotropic and incompressible material at the point is the same as that in a homogeneous cylinder. Here R_in and R_ou equal, respectively, the inner and the outer radius of the undeformed cylinder and R the radial coordinate of a point in the unstressed reference configuration.     

Material instability criterion near a notch-tip under locally adiabatic deformations of thermoviscoplastic materials

A material instability criterion for locally adiabatic plane strain deformations of a thermoviscoplastic material near a notch-tip is proposed. It is used to rank eight materials according to their susceptibility to instability.     

Simple and efficient synthesis of substituted 2-pyrrolidinones, 2-pyrrolones, and pyrrolidines from enaminones of Baylis-Hillman derivatives of 3-isoxazolecarbaldehydes

The enaminones, generated from derivatives of appropriately substituted Baylis-Hillman adducts of 3-isoxazolecarbaldehydes, undergo intramolecular ring-closure reactions to afford substituted 2-pyrrolidinones, 1,5-dihydro-2-pyrrolones, and N-substituted pyrrolidines in good yields.