Interaction of ultrasonic waves with structural damage: A diffraction analogy

This study investigates the interaction of ultrasonic waves and structural damage, i.e., cracking and corrosion. It is shown that cracking and corrosion damage produces a diffraction pattern that resembles that associated with the traditional physics of wave motion. The extension of this hypothesis implies that it may be possible to use a simple ripple tank to investigate how to best detect/sense and size a given damage state, e.g., corrosion. We also find that cracking, and corrosion damage, has a significant effect on both the amplitude and period of the waveform and also on the local (apparent) refractive index of the material and that these effects have the potential to be used as damage indicators.     

Assessment of multiple flat elliptical cracks with interactions

The failure of aging aircraft, pressure vessels and many welded structures is frequently due to elliptical cracks, which arise due to in service operation or the initial fabrication processes. Cracks have the potential to interact. Determination of the residual strength of structure requires an accurate knowledge of the stress intensity factor distribution around the crack front. When interacting cracks prevail, the lack of interaction effect in among multiple cracks may lead to an inadequate evaluation. A hybrid formulation capable of representing stiffness change is developed. This enables the accurate analysis of multiple load path structures containing multiple three dimensional cracks. This procedure complement the standard finite element alternating technique.     

Main group supramolecular chemistry

Metal directed self-assembly has yielded a wide array of two- and three-dimensional structures with fascinating new chemical properties. These structures have typically been prepared utilizing transition metals as directing units, owing to the well-defined coordination preferences these metals exhibit. An area of growing research interest involves the preparation of structures containing main group elements as directing units. This tutorial review surveys the wide range of structure types available through this approach, specifically covering unique structure types accessible from the unusual coordination geometries often exhibited by the elements in Groups 12-17 of the periodic table. This review should be of interest to supramolecular and main group chemists, and researchers in the fields of crystal engineering, host-guest chemistry, and molecular recognition.     

Polymer-drug conjugates: Manipulation of drug delivery kinetics

Three methods of manipulating the kinetics of hydrolysis of polymer conjugates were evaluated. It was demonstrated that either first-order, zero-order or S-shaped kinetic profiles could be achieved by systematic changes in the chemical composition of several series of model side-chain substituted polyacrylates. The changes in kinetics were shown to arise from an increase in the rate constant during solvolysis, resulting from predictable changes in either the water content, secondary structure, or LCST of the polymer conjugate.     

Vapor Pressure and Heat of Sublimation of Crystal Polymorphs

In order to determine the applicability of vapor pressure studies on polymorphic modifications, pairs of enantiotropically related modifications of caffeine, theophylline and carbamazepine were investigated. The studies were performed over a wide temperature range (71 to 191°C) and accordingly over a wide vapor pressure range (0.02 to 400 Pa) using an automatic instrument constructed on the basis of the gas saturation principle. This instrument enables an analytical determination of the main component and the impurities present by the chromatographic separation of the substances transported in the gas flow. Therefore, the real partial pressure of the main component can be measured. Due to the high precision of the applied method it was possible to determine partial pressure curves and the thermodynamic transition temperature — the point at which the vapor pressure of two crystal polymorphs is equal. The thermodynamic transition temperatures of caffeine and theophylline were determined to be 136 and 232°C, respectively. These values are in agreement with experimental or calculated values derived from DSC investigations but are more reliable. Vapor pressure measurements of carbamazepine are only meaningful in the low temperature range due to its decomposition at high temperatures. The thermodynamics, advantages and limits of vapor pressure determinations of polymorphic modifications are discussed.This revised version was published online in November 2005 with corrections to the Cover Date.     

Electrospun dextran fibrous membranes

Ultra-fine fiber mats of dextran (powder; M _w = 64,000–76,000 Da) were fabricated by electrospinning, using water as the solvent. The effects of solution concentration (i.e., 0.7–1.3 g mL⁻¹) and applied electric field (9–21 kV/15 cm) on morphological appearance and size of the obtained fibers were investigated. Under a fixed electric field of 15 kV/15 cm and a fixed solution flow rate of 0.25 mL h⁻¹, beaded fibers were observed up to a critical concentration of about 0.9 g mL⁻¹, beyond which only smooth fibers were obtained. The average diameter of these fibers increased monotonically with increasing the solution concentration (i.e., from ∼290 to ∼1950 nm). For the dextran solutions investigated, increasing the electric field generally caused the diameters of the obtained fibers to increase, with the average diameter of the obtained fibers ranging between 520 and 1760 nm. To improve the usefulness of the electrospun dextran fiber mats in an aqueous medium, cross-linking with glutaraldehyde was necessary. The effects of curing temperature (i.e., 70–90 °C), curing time (i.e., 3–48 h), and added MgCl₂ catalyst (i.e., 0.01–0.03 g) on physical integrity of the cross-linked dextran membranes in water were investigated. Both the swelling and the weight loss in water of the cross-linked membranes were generally found to decrease with increasing curing temperature, curing time, and MgCl₂ loading and the cross-linking did not affect the morphology of the obtained membranes.     

Three-dimensional structure optimal design for extending fatigue life by using biological algorithm

This paper presents some applications of a new structural shape optimization procedure for maximizing fatigue life or inspection intervals for damage tolerant structures. In this approach, a new and simple method, which we termed FAST (Failure Analysis of Structures), for estimating the stress intensity factor for cracks at a notch, as well as an extension of the biological algorithm was employed to study the problem of optimization with fatigue life as the design objective. Research by the authors has demonstrated that the optimum shape for minimizing stress is not necessarily the optimum shape for static strength or fatigue life of a damage tolerant structure. The examples are presented that highlight this difference. The optimal shapes for stress are compared with optimized shapes found for static strength with different crack lengths. These are also compared with optimized shapes found for maximum fatigue life. The choice of initial crack size was found to have a significant effect on the optimal shapes for the structures presented.     

A biospectroscopic interrogation of fine needle aspirates points towards segregation between graded categories: an initial study towards diagnostic screening

Fine needle aspirates (FNAs) of suspicious breast lesions are often used to aid the diagnosis of female breast cancer. Biospectroscopy tools facilitate the acquisition of a biochemical cell fingerprint representative of chemical bonds present in a biological sample. The mid-infrared (IR; 4,000–400 cm⁻¹) is absorbed by the chemical bonds present, allowing one to derive an absorbance spectrum. Complementary to IR spectroscopy, Raman spectroscopy measures the scattering by chemical bonds following excitation by a laser to generate an intensity spectrum. Our objective was to apply these methods to determine whether a biospectroscopy approach could objectively segregate different categories of FNAs. FNAs of breast tissue were collected (n = 48) in a preservative solution and graded into categories by a cytologist as C1 (non-diagnostic), C2 (benign), C3 (suspicious, probably benign) or C5 (malignant) [or C4 (suspicious, probably malignant); no samples falling within this category were identified during the collection period of the study]. Following washing, the cellular material was transferred onto BaF₂ (IR-transparent) slides for interrogation by Raman or Fourier-transform IR (FTIR) microspectroscopy. In some cases where sufficient material was obtained, this was transferred to low-E (IR-reflective) glass slides for attenuated total reflection–FTIR spectroscopy. The spectral datasets produced from these techniques required multivariate analysis for data handling. Principal component analysis followed by linear discriminant analysis was performed independently on each of the spectral datasets for only C2, C3 and C5. The resulting scores plots revealed a marked overlap of C2 with C3 and C5, although the latter pair were both significantly segregated (P < 0.001) in the Raman spectra. Good separation was observed between C3 and C5 in all three spectral datasets. Analysis performed on the average spectra showed the presence of three distinct cytological groups. Our findings suggest that biospectroscopy tools coupled with multivariate analysis may support the current FNA tests whilst increasing the sensitivity and associated reliability for improved diagnostics.     

Effect of gamma radiation on dilute aqueous solutions and thin films of N-succinyl chitosan

N-Succinyl chitosan (N-SC) products with various degrees of substitution were synthesized by a direct reaction between chitosan and succinic anhydride. The susceptibility of the as-synthesized polymers to degradation upon their exposure to γ-ray radiation was investigated. The results were compared with the as-received chitosan. The size exclusion chromatographic results showed that chitosan and N-SC products in their dilute aqueous solution state were more subservient to degradation by γ-ray radiation than in their solid film state, despite the much less exposure to the radiation (i.e., 5-30 kGy for the solutions versus 20-100 kGy for the films). Increasing the radiation dose resulted in the rather monotonous decrease in the molecular weights of the polymers. Structural analyses of the irradiated polymers by Fourier-transformed infrared spectroscopy (FT-IR) and UV-visible spectrophotometry indicated the increase in the amount of carbonyl groups with the radiation dose. The formation of the carbonyl groups suggested that the radiolysis of chitosan and N-SC products occurred at the glycosidic linkages. In addition, FT-IR, elemental analysis and proton nuclear magnetic resonance spectroscopy (¹H NMR) results suggested that γ-ray radiation affected both the N-acetyl and N-substituted groups on the polymer chains.