Insight into industrial PLA aging process by complementary use of rheology,HPLC, and MALDI

Nowadays, there is a growing availability of biodegradable industrial materials intended to food contact applications whose service life behavior needs to be further investigated. This article is focused on the degradation of two materials based on polylactic acid. The correlation between the rate of degradation and the amount of trapped degradation products was investigated applying three characterization techniques in parallel, namely rheology, high‐performance liquid chromatography (HPLC), and matrix‐assisted laser desorption/ionization (MALDI). The rate of degradation was studied through the evaluation of their rheological properties and calculation of the number of average molecular weights, and weight‐average molecular weights. Water‐soluble oligomers and lactic acid were quantified by HPLC‐ultraviolet. Changes in cyclic and linear oligomers were monitored by MALDI‐time‐of‐flight mass spectrometry. Specimens of 4‐mm thickness of each biopolymer were subjected to hydrolysis in deionized water up to 6 months at two temperatures, simulating service conditions of food packaging. The diminution in viscosity and consequently in molecular weight distribution (20–60%) showed the degradation of the molecular structure of both polylactic acids. The chain scission was followed through the increasing values of lactic acid and hydrolyzed oligomers (twofold to eightfold), and the predominant signal of the linear oligomers over the cyclic ones with aging. Rheology, HPLC, and MALDI showed to be complementary tools to better understand the changes in the molecular structure. The obtained results showed the necessity of adding suitable stabilizers for each particular food packaging application. Copyright © 2013 John Wiley & Sons, Ltd.     

Physical properties (thermal,thermomechanical, magnetic,and adhesive) of some smart orthodontic wires

Thermal, thermomechanical, and caloric properties of commercial orthodontic wires (produced by Natural Orthodontics Corp., USA) with cylindrical and rectangular geometry were studied. Depending on the applied forces, there were identified the range of elasticity, the elasticity–viscoelasticity coexistence domain and the domain in which a maximum force of 18 N is applied, for the orthodontic wires. When increasing the thickness of orthodontic wires, deformation decreases. The Controlled Force Module, in the tension mode, was used for the determination of the orthodontic wires elongation at application of the stretching forces from 0 to 13 N, at 35 °C, maintaining each static force value for 3 min. The increase in the cross-sectional area of the orthodontic wires disfavors the process of elongation of the sample, at the same applied static force. Using the Multi-Frequency–Strain–Stress modulus, in the tension mode, DMA cyclic heating–cooling measurements were performed. The measured physical quantities for orthodontic wires were Storage Modulus, Loss Modulus, Tanδ and Stiffness, at heating and cooling. Thus, the characteristic temperatures of the phase transitions (A_s, A_f, M_s, M_f), of all the studied orthodontic wires were identified. Also, the values of the elasticity modulus (Young’s Modulus) of the orthodontic wires were calculated at 35 °C. With the DSC Q200 device, using temperature-modulated differential scanning calorimetry method, a multi-step temperature variation program, was applied to a rectangular wire, in three stages (cooling–heating–cooling). Through the interpretation of heat fluxes (reversible, irreversible and total), the phase transitions in the formation of martensite, austenite, but also of the rombohedral phase (R-phase), were identified. Formations of austenite and martensite were also evidenced by the classical DSC method, but the classical DSC method also enabled the R-phase identification. The adherence of some food dyes on the orthodontic wires, as well as the modification of the surface roughness of the orthodontic wire after the deposition of the food dye, was also studied. By magnetic measurements, it was established that the orthodontic wires had paramagnetic properties at room temperature, and nitinol was a mixture of 49.2% austenite and 50.8% martensite.

     

Compatibility study of tobramycin and pharmaceutical excipients using differential scanning calorimetry,FTIR, DRX,and HPLC

Differential scanning calorimetry (DSC), isothermal stress testing–Fourier transform infrared spectroscopy (IST–FTIR), isothermal stress testing–high-performance liquid chromatography, and powder X-ray diffraction (PDRX) were used as screening techniques for assessing the compatibility of tobramycin with some currently employed ophthalmic excipients. In the first phase of the study, DSC was used as a tool to detect any interaction. The absolute value of the difference between the enthalpy of the pure tobramycin melting peak and that of its melting peak in the different analyzed mixtures was chosen as a parameter of the drug–excipient interaction degree. DSC results demonstrated that benzalkonium chloride, monobasic sodium phosphate, boric acid, edetate disodium, sodium metabisulfite, thimerosal, and potassium sorbate interact with tobramycin. Taking into account these results, it could be suggested that some of the changes observed in the IST–FTIR spectra of binary blends of tobramycin and some of the excipients would account for a possible interaction between the mixture component. In this study, PDRX did not provide much information, since only tobramycin–thimerosal interactions could be detected. DSC and IST–FTIR are suitable and simple methods for the detection of potential incompatibilities between active pharmaceutical ingredient (API) and excipients.

     

A note on the two-stage hybrid flow shop problem with dedicated machines

In this paper we introduce a new dominance rule for the two-stage hybrid flow shop problem with dedicated machines. The rule is then used to construct a dominating set. The efficiency of the proposed rule is shown through an analysis of the dominating set cardinality.     

Theoretical prediction of the damping of a railway wheel with sandwich-type dampers

This paper presents a procedure for predicting the damping added to a railway wheel when sandwich-type dampers are installed. Although there are different ways to reduce the noise generated by a railway wheel, most devices are based on the mechanism of increasing wheel damping. This is why modal damping ratios are a clear indicator of the efficiency of the damping device and essential when a vibro-acoustic study of a railway wheel is carried out. Based on a number of output variables extracted from the wheel and damper models, the strategy explained herein provides the final damping ratios of the damped wheel. Several different configurations are designed and experimentally tested. Theoretical and experimental results agree adequately, and it is demonstrated that this procedure is a good tool for qualitative comparison between different solutions in the design stages.     

Asymmetric Carboxycyanation of Aldehydes by Cooperative AlF/Onium Salt Catalysts: from Cyanoformate to KCN as Cyanide Source

Asymmetric 1,2-additions of cyanide yield enantioenriched cyanohydrins as versatile chiral building blocks. Next to HCN, volatile organic cyanide sources are usually used. Among them, cyanoformates are more attractive on technical scale than TMSCN for cost reasons, but catalytic productivity is usually lower. Here, the development of a new strategy for cyanations is described, in which this activity disadvantage is overcome. A Lewis acidic Al center cooperates with an aprotic onium moiety within a remarkably robust bifunctional Al–F–salen complex. This allowed for unprecedented turnover numbers of up to 10⁴. DFT studies suggest an unexpected unique trimolecular pathway in which the ammonium bound cyanide attacks the aldehyde, which itself is activated by the carbonyl group of the cyanoformate binding to the Al center. In addition, a novel practical carboxycyanation method was developed that makes use of KCN as the sole cyanide source. The use of a pyrocarbonate as carboxylating reagent provided the best results.     

Synthesis and Biological Evaluation of RGD Peptidomimetic–Paclitaxel Conjugates Bearing Lysosomally Cleavable Linkers

Two small‐molecule–drug conjugates (SMDCs, 6 and 7 ) featuring lysosomally cleavable linkers (namely the Val–Ala and Phe–Lys peptide sequences) were synthesized by conjugation of the α_vβ₃‐integrin ligand cyclo[DKP–RGD]‐CH₂NH₂ ( 2 ) to the anticancer drug paclitaxel (PTX). A third cyclo[DKP–RGD]–PTX conjugate with a nonpeptide “uncleavable” linker ( 8 ) was also synthesized to be tested as a negative control. These three SMDCs were able to inhibit biotinylated vitronectin binding to the purified α_Vβ₃‐integrin receptor at nanomolar concentrations and showed good stability at pH 7.4 and pH 5.5. Cleavage of the two peptide linkers was observed in the presence of lysosomal enzymes, whereas conjugate 8 , which possesses a nonpeptide “uncleavable” linker, remained intact under these conditions. The antiproliferative activities of the conjugates were evaluated against two isogenic cell lines expressing the integrin receptor at different levels: the acute lymphoblastic leukemia cell line CCRF‐CEM (α_Vβ₃?) and its subclone CCRF‐CEM α_Vβ₃ (α_Vβ₃+). Fairly effective integrin targeting was displayed by the cyclo[DKP–RGD]–Val–Ala–PTX conjugate ( 6 ), which was found to differentially inhibit proliferation in antigen‐positive CCRF‐CEM α_Vβ₃ versus antigen‐negative isogenic CCRF‐CEM cells. The total lack of activity displayed by the “uncleavable” cyclo[DKP–RGD]–PTX conjugate ( 8 ) clearly demonstrates the importance of the peptide linker for achieving the selective release of the cytotoxic payload.