Influence of chain structure on crystal polymorphism of poly(lactic acid). Part 1: effect of optical purity of the monomer

The influence of chain structure on crystal polymorphism of poly(lactic acid) (PLA) with high l-lactic acid content (97.8–100 %) is detailed in this contribution. Upon usual processing conditions of PLA, only α and α′ crystals grow, which makes these two polymorphs of major interest for research. The two crystal modifications have similar chain packing, which complicates their quantitative analysis by diffraction methods. The two crystal modifications are instead easily identified by analysis of the crystallization kinetics, which varies not only with temperature, but also with crystal polymorphism. The dependence of the rate of ordering on temperature shows two distinct maxima around 105–110 and 120–125 °C, which are related to growth of α′ and α crystals, respectively. Addition of d-lactic acid co-units leads to a decrease of the overall crystallization rate of PLA, as well as of the rate of spherulite growth (G) of both the crystal modifications. The relative crystallization rates of α and α′ forms are highly affected by stereoregularity, especially in the PLA grades that have a high crystallization rate. A high d-lactic acid content results not only in an overall slower crystal growth, but also in a varied temperature range where each of the two crystal modifications prevail, with a shift to lower temperatures of both the maxima of the G vs. temperature plots, indicating that inclusion of d-lactic acid units in the PLA chain affects crystallization rate of both α and α′ crystal modifications.     

Dos(e)Age: Role of Dose and Age in the Long-Term Effect of Cannabinoids on Cognition

Cannabis is still the most widely used illicit drug around the world. While its use has always been prevalent among adolescents, recent evidence suggests that its consumption is also increasing among other population groups, such as pregnant women and aged people. Given the known impact of cannabis on brain development and behavior, it is important to dissect the possible long-term impact of its use across different age groups, especially on measures of cognitive performance. Animal models of cannabinoid exposure have represented a fundamental tool to characterize the long-lasting consequences of cannabinoids on cognitive performance and helped to identify possible factors that could modulate cannabinoids effects in the long term, such as the age of exposure and doses administered. This scoping review was systematically conducted using PubMed and includes papers published from 2015 to December 2021 that examined the effects of cannabinoids, either natural or synthetic, on cognitive performance in animal models where exposure occurred in the prenatal period, during adolescence, or in older animals. Overall, available data clearly point to a crucial role of age in determining the long-term effect of cannabinoid on cognition, highlighting possible detrimental consequences during brain development (prenatal and adolescent exposure) and beneficial outcomes in old age. In contrast, despite the recent advances in the field, it appears difficult to clearly establish a possible role of dosage in the effects of cannabinoids on cognition, especially when the adolescent period is taken into account.     

<Emphasis Type="Italic">parkin</Emphasis> counteracts symptoms in a <Emphasis Type="Italic">Drosophila</Emphasis> model of Parkinson's disease

Background

Parkinson's disease, a prevalent neurodegenerative disease, is characterized by the reduction of dopaminergic neurons resulting in the loss of motor control, resting tremor, the formation of neuronal inclusions and ultimately premature death. Two inherited forms of PD have been linked to mutations in the α-synuclein and parkin genes. The parkin protein functions as an ubiquitin ligase targeting specific proteins for degradation. Expression of human α-synuclein in Drosophila neurons recapitulates the loss of motor control, the development of neuronal inclusions, degeneration of dopaminergic neurons and the ommatidial array to provide an excellent genetic model of PD.

Results

To investigate the role of parkin, we have generated transgenic Drosophila that conditionally express parkin under the control of the yeast UAS enhancer. While expression of parkin has little consequence, co-expression of parkin with α-synuclein in the dopaminergic neurons suppresses the α-synuclein-induced premature loss of climbing ability. In addition directed expression of parkin in the eye counteracts the α-synuclein-induced degeneration of the ommatidial array. These results show that parkin suppresses the PD-like symptoms observed in the α-synuclein-dependent Drosophila model of PD.

Conclusion

The highly conserved parkin E3 ubiquitin ligase can suppress the damaging effects of human α-synuclein. These results are consistent with a role for parkin in targeting α-synuclein to the proteasome. If this relationship is conserved in humans, this suggests that up-regulation of parkin should suppress α-synucleinopathic PD. The development of therapies that regulate parkin activity may be crucial in the treatment of PD.

     

Liquid-crystalline phase behavior of a colloidal rod-plate mixture

The phase behavior of rod-plate mixtures was investigated using model systems containing unambiguously rod- and plate-shaped colloids. We find that the theoretically disputed biaxial nematic phase is unstable with respect to demixing into an isotropic and two uniaxial nematic phases. The phase behavior at very high densities is exceptionally rich and includes the coexistence of up to four different liquid crystalline phases, which stem from the coupling between the employed particle shapes and polydispersity.     

Atmospheric and soil degradation of aliphatic-aromatic polyester films

The degradation of an aliphatic-aromatic biodegradable polyester film was studied under conditions of solar exposure and soil burial in a tropical area. Film samples were evaluated for changes over 40 weeks by visual examination, scanning electronic microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, mechanical properties, molecular weight, gel content, and thermal properties. Photodegradation played a major role in the atmospheric degradation of the film, causing it to lose integrity and mechanical properties after week 8 due to main chain scission and crosslinking. SEM micrographs and FTIR spectra indicated that photodegradation started at the exposed side of the film and propagated through the polymer matrix after week 8. FTIR spectra also indicated that subsequent photooxidation processes took place. The reduction of molecular weight of the soil burial samples was much slower than that of the non-crosslinked portion of solar exposed film samples. The reduction of number average molecular weight of the non-crosslinked solar exposed samples followed a first order reaction, whereas the soil burial samples show a surface erosion biodegradation behavior. The relationship among total solar radiation, gel content and number average molecular weight indicated that an accumulated total solar radiation of 800 MJ/m², reached in approximately 7 weeks at the exposure site, is required for PBAT mulch film integrity loss.     

Cross-sections for deuteron photo-disintegration from 139 to 832 MeV

The cross-sections for deuteron photo-disintegration have been measured at nine c.m. angles from 37 to 143 degrees. The minimum and maximum photon energies have been 139 and 832 MeV respectively. The results are in agreement with earlier data above 300 MeV, but are significantly larger below 200 MeV, the discrepancies being up to 50% at the lowest energies measured.     

Fast atom bombardment mass spectrometry of carbobenzyloxy-protected amino acids and peptides

The positive fast atom bombardment (FAB) mass spectra of 15 N-carbobenzyloxy derivatives of α-amino acids are presented together with those of some synthetic peptides containing other widely employed protecting groups. The data obtained allow a fragmentation pattern to be established for the N-carbobenzyloxy moiety and to obtain detailed structural information on the main fragment ions. A study of the ion current ratio vs. time pattern shows that important fragments derive from the parent protonated molecule through FAB-induced condensed-phase reactions.