Minimizing the Reorganization Energy of Cobalt Redox Mediators Maximizes Charge Transfer Rates from Quantum Dots.

Light-induced charge separation is at the very heart of many solar harvesting technologies. The reduction of energetic barriers to charge separation and transfer increases the rate of separation and the overall efficiency of these technologies. Here we report that the internal reorganization energy of the redox acceptor, the movement of the atoms with changing charge, has a profound effect on the charge transfer rates from donor quantum dots. We experimentally studied and modelled with Marcus Theory charge transfer to cobalt complexes that have similar redox potentials covering 350 mV, but vastly different reorganization energies spanning 2 eV. While the driving force does influence the electron transfer rates, the reorganization energies had a far more profound effect, increasing charge transfer rates by several orders of magnitude. Our studies suggest that careful design of redox mediators to minimize reorganization energy is an untapped route to drastically increase the efficiency of quantum dot applications that feature charge transfer.

Combination of Computational Techniques to Obtain High-Quality Gelatin-Base Gels from Chicken Feet.

With the increasing global population, it has become necessary to explore new alternative food sources to meet the increasing demand. However, these alternatives sources should not only be nutritive and suitable for large scale production at low cost, but also present good sensory characteristics. Therefore, this situation has influenced some industries to develop new food sources with competitive advantages, which require continuous innovation by generating and utilising new technologies and tools to create opportunities for new products, services, and industrial processes. Thus, this study aimed to optimise the production of gelatin-base gels from chicken feet by response surface methodology (RSM) and facilitate its sensorial classification by Kohonen's self-organising maps (SOM). Herein, a 22 experimental design was developed by varying sugar and powdered collagen contents to obtain grape flavoured gelatin from chicken feet. The colour, flavour, aroma, and texture attributes of gelatines were evaluated by consumers according to a hedonic scale of 1-9 points. Least squares method was used to develop models relating the gelatin attributes with the sugar content and collagen mass, and their sensorial qualities were analysed and classified using the SOM algorithm. Results showed that all gelatin samples had an average above six hedonic points, implying that they had good consumer acceptance and can be marketed. Furthermore, gelatin D, with 3.65-3.80% (w/w) powdered collagen and 26.5-28.6% (w/w) sugar, was determined as the best. Thus, the SOM algorithm proved to be a useful computational tool for comparing sensory samples and identifying the best gelatin product.

Valorization of Chicken Feet By-Product of the Poultry Industry: High Qualities of Gelatin and Biofilm from Extraction of Collagen.

In this research, products with high quality were obtained from natural sources. The sensorial qualities, chemical characterization, and physical properties of gelatin extracted from chicken feet were compared with commercial gelatins. The extraction process was performed using acetic acid on a concentration ranging from 0.318% to 3.682%, processing time between 1.0 h and 8.4 h and extraction temperature between 43.3 °C and 76.8 °C. After the end of each assay, the yield was measured. Results showed that, under the best conditions, the collagen extraction yield was above 8%, and comprised 78.525 g/100 g of protein. Collagen analyzed by ICP-MS was composed of 99.44% of macro-minerals that are of great importance to human health. ATR-FTIR analysis showed that approximately 70.90% of the total protein from chicken feet is collagen, whereas, in commercial gelatin, only 30.31% is collagen. When comparing chicken gelatin with commercial gelatin, most sensory attributes were similar and chicken gelatin gained acceptance by more than 80% of the consumers. Additionally, the collagen films obtained from chicken feet and swine showed water absorption, odors, and texture characteristics similar to commercial material, such as latex and celofane. Consequently, due to its similarity to human skin, it is possible to apply it as a biocurative.

Cobalt cage complexes as mediators of protein electron transfer.

A selection of cobalt (III)/(II) macrobicyclic 'sarcophagine' (sar) cage complexes with N3S3 mixed donor sets but differing in a single apical substituent has been chosen to span a redox potential range of +150 to -150 mV vs the normal hydrogen electrode and thus acts as redox buffers in protein spectroelectrochemistry and redox potentiometry. The cobalt(III) cage complexes are all based on the same parent structure [Co(XMeN3S3sar)]3+, where X, the variable apical substituent, is -NO2, -Cl, -OH, -NH2, or -NMe 3+ , and a methyl group occupies the opposite apical position. The X-ray crystal structures of selected members of this series are reported. Changes to the apical substituent X enable the CoIII/II redox potential to be tuned across a range of more than 200 mV by the inductive effects of the functional group. The pH dependence of the redox potential enabled the pK a values of some functional groups to be determined. The complexes were successfully employed as electron transfer mediators in the spectroelectrochemical investigation of a variety of heme proteins.

Influence of tumour condition on the macrophage activity in Candida albicans infection.

To better understand the interactions between opportunistic fungi and their hosts, we investigated hydrogen peroxide (H2O2), nitric oxide and TNF-alpha production by peritoneal macrophages from Ehrlich tumour-bearing mice (TBM) during microbial infections. For this purpose, TBM at days 7, 14 and 21 of tumour progression were inoculated intraperitoneally with C. albicans and evaluated after 24 and 72 h. We observed that TBM showed significant increases in H2O2, TNF-alpha levels and fungal clearance at day 7 after C. albicans infection. However, as the tumour advanced, there was a progressive decline in the release of H2O2 and TNF-alpha that was paired with the dissemination of C. albicans. These results demonstrate that protective macrophage activities against Candida albicans are limited to the initial stages of tumour growth; continued solid tumour growth weakened the macrophage response and as a consequence, weakened the host's susceptibility to opportunistic infections.

Influence of tumour condition on the Macrophage Activity in Candida albicans infection

To better understand the interactions between opportunistic fungi and their hosts, we investigated hydrogen peroxide (H2O2), nitric oxide and TNF-alpha production by peritoneal macrophages from Ehrlich tumour-bearing mice (TBM) during microbial infections. For this purpose, TBM at days 7, 14 and 21 of tumour progression were inoculated intraperitoneally with C. albicans and evaluated after 24 and 72 h. We observed that TBM showed significant increases in H2O2, TNF-alpha levels and fungal clearance at day 7 after C. albicans infection. However, as the tumour advanced, there was a progressive decline in the release of H2O2 and TNF-alpha that was paired with the dissemination of C. albicans. These results demonstrate that protective macrophage activities against Candida albicans are limited to the initial stages of tumour growth; continued solid tumour growth weakened the macrophage response and as a consequence, weakened the host's susceptibility to opportunistic infections