Michaelcrabtree3124

A family of four push-pull porphyrazines of A3B type, where each unit A contains two peripheral propyl chains and the unit B is endowed with a carboxylic acid, were prepared. The carboxylic acid was attached to the β-position of the pyrrolic unit, either directly (Pz 10), or through cyanovinyl (Pz 11) and phenyl (Pz 7) groups. The fourth Pz (14) consisted in a pyrazinoporphyrazine wherein the dinitrogenated heterocycle provided intrinsic donor-acceptor character to the macrocycle and contained a carboxyphenyl substituent. The direct attachment of the carboxylic acid functions and their linkers to the porphyrazine core produces stronger perturbation on the electronic properties of the macrocycle, with respect to their connection through fused benzene or pyrazine rings in TT112 and 14, respectively. The HOMO and LUMO energies of the Pzs, which were estimated with DFT calculations, show little variation within the series, except upon introduction of the cyanovinyl spacer, which produces a decrease in both frontier orbital energetic levels. This effective interaction of cyanovinyl substitution with the macrocycle is also evidenced in UV/Vis spectroscopy, where a large splitting of the Q-band indicates strong desymmetrization of the Pz. The performance of the four Pzs as photosensitizers in DSSCs were also investigated.Disrupted endothelial metabolism is linked to endothelial dysfunction and cardiovascular disease. Targeted metabolic inhibitors are potential therapeutics; however, their systemic impact on endothelial metabolism remains unknown. In this study, we combined stable isotope labeling with 13C metabolic flux analysis (13C MFA) to determine how targeted inhibition of the polyol (fidarestat), pentose phosphate (DHEA), and hexosamine biosynthetic (azaserine) pathways alters endothelial metabolism. Glucose, glutamine, and a four-carbon input to the malate shuttle were important carbon sources in the baseline human umbilical vein endothelial cell (HUVEC) 13C MFA model. We observed two to three times higher glutamine uptake in fidarestat and azaserine-treated cells. Fidarestat and DHEA-treated HUVEC showed decreased 13C enrichment of glycolytic and TCA metabolites and amino acids. Azaserine-treated HUVEC primarily showed 13C enrichment differences in UDP-GlcNAc. 13C MFA estimated decreased pentose phosphate pathway flux and increased TCA activity with reversed malate shuttle direction in fidarestat and DHEA-treated HUVEC. In contrast, 13C MFA estimated increases in both pentose phosphate pathway and TCA activity in azaserine-treated cells. learn more These data show the potential importance of endothelial malate shuttle activity and suggest that inhibiting glycolytic side branch pathways can change the metabolic network, highlighting the need to study systemic metabolic therapeutic effects.The pavement inspection task, which mainly includes crack and garbage detection, is essential and carried out frequently. The human-based or dedicated system approach for inspection can be easily carried out by integrating with the pavement sweeping machines. This work proposes a deep learning-based pavement inspection framework for self-reconfigurable robot named Panthera. Semantic segmentation framework SegNet was adopted to segment the pavement region from other objects. Deep Convolutional Neural Network (DCNN) based object detection is used to detect and localize pavement defects and garbage. Furthermore, Mobile Mapping System (MMS) was adopted for the geotagging of the defects. The proposed system was implemented and tested with the Panthera robot having NVIDIA GPU cards. The experimental results showed that the proposed technique identifies the pavement defects and litters or garbage detection with high accuracy. The experimental results on the crack and garbage detection are presented. It is found that the proposed technique is suitable for deployment in real-time for garbage detection and, eventually, sweeping or cleaning tasks.Meat products represent a significant share of US consumer food expenditures. The COVID-19 pandemic directly impacted both demand and supply of US beef and pork products for a prolonged period, resulting in a myriad of economic impacts. The complex disruptions create significant challenges in isolating and inferring consumer-demand changes from lagged secondary data. Thus, we turn to novel household-level data from a continuous consumer tracking survey, the Meat Demand Monitor, launched in February 2020, just before the US pandemic. We find diverse impacts across US households related to "hoarding" behavior and financial confidence over the course of the pandemic. Combined, these insights extend our understanding of pandemic impacts on US consumers and provide a timely example of knowledge enabled by ongoing and targeted household-level data collection and analysis.We aimed to evaluate whether the duration and stage of acute kidney injury (AKI) are associated with the occurrence of chronic kidney disease (CKD) in patients undergoing cardiac or thoracic aortic surgery. A total of 2009 cases were reviewed. The patients with postoperative AKI stage 1 and higher stage were divided into transient (serum creatinine elevation ≤48 h) or persistent (>48 h) AKI, respectively. Estimated glomerular filtration rate (eGFR) values during three years after surgery were collected. Occurrence of new-onset CKD stage 3 or higher or all-cause mortality was determined as the primary outcome. Multivariable Cox regression and Kaplan-Meier survival analysis were performed. The Median follow-up of renal function after surgery was 32 months. The cumulative incidences of our primary outcome at one, two, and three years after surgery were 19.8, 23.7, and 26.1%. There was a graded significant association of AKI with new-onset CKD during three years after surgery, except for transient stage 1 AKI (persistent stage 1 HR 3.11, 95% CI 2.62-4.91; transient higher stage HR 4.07, 95% CI 2.98-6.11; persistent higher stage HR 13.36, 95% CI 8.22-18.72). There was a significant difference in survival between transient and persistent AKI at the same stage. During three years after cardiac surgery, there was a significant and graded association between AKI stages and the development of new-onset CKD, except for transient stage 1 AKI. This association was stronger when AKI lasted more than 48 h at the same stage. Both duration and severity of AKI provide prognostic value to predict the development of CKD.