Evaluating the polymerization effectiveness and biocompatibility of bio-sourced, visible light-based photoinitiator systems.

The use of photopolymerization is expanding across a multitude of biomedical applications, from drug delivery to bioprinting. Many of these current and emerging photopolymerization systems employ visible light, as motivated by safety and energy efficiency considerations. However, the "library" of visible light initiators is limited compared with the wealth of options available for UV polymerization. Furthermore, the synthesis of traditional photoinitiators relies on diminishing raw materials, and several traditional photoinitiators are considered emerging environmental contaminants. As such, there has been recent focus on identifying and characterizing biologically sourced, visible light-based photoinitiator systems that can be effectively used in photopolymerization applications. In this regard, several bio-sourced molecules have been shown to act as photoinitiators, primarily through Type II photoinitiation mechanisms. However, whether bio-sourced molecules can also act as effective synergists in these reactions remains unknown. In this study, we evaluated the effectiveness of bio-sourced synergist candidates, with a focus on amino acids, due to their amine functional groups, in combination with two bio-sourced photoinitiator molecules: riboflavin and curcumin. We tested the effectiveness of these photoinitiator systems under both violet (405 nm) and blue (460-475 nm) light using photo-rheology. We found that several synergist candidates, namely lysine, arginine, and histidine, increased the polymerization effectiveness of riboflavin when used with both violet and blue light. With curcumin, we found that almost all tested synergist candidates slightly decreased the polymerization effectiveness compared with curcumin alone under both light sources. These results show that bio-sourced molecules have the potential to be used as synergists with bio-sourced photoinitiators in visible light photopolymerization. However, more work must be done to fully characterize these reactions and to investigate more synergist candidates. Ultimately, this information is expected to expand the range of available visible light-based photoinitiator systems and increase their sustainability.

Rush hour-and-a-half: Traffic is spreading out post-lockdown.

Traffic congestion is ubiquitous in major cities around the world. Congestion is associated with a slew of negative effects, including delays and local air pollution. Because of the negative effects of congestion, governments invest billions of dollars into the highway system to try to reduce congestion and accommodate peak-hour automobile travel demand. The COVID-19 pandemic presented a significant disruption to transportation systems globally. One impact was a drastic reduction in travel, leading to free-flowing traffic conditions in many previously-congested cities. As lockdowns eased, traffic volumes returned to near-normal levels. However, the temporal pattern of demand may differ, due to increased remote work or other factors. In this article, we examine the temporal distribution of highway demand in California, using data from over 3,500 traffic sensors. We find that peak-hour automobile travel is spreading in the post-lockdown period. In addition to decreased traffic congestion, this finding also has implications for infrastructure investment. Roadways are generally sized based on peak-hour demand. As the peaks spread, some highway construction project may prove unnecessary. It may be possible to reallocate road space to other uses with fewer tradeoffs in terms of traffic congestion.

Uncovering Structure-Activity Relationships in Pt/CeO2 Catalysts for Hydrogen-Borrowing Amination.

The hydrogen-borrowing amination of alcohols is a promising route to produce amines. In this study, experimental parameters involved in the preparation of Pt/CeO2 catalysts were varied to assess how physicochemical properties influence their performance in such reactions. An amination reaction between cyclopentanol and cyclopentylamine was used as the model reaction for this study. The Pt precursor used in the catalyst synthesis and the properties of the CeO2 support were both found to strongly influence catalytic performance. Aberration corrected scanning transmission electron microscopy revealed that the most active catalyst comprised linearly structured Pt species. The formation of these features, a function result of epitaxial Pt deposition along the CeO2 [100] plane, appeared to be dependent on the properties of the CeO2 support and the Pt precursor used. Density functional theory calculations subsequently confirmed that these sites were more effective for cyclopentanol dehydrogenation-considered to be the rate-determining step of the process-than Pt clusters and nanoparticles. This study provides insights into the desirable catalytic properties required for hydrogen-borrowing amination but has relevance to other related fields. We consider that this study will provide a foundation for further study in this atom-efficient area of chemistry.

The COVID-19 pandemic and the future of telecommuting in the United States.

This study focuses on an important transport-related long-term effect of the COVID-19 pandemic in the United States: an increase in telecommuting. Analyzing a nationally representative panel survey of adults, we find that 40-50% of workers expect to telecommute at least a few times per month post-pandemic, up from 24% pre-COVID. If given the option, 90-95% of those who first telecommuted during the pandemic plan to continue the practice regularly. We also find that new telecommuters are demographically similar to pre-COVID telecommuters. Both pre- and post-COVID, higher educational attainment and income, together with certain job categories, largely determine whether workers have the option to telecommute. Despite growth in telecommuting, approximately half of workers expect to remain unable to telecommute and between 2/3 and 3/4 of workers expect their post-pandemic telecommuting patterns to be unchanged from their pre-COVID patterns. This limits the contribution telecommuting can make to reducing peak hour transport demand.

Subjective variables in travel behavior models: a critical review and Standardized Transport Attitude Measurement Protocol (STAMP).

Understanding people's travel behavior is necessary for achieving goals such as increased bicycling and walking, decreased traffic congestion, and adoption of clean-fuel vehicles. To understand underlying motivations, researchers increasingly are adding subjective variables to models of travel behavior. This article presents a systematic review of 158 such studies. Nearly every reviewed article finds subjective variables to be predictive of transport outcomes. However, the 158 reviewed studies include 2864 distinct subjective survey questions. This heterogeneity makes it difficult to reach definitive conclusions about which subjective variables are most important for which transport outcomes. In addition to heterogeneity, challenges of this literature also include an unclear direction of causality and tautological relationships between some subjective variables and behavior. Within the constraints imposed by these challenges, we attempt to evaluate the explanatory power of subjective variables, which subjective variables matter most for which transport choices, and whether the answers to these questions vary between continents. To reduce heterogeneity in future studies, we introduce the Standardized Transport Attitude Measurement Protocol, which identifies a curated set of subjective questions. We have also developed an open-access database of the reviewed studies, including all subjective survey questions and models, with an interactive, searchable interface.

The Long-Term effects of COVID-19 on travel behavior in the United States: A panel study on work from home, mode choice, online shopping, and air travel.

A critical challenge facing transportation planners is to identify the type and the extent of changes in people's activity-travel behavior in the post-Covid-19 pandemic world. In this study, we investigate the travel behavior evolution by analyzing a longitudinal two-wave panel survey data conducted in the United States from April 2020 to May 2021. Encompassing nearly 3,000 respondents across different states, we explored the effects of the pandemic on four major categories of work from home, travel mode choice, online shopping, and air travel. We utilized descriptive and econometric measures, including random effects ordered probit models, to shed light on the pandemic-induced changes and the underlying factors affecting the future of mobility in the post-pandemic world. Upon concrete evidence, our findings substantiate significant observed (i.e., during the pandemic) and expected (i.e., after the pandemic) changes in people's habits and preferences. According to our results, 48% of the respondents anticipate having the option to WFH after the pandemic, which indicates an approximately 30% increase compared to the pre-pandemic period. In the post-pandemic period, auto and transit commuters are expected to be 9% and 31% less than pre-pandemic, respectively. A considerable rise in hybrid work and grocery online shopping is expected. Moreover, 41% of pre-covid business travelers expect to have fewer flights (after the pandemic) while only 8% anticipate more, compared to the pre-pandemic.

A database of travel-related behaviors and attitudes before, during, and after COVID-19 in the United States.

The COVID-19 pandemic has impacted billions of people around the world. To capture some of these impacts in the United States, we are conducting a nationwide longitudinal survey collecting information about activity and travel-related behaviors and attitudes before, during, and after the COVID-19 pandemic. The survey questions cover a wide range of topics including commuting, daily travel, air travel, working from home, online learning, shopping, and risk perception, along with attitudinal, socioeconomic, and demographic information. The survey is deployed over multiple waves to the same respondents to monitor how behaviors and attitudes evolve over time. Version 1.0 of the survey contains 8,723 responses that are publicly available. This article details the methodology adopted for the collection, cleaning, and processing of the data. In addition, the data are weighted to be representative of national and regional demographics. This survey dataset can aid researchers, policymakers, businesses, and government agencies in understanding both the extent of behavioral shifts and the likelihood that changes in behaviors will persist after COVID-19.

The potential stickiness of pandemic-induced behavior changes in the United States.

Human behavior is notoriously difficult to change, but a disruption of the magnitude of the COVID-19 pandemic has the potential to bring about long-term behavioral changes. During the pandemic, people have been forced to experience new ways of interacting, working, learning, shopping, traveling, and eating meals. A critical question going forward is how these experiences have actually changed preferences and habits in ways that might persist after the pandemic ends. Many observers have suggested theories about what the future will bring, but concrete evidence has been lacking. We present evidence on how much US adults expect their own postpandemic choices to differ from their prepandemic lifestyles in the areas of telecommuting, restaurant patronage, air travel, online shopping, transit use, car commuting, uptake of walking and biking, and home location. The analysis is based on a nationally representative survey dataset collected between July and October 2020. Key findings include that the "new normal" will feature a doubling of telecommuting, reduced air travel, and improved quality of life for some.

Correction: Mechanical rigidity of a shape-memory metal-organic framework increases by crystal downsizing.

Correction for 'Mechanical rigidity of a shape-memory metal-organic framework increases by crystal downsizing' by Al A. Tiba et al., Chem. Commun., 2021, 57, 89-92, DOI: 10.1039/D0CC05684G.

Mechanical rigidity of a shape-memory metal-organic framework increases by crystal downsizing.

Soft porous nanocrystals with a pronounced shape-memory effect exhibit two- to three-fold increase in elastic modulus compared to the microcrystalline counterpart as determined by atomic force microscopy nanoindentation. The increase in rigidity is consistent with the known shape-memory effect displayed by the framework solid at the nanoscale. Crystal downsizing can offer new avenues for tailoring the mechanical properties of metal-organic frameworks.

Hydromorphone versus morphine: a historical cohort study to evaluate the quality of postoperative analgesia.

PURPOSE: Opioids are the most widely used therapy for pain during the postoperative period. It has been suggested by some that hydromorphone is clinically superior. Our primary objective was to determine if there is a difference in postoperative pain score ratings between adult patients receiving intravenous hydromorphone vs intravenous morphine on discharge from the post-anesthesia care unit (PACU). METHODS: For this historical cohort study, convenience sampling was used to identify the first 605 patients ≥ 18 yr undergoing elective, non-cardiac surgery. Patients were categorized based on treatment in the PACU with hydromorphone (n = 326) or morphine (n = 279). Pain scores (scale of 0-10), nausea/vomiting (scale of 0-3), pruritis (scale of 0-3), and sedation (scale of 0-4), as well as total opioid dose administered from arrival in the PACU until readiness to discharge were evaluated. RESULTS: For the primary outcome of pain reported at discharge from the PACU, there was no significant difference between the mean (standard deviation) hydromorphone numeric rating scale (NRS) [2.8 (1.6)] and the morphine NRS [2.5 (1.5)] after adjusting for potential confounders (adjusted mean difference, 0.10; 95% confidence interval, -0.21 to 0.42; P = 0.53). Similarly, there were no significant between-group differences in length of stay in the PACU, satisfactory analgesia, nausea/vomiting, and sedation. CONCLUSION: This study serves to help guide the decision-making process for selecting either morphine or hydromorphone for acute postoperative analgesia. Overall, we found no significant difference for analgesia or for common opioid-related adverse effects between these two opioids in the postoperative period at the time of discharge from the PACU. Furthermore, according to this data, the equipotency ratio of hydromorphone to morphine is closer to 1:6.5 rather than the commonly employed 1:5 ratio.

RéSUMé: OBJECTIF: Les opioïdes sont le traitement le plus fréquemment utilisé pour prendre en charge la douleur postopératoire. Certains auteurs suggèrent que l'hydromorphone est supérieure d'un point de vue clinique. Notre objectif principal était de déterminer s'il existait une différence dans les scores de douleur postopératoire entre des patients adultes ayant reçu de l'hydromorphone intraveineuse comparativement à de la morphine intraveineuse lors de leur congé de la salle de réveil. MéTHODE: Pour cette étude de cohorte historique, un échantillonnage de commodité a été utilisé pour identifier les premiers 605 patients ≥ 18 ans subissant une chirurgie non cardiaque non urgente. Les patients ont été catégorisés en fonction du traitement reçu à la salle de réveil, soit hydromorphone (n = 326) ou morphine (n = 279). Les scores de douleur (échelle de 0-10), les nausées et vomissements (échelle de 0-3), le prurit (échelle de 0-3) et la sédation (échelle de 0-4), ainsi que la dose totale d'opioïdes administrés entre l'arrivée en salle de réveil et le moment de recevoir le congé ont été évalués. RéSULTATS: En ce qui touche à notre critère d'évaluation principal de douleur rapportée au moment du congé de la salle de réveil, aucune différence significative n'a été observée entre le score moyen (écart type) de l'hydromorphone sur l'échelle d'évaluation numérique (EEN) [2,8 (1,6)] et celui de la morphine [2,5 (1,5)] après avoir ajusté les valeurs pour tenir compte des facteurs de confusion potentiels (différence moyenne ajustée, 0,10; intervalle de confiance 95 %, -0,21 à 0,42; P = 0,53). De la même manière, aucune différence intergroupe significative n'a été observée en matière de durée de séjour à la salle de réveil, d'analgésie satisfaisante, de nausées et vomissements, et de sédation. CONCLUSION: Cette étude sert à guider le processus de prise de décision lors du choix de la morphine ou de l'hydromorphone pour l'analgésie postopératoire aiguë. Globalement, nous n'avons observé aucune différence significative dans l'analgésie procurée ou les effets secondaires néfastes liés aux opioïdes entre ces deux molécules en période postopératoire au moment du congé de la salle de réveil. En outre, selon ces données, le ratio d'efficacité équivalente de l'hydromorphone par rapport à la morphine est plus proche de 1:6,5 que du ratio fréquemment utilisé de 1:5.

Metabolic analyses elucidate non-trivial gene targets for amplifying dihydroartemisinic acid production in yeast.

Synthetic biology enables metabolic engineering of industrial microbes to synthesize value-added molecules. In this, a major challenge is the efficient redirection of carbon to the desired metabolic pathways. Pinpointing strategies toward this goal requires an in-depth investigation of the metabolic landscape of the organism, particularly primary metabolism, to identify precursor and cofactor availability for the target compound. The potent antimalarial therapeutic artemisinin and its precursors are promising candidate molecules for production in microbial hosts. Recent advances have demonstrated the production of artemisinin precursors in engineered yeast strains as an alternative to extraction from plants. We report the application of in silico and in vivo metabolic pathway analyses to identify metabolic engineering targets to improve the yield of the direct artemisinin precursor dihydroartemisinic acid (DHA) in yeast. First, in silico extreme pathway (ExPa) analysis identified NADPH-malic enzyme and the oxidative pentose phosphate pathway (PPP) as mechanisms to meet NADPH demand for DHA synthesis. Next, we compared key DHA-synthesizing ExPas to the metabolic flux distributions obtained from in vivo (13)C metabolic flux analysis of a DHA-synthesizing strain. This comparison revealed that knocking out ethanol synthesis and overexpressing glucose-6-phosphate dehydrogenase in the oxidative PPP (gene YNL241C) or the NADPH-malic enzyme ME2 (YKL029C) are vital steps toward overproducing DHA. Finally, we employed in silico flux balance analysis and minimization of metabolic adjustment on a yeast genome-scale model to identify gene knockouts for improving DHA yields. The best strategy involved knockout of an oxaloacetate transporter (YKL120W) and an aspartate aminotransferase (YKL106W), and was predicted to improve DHA yields by 70-fold. Collectively, our work elucidates multiple non-trivial metabolic engineering strategies for improving DHA yield in yeast.