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A series of multicyclic hydrocarbons were synthesized in high yield and under mild conditions from 2,5-hexanedione, cyclohexanone and cyclopentanone, on a scale of 200 g.
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With pedestrian and bicycle safety as the focus, this study investigates the role of urban form, burdened communities (BCs), and demographics at the national level. Urban form can contribute to segregation, limiting access to crucial resources such as safe infrastructure, essential services, and economic opportunities. Leveraging recent data, this research applies six key indicators to identify BCs based on various socioeconomic and environmental factors. Here, the study creates a unique database combining 10 years of pedestrian-bicycle-involved fatal crashes with data for the 71,729 census tracts with burden indicators and census data. The data are analyzed using descriptives and rigorous zero-hurdle negative binomial models, which account for excessive zeros observed in the data. The inference-based analysis results reveal a positive correlation between burden indicators and pedestrian-bicycle-involved fatal crash occurrences, alongside a heightened risk in areas with high-intensity development. Higher Black, American Indian, or Alaska Native populations are associated with more fatal crashes. The study offers novel insights into safety dynamics across different contexts characterized by urban forms, BCs, and demographics. The study underscores the importance of targeted interventions to enhance pedestrian and bicycle safety.
Dock-less bicycle-sharing programs have been widely accepted as an efficient mode to benefit health and reduce congestions. And modeling and prediction has always been a core proposition in the field of transportation. Most of the existing demand prediction models for shared bikes take regions as research objects; therefore, a POI-based method can be a beneficial complement to existing research, including zone-level, OD-level, and station-level techniques. Point of interest (POI) is the location description of spatial entities, which can reflect the cycling route characteristics for both commuting and noncommuting trips to a certain extent, and is also the main generating point and attraction point of shared-bike travel flow. In this study, we make an effort to model a POI-level cycling demand with a Bayesian hierarchical method. The proposed model combines the integrated nested Laplace approximation (INLA) and random partial differential equation (SPDE) to cope with the huge computation in the modeling process. In particular, we have adopted the dock-less bicycle-sharing rental records of Mobike as a case study to validate our method; the study area was one of the fastest growing urban districts in Shanghai in August 2016. The operation results show that the method can help better understand, measure, and characterize spatiotemporal patterns of bike-share ridership at the POI level and quantify the impact of the spatiotemporal effect on bicycle-sharing use.
Herein we report that ene reductases (EREDs) can facilitate an unprecedented intramolecular β-C–H functionalization reaction for the synthesis of bridged bicyclic nitrogen heterocycles containing the 6-azabicyclo[3.2.1]octane scaffold. To streamline the synthesis of these privileged motifs, we developed a gram-scale one-pot chemoenzymatic cascade by combining iridium photocatalysis with EREDs, using readily available N-phenylglycines and cyclohexenones that can be obtained from biomass. Further derivatization using enzymatic or chemical methods can convert 6-azabicyclo[3.2.1]octan-3-one into 6-azabicyclo[3.2.1]octan-3α-ols, which can be potentially utilized for the synthesis of azaprophen and its analogues for drug discovery. Here, mechanistic studies revealed the reaction requires oxygen, presumably to produce oxidized flavin, which can selectively dehydrogenate the 3-substituted cyclohexanone derivatives to form the α,β-unsaturated ketone, which subsequently undergoes spontaneous intramolecular aza-Michael addition under basic conditions.
Herein we report that ene reductases (EREDs) can facilitate an unprecedented intramolecular β-C–H functionalization reaction for the synthesis of bridged bicyclic nitrogen heterocycles containing the 6-azabicyclo[3.2.1]octane scaffold. To streamline the synthesis of these privileged motifs, we developed a gram-scale one-pot chemoenzymatic cascade by combining iridium photocatalysis with EREDs, using readily available N-phenylglycines and cyclohexenones that can be obtained from biomass. Further derivatization using enzymatic or chemical methods can convert 6-azabicyclo[3.2.1]octan-3-one into 6-azabicyclo[3.2.1]octan-3α-ols, which can be potentially utilized for the synthesis of azaprophen and its analogues for drug discovery. Furthermore, mechanistic studies revealed the reaction requires oxygen, presumably to produce oxidized flavin, which can selectively dehydrogenate the 3-substituted cyclohexanone derivatives to form the α,β-unsaturated ketone, which subsequently undergoes spontaneous intramolecular aza-Michael addition under basic conditions.
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W(NCPh 3 )(OSiPh 3 ) 2 (C7H 12 ) (1) and W(NAd)(OSiPh 3 ) 2 (C 7 H 12 ) (2) undergo photochemical α-hydrogen abstraction to form alkylidenes. Transient absorption studies suggest that fast W–C homolysis precedes thermal α-hydrogen abstraction. Radical trapping experiments in the presence of 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) support formation of an alkyl radical in these reactions. DFT calculations of models of 1 and 2 are also consistent with formation of W(V)-alkyl-radical intermediates that ultimately abstract an α-hydrogen to form the alkylidene. This article provides evidence for W–C bond cleavage in reac-tions that convert catalytically inactive d 0 tungstacyclopentanes into metathesis-active alkylidenes.
Gas-fermenting acetogens can upgrade one-carbon (C1) compounds (such as CO2 and CO) to the two-carbon (C2) metabolite acetyl coenzyme A (CoA) and convert sugar feedstocks to acetyl-CoA with minimal CO2 emissions. Fulfilling the biosynthetic potential of these microbes requires overcoming challenges in pathway engineering. Here we design a synthetic acetyl-CoA bi-cycle-in addition to the natural carbon-fixing pathways-for C2 metabolite synthesis. This pathway produces an acetyl-CoA by fixation of two CO2 equivalents via three functional modules acting in sequence: carbon fixation, gluconeogenesis and non-oxidative glycolysis. The pathway was examined by in silico thermodynamic and kinetic analyses. The prototypic pathway was implemented in a syngas-fermenting organism, Clostridium ljungdahlii DSM 13528, by expressing a heterologous phosphoketolase that can work with other native enzymes in the host acetogen. The carbon conversion pathway is possible under various growth conditions and is independent of the Wood-Ljungdahl pathway for the valorization of H2 and CO2. This study reports the improvement of carbon conversion using a reductive acetyl-CoA bi-cycle and the potential impact of redox homoeostasis in the acetogenic host for industrial applications of gas fermentation.
Toxic organochloride molecules are widely used in industry for various purposes. With their high volatility, the direct detection of organochlorides in environmental samples is challenging. Here, a new organochloride detection mechanism using 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) is introduced to simplify a sensing method with higher detection sensitivity. Three types of organochloride compounds-trichloroethylene (TCE), dichloromethane (DCM), and dichlorodiphenyltrichloroethane (DDT)—were targeted to understand DCM conjugation chemistry by using nuclear magnetic resonance (NMR) and liquid chromatography with a mass spectrometer (LC-MS). 13C-NMR spectra and LC-MS data indicated that DBN can be labeled on these organochloride compounds by chlorine–nitrogen interaction. Furthermore, to demonstrate the organochloride sensing capability, the labeling yield and limit of detection were determined by a colorimetric assay as well as micellar electrokinetic chromatography (MEKC). The interaction with DBN was most appreciable for TCE, among other organochlorides. TCE was detected at picomolar levels, which is two orders of magnitude lower than the maximum contaminant level set by the United States Environmental Protection Agency. MEKC, in conjunction with this DBN-labeling method, enables us to develop a field-deployable sensing platform for detecting toxic organochlorides with high sensitivity.
The oxygen-evolving complex (OEC) of Photosystem II (PSII) catalyzes light-driven water oxidation, a process necessary to sustain Earth’s atmospheric oxygen. Oxygen yields measured during single-turnover flash sequences exhibit period-four oscillations, which form the basis of the Joliot–Kok (S-state) model. However, when the oscillations of other processes contribute to the measured oxygen yield, fitting methods can conflate these signals and distort estimates of inefficiencies and initial S-state populations. To address this, we applied the empirical wavelet transform (EWT) as a model-independent method to separate overlapping oscillators and capture damping dynamics that are not well represented in Fourier analysis. We tested this framework on polarographic flash-oxygen traces from both our Synechocystis sp. PCC 6803 thylakoid membrane preparations and archival datasets on Chlorella and isolated chloroplasts. EWT consistently resolves the expected period-four component alongside a distinct binary oscillation. Simulations suggest that fitting this isolated period-four signal recovers VZAD parameters more accurately than analysis of raw traces, yielding different estimates for S-state distributions and transition probabilities. Notably, this binary oscillation aligns closely with semiquinone dynamics predicted solely from period-four fit parameters. These findings indicate that EWT can effectively distinguish complex signals in oxygen evolution, offering a framework potentially applicable to other spectroscopic probes of the S-state cycle.
Cities and communities continue to expand pedestrian and bicycle infrastructure as part of their sustainable mobility and post-pandemic recovery plans. However, the emergence of micro-mobility (e.g., electric bicycles) has created new challenges for urban transport planning. As the popularity of micro-mobility modes has grown, so have safety concerns due to rising injuries, thus challenging many cities to come up with regulatory measures that enable efficient access while minimizing negative impacts from micro-mobility. Leveraging the Open-Source Tool (Mobility Energy Productivity metric), powered by an open-source dataset (OpenStreetMap), and enhanced through the incorporation of perceived discomfort (level-of-traffic stress), this research study focuses on evaluating the accessibility implications of infrastructure planning and regulatory measures for micro-mobility. Five scenarios pertaining to level of traffic stress, sidewalk access, traffic calming, and bike lane coverage were tested in the Denver-Aurora region in Colorado. Maximum improvements in energy-efficient access are realized when allowing sidewalks for micro-mobility use. Cities and planning agencies could leverage this information to assess sidewalk use policies for micro-mobility, while ensuring pedestrian safety and ADA access. Results indicate that expansion of bicycle lane coverage yields 11% accessibility benefits for micro-mobility compared to implementing traffic calming measures yielding 3% accessibility improvements. Further, it was observed most of the population in the Denver-Aurora region is experiencing lower accessibility in-part due to presence of a high-stress connections in the network. Although not generalizable, the use of open-source data and access calculation methodology, make this analysis reproducible and transferable to other locations.
Developing a powerful bifunctional catalyst for tandem reactions is essential to the future carbon neutrality by reducing the energy consumption in chemical industries. Herein, mesoporous zeolite-encapsulated palladium (Pd) nanoparticles (Pd@meso-ZSM-5) synthesized via emulsification-demulsification followed by a dry-gel transformation method were demonstrated to have a remarkable catalytic performance for a one-pot multiple tandem reaction of cyclic ketones (cyclopentanone, cyclohexanone) to bicyclic alkanes (bicyclopentane, bicyclohexane). Compared with supported catalysts (Pd/meso-ZSM-5) and microporous zeolite-encapsulated catalysts (Pd@ZSM-5) with a primary product of monocyclic alkane (cyclopentane, cyclohexane), Pd@meso-ZSM-5 shows much higher catalytic efficiency for the bicyclic alkanes synthesis, which was previously unattainable in the conventional two-step synthesis route. Controlled experiments and detailed characterizations show that mesoporosity provides sufficient space for the generation and diffusion of large molecular intermediates, and the intimate acid-Pd interface promotes the conversion of intermediates. As a result, this work proposes a design strategy for a mesoporous zeolite-encapsulated metal catalyst, which efficiently provides cooperative acid-hydrogenation catalysis.