Bioinspired light-driven chloride pump with helical porphyrin channels.

Halorhodopsin, a light-driven chloride pump, utilizes photonic energy to drive chloride ions across biological membranes, regulating the ion balance and conveying biological information. In the light-driven chloride pump process, the chloride-binding chromophore (protonated Schiff base) is crucial, able to form the active center by absorbing light and triggering the transport cycle. Inspired by halorhodopsin, we demonstrate an artificial light-driven chloride pump using a helical porphyrin channel array with excellent photoactivity and specific chloride selectivity. The helical porphyrin channels are formed by a porphyrin-core star block copolymer, and the defects along the channels can be effectively repaired by doping a small number of porphyrins. The well-repaired porphyrin channel exhibits the light-driven Cl- migration against a 3-fold concentration gradient, showing the ion pumping behavior. The bio-inspired artificial light-driven chloride pump provides a prospect for designing bioinspired responsive ion channel systems and high-performance optogenetics.

One Porphyrin Per Chain Self-Assembled Helical Ion-Exchange Channels for Ultrahigh Osmotic Energy Conversion.

Ion-exchange membranes (IEMs) convert osmotic energy into electricity when embedded in a reverse electrodialysis cell. IEMs with both high permselectivity and ionic conductivity are highly needed to increase the energy conversion efficiency. The ionic conductivity can be improved by increasing the content of immobile charge carriers, but it is always accompanied by undesirable permselectivity decrease due to excess swelling. Until now, breaking the permselectivity-conductivity tradeoff still has remained a challenge. Here, we demonstrate a membrane with the least ion-exchange capacity (∼10-2 mequiv g-1), generating an ultrahigh power density of 19.3 W m-2 at a 50-fold concentration ratio. The membrane is made of a porphyrin-core four-star block copolymer (p-BCP), forming the high-density helical porphyrin channels (∼1011 cm-2) under the synergistic effect of BCP self-assembly and porphyrin π-π stacking. The porphyrin channel shows high Cl- selectivity and high conductivity, benefiting high-performance osmotic energy conversion. This economic and facile membrane design strategy provides a promising approach to developing a new generation of IEMs.

The Activating Effect of Strong Acid for Pd-Catalyzed Directed C-H Activation by Concerted Metalation-Deprotonation Mechanism.

A computational study on the origin of the activating effect for Pd-catalyzed directed C-H activation by the concerted metalation-deprotonation (CMD) mechanism is conducted. DFT calculations indicate that strong acids can make Pd catalysts coordinate with directing groups (DGs) of the substrates more strongly and lower the C-H activation energy barrier. For the CMD mechanism, the electrophilicity of the Pd center and the basicity of the corresponding acid ligand for deprotonating the C-H bond are vital to the overall C-H activation energy barrier. Furthermore, this rule might disclose the role of some additives for C-H activation.

Visible-Light-Induced Selective Defluoroborylation of Polyfluoroarenes, gem-Difluoroalkenes, and Trifluoromethylalkenes.

Fluorinated organoboranes serve as versatile synthetic precursors for the preparation of value-added fluorinated organic compounds. Recent progress has been mainly focused on the transition-metal catalyzed defluoroborylation. Herein, we report a photocatalytic defluoroborylation platform through direct B-H activation of N-heterocyclic carbene boranes, through the synergistic merger of a photoredox catalyst and a hydrogen atom transfer catalyst. This atom-economic and operationally simple protocol has enabled defluoroborylation of an extremely broad scope of multifluorinated substrates including polyfluoroarenes, gem-difluoroalkenes, and trifluoromethylalkenes in a highly selective fashion. Intriguingly, the defluoroborylation protocol can be transition-metal free, and the regioselectivity obtained is complementary to the reported transition-metal-catalysis in many cases.

Designing new Togni reagents by computation.

New trifluoromethylating reagents are designed via computational studies inspired by Togni's experimental research. Trans influence and steric effects are important for this rational design. We have found that the Togni derivative with X = SO2 is the best choice based on its high reactivity and its potential synthesis.

Photo-induced Decarboxylative Heck-Type Coupling of Unactivated Aliphatic Acids and Terminal Alkenes in the Absence of Sacrificial Hydrogen Acceptors.

1,2-Disubstituted alkenes such as vinyl arenes, vinyl silanes, and vinyl boronates are among the most versatile building blocks that can be found in every sector of chemical science. We herein report a noble-metal-free method of accessing such olefins through a photo-induced decarboxylative Heck-type coupling using alkyl carboxylic acids, one of the most ubiquitous building blocks, as the feedstocks. This transformation was achieved in the absence of external oxidants through the synergistic combination of an organo photo-redox catalyst and a cobaloxime catalyst, with H2 and CO2 as the only byproducts. Both control experiments and DFT calculations supported a radical-based mechanism, which eventually led to the development of a selective three-component coupling of aliphatic carboxylic acids, acrylates, and vinyl arenes. More than 90 olefins across a wide range of functionalities were effectively synthesized with this simple protocol.

A Twist of the Twist Mechanism, 2-Iodoxybenzoic Acid (IBX)-Mediated Oxidation of Alcohol Revisited: Theory and Experiment.

2-Iodoxybenzoic acid (IBX) is an important species for the oxidation of alcohols to aldehydes or ketones. An often-cited mechanism involving a hypervalent twist as the rate-determining step (RDS) is inconsistent with kinetic isotope effect (KIE) experiments. The computations with larger basis sets reveal that the reductive elimination involving the C-H bond cleavage is the RDS (rate-determining step). Further computational/experimental studies suggest that the reactivity can be improved by adjusting the trans influence with Lewis acids.

The effect of Operation 24 Hours on reducing collision in the City of Edmonton.

In the City of Edmonton, in order to reduce the prevalence of collisions, the Operation 24 Hours program (OPS24) was developed by using existing police and transportation services resources. The program uses traditional manned police speed enforcement method, which are supplemented by traffic safety messages displayed on permanent and mobile dynamic messaging signs (DMS). In this paper, collision data analysis was performed by looking at the daily number of collisions from 2008 to 2011 that covers 28 Operation 24 Hours (OPS24) events. The objective of the collision data analysis is to analyze if there is a reduction in collision frequencies after OPS24 was held and examined how long the collision reduction effect last. Weather factors such as temperature, thickness of snow, and wind gust have been considered by many as a great influence on collision occurrences, especially in a city with long and cold winter such as Edmonton. Therefore, collision modeling was performed by considering these external weather factors. To analyze the linear and periodic trend of different collision types (injury, fatal, and property damage only (PDO)) and examine the influence of weather factors on collisions, negative binomial time series model that accounts for seasonality and weather factors was used to model daily collision data. The modeling also considered collision proportion to account for missing traffic volume data; the Gaussian time series model that accounts for seasonality and weather factors was used to model collision proportion. To estimate the collision trend and test for changes in collision levels before/after OPS24, interrupted time series model with segmented regression was used. While for estimating how long the effect of the OPS24 last, change point method was applied.

[Spectral reflectance response of plant leaf to simulated UVB stress].

In the present study, we evaluate the relative content of chlorophyll and spectral reflectance variations in the visible light under different intensity of UVB (L-UVB, CK and UVB) of three typical evergreen broadleaf plants in China subtropical area. In different simulated UVB condition, the experiment shows that different tree species have different UVB sensitivity, and chlorophyll content varies greatly with species, and the chlorophyll relative content with the filter UVB w as significantly higher than with enhanced UVB. In the spectral reflectance of the visible part, it is generally higher with enhanced UVB's treatment than with L-UVB treatment; and any treatments present adaptation, species under different stress. After roles of the different UVB intensity, for each tree species the visible part of the spectral reflectance shows difference between green and red mainly. The study results show that the subtropical evergreen broad-leaved species has a strong sensitivity to the UVB, and UVB response of different tree species varies greatly.