Solar-Driven Continuous CO2 Reduction to CO and CH4 using Heterogeneous Photothermal Catalysts: Recent Progress and Remaining Challenges.

The urgent need to reduce the carbon dioxide level in the atmosphere and keep the effects of climate change manageable has brought the concept of carbon capture and utilization to the forefront of scientific research. Amongst the promising pathways for this conversion, sunlight-powered photothermal processes, synergistically using both thermal and non-thermal effects of light, have gained significant attention. Research in this field focuses both on the development of catalysts and continuous-flow photoreactors, which offer significant advantages over batch reactors, particularly for scale-up. Here, we focus on sunlight-driven photothermal conversion of CO2 to chemical feedstock CO and CH4 as synthetic fuel. This review provides an overview of the recent progress in the development of photothermal catalysts and continuous-flow photoreactors and outlines the remaining challenges in these areas. Furthermore, it provides insight in additional components required to complete photothermal reaction systems for continuous production (e. g., solar concentrators, sensors and artificial light sources). In addition, our review emphasizes the necessity of integrated collaboration between different research areas, like chemistry, material science, chemical engineering, and optics, to establish optimized systems and reach the full potential of this technology.

Scale-Up of a Heterogeneous Photocatalytic Degradation Using a Photochemical Rotor-Stator Spinning Disk Reactor.

Many chemical reactions contain heterogeneous reagents, products, byproducts, or catalysts, making their transposition from batch to continuous-flow processing challenging. Herein, we report the use of a photochemical rotor-stator spinning disk reactor (pRS-SDR) that can handle and scale solid-containing photochemical reaction conditions in flow. Its ability to handle slurries was showcased for the TiO2-mediated aerobic photodegradation of aqueous methylene blue. The use of a fast rotating disk imposes high shear forces on the multiphase reaction mixture, ensuring its homogenization, increasing the mass transfer, and improving the irradiation profile of the reaction mixture. The pRS-SDR performance was also compared to other lab-scale reactors in terms of water treated per reactor volume and light power input.

Combatting cyanobacteria with hydrogen peroxide: a laboratory study on the consequences for phytoplankton community and diversity.

Experiments with different phytoplankton densities in lake samples showed that a high biomass increases the rate of hydrogen peroxide (HP) degradation and decreases the effectiveness of HP in the selective suppression of dominant cyanobacteria. However, selective application of HP requires usage of low doses only, accordingly this defines the limits for use in lake mitigation. To acquire insight into the impact of HP on other phytoplankton species, we have followed the succession of three phytoplankton groups in lake samples that were treated with different concentrations of HP using a taxa-specific fluorescence emission test. This fast assay reports relatively well on coarse changes in the phytoplankton community; the measured data and the counts from microscopical analysis of the phytoplankton matched quite well. The test was used to pursue HP application in a Planktothrix agardhii-dominated lake sample and displayed a promising shift in the phytoplankton community in only a few weeks. From a low-diversity community, a change to a status with a significantly higher diversity and increased abundance of eukaryotic phytoplankton species was established. Experiments in which treated samples were re-inoculated with original P. agardhii-rich lake water demonstrated prolonged suppression of cyanobacteria, and displayed a remarkable stability of the newly developed post-HP treatment state of the phytoplankton community.

Simulation of the rate of transfer of antibiotic resistance between Escherichia coli strains cultured under well controlled environmental conditions.

It was demonstrated that the tetracycline resistance plasmid in Escherichia coli resembling K-12 23:06 containing the E. coli plasmid DM0133 could be transferred to tetracycline sensitive E. coli K-12 MG1655 YFP. The sensitive recipient strain has a slight metabolic advantage in continuous fermentation in absence of tetracycline pressure and as a result the numbers of the resistant recipient strain increase during fermentation. In presence of tetracycline pressure the sensitive strain is eliminated, but when it acquires tetracycline resistance the strain has still the same metabolic advantage as its sensitive parent strain in absence of tetracycline. Here a model will be shown that could explain the rate of transformation of a sensitive into a resistant recipient strain and its subsequent growth during continuous fermentation. According to the model the probability of formation of mutants would be much higher at the dilution rate of 0.09 compared to 0.28, whereas the growth of mutants would be much faster at high dilution rate. The growth model shows how the recipient mutants and the donor cells behave in relation to the dilution rate and the number of mutants. Apart from a deterministic model describing the growth rate of both the donor strain and the resistant recipient strain a stochastic model was developed that is particularly useful when low numbers of mutants are formed.

Interaction between mutations and regulation of gene expression during development of de novo antibiotic resistance.

Bacteria can become resistant not only by horizontal gene transfer or other forms of exchange of genetic information but also by de novo by adaptation at the gene expression level and through DNA mutations. The interrelationship between changes in gene expression and DNA mutations during acquisition of resistance is not well documented. In addition, it is not known whether the DNA mutations leading to resistance always occur in the same order and whether the final result is always identical. The expression of >4,000 genes in Escherichia coli was compared upon adaptation to amoxicillin, tetracycline, and enrofloxacin. During adaptation, known resistance genes were sequenced for mutations that cause resistance. The order of mutations varied within two sets of strains adapted in parallel to amoxicillin and enrofloxacin, respectively, whereas the buildup of resistance was very similar. No specific mutations were related to the rather modest increase in tetracycline resistance. Ribosome-sensed induction and efflux pump activation initially protected the cell through induction of expression and allowed it to survive low levels of antibiotics. Subsequently, mutations were promoted by the stress-induced SOS response that stimulated modulation of genetic instability, and these mutations resulted in resistance to even higher antibiotic concentrations. The initial adaptation at the expression level enabled a subsequent trial and error search for the optimal mutations. The quantitative adjustment of cellular processes at different levels accelerated the acquisition of antibiotic resistance.

Effect of growth rate and selection pressure on rates of transfer of an antibiotic resistance plasmid between E. coli strains.

Antibiotic resistance increases costs for health care and causes therapy failure. An important mechanism for spreading resistance is transfer of plasmids containing resistance genes and subsequent selection. Yet the factors that influence the rate of transfer are poorly known. Rates of plasmid transfer were measured in co-cultures in chemostats of a donor and a acceptor strain under various selective pressures. To document whether specific mutations in either plasmid or acceptor genome are associated with the plasmid transfer, whole genome sequencing was performed. The DM0133 TetR tetracycline resistance plasmid was transferred between Escherichia coli K-12 strains during co-culture at frequencies that seemed higher at increased growth rate. Modeling of the take-over of the culture by the transformed strain suggests that in reality more transfer events occurred at low growth rates. At moderate selection pressure due to an antibiotic concentration that still allowed growth, a maximum transfer frequency was determined of once per 10(11) cell divisions. In the absence of tetracycline or in the presence of high concentrations the frequency of transfer was sometimes zero, but otherwise reduced by at least a factor of 5. Whole genome sequencing showed that the plasmid was transferred without mutations, but two functional mutations in the genome of the recipient strain accompanied this transfer. Exposure to concentrations of antibiotics that fall within the mutant selection window stimulated transfer of the resistance plasmid most.

Stretch reflex responses in Complex Regional Pain Syndrome-related dystonia are not characterized by hyperreflexia.

OBJECTIVE: To evaluate if hyperreflexia (exaggerated reflexes) due to disinhibition is associated with dystonia in Complex Regional Pain Syndrome (CRPS). METHODS: Stretch reflexes at the wrist were assessed in healthy controls (n=10) and CRPS-patients with dystonia (n=10). Subjects exerted a wrist flexion torque of 5% of maximum voluntary contraction torque (T(MVC)) to a manipulandum which applied ramp-and-hold stretches to the wrist flexors. Since reflex responses scale with background contraction, controls additionally performed the task at 1% and 3% T(MVC) to attain similar torques as patients who have reduced T(MVC). The M1 onset and the magnitudes of the short latency M1 and long latency M2 were assessed using the electromyographic signals (EMG) of the flexor carpi radialis. EMG of the extensor carpi radialis was recorded to monitor cocontraction. RESULTS: Compared to controls, patients had a substantially reduced T(MVC). Ramp velocity had a significant effect on M1 onset time and magnitude. CONCLUSIONS: Since M1 magnitude decreased with flexion torque, no significant difference was found between patients and controls at 5% T(MVC), while comparison at similar absolute torques (controls at 1% T(MVC)) resulted in significantly smaller M1 magnitudes for patients with dystonia. SIGNIFICANCE: This study suggests that CRPS-patients with dystonia are not hyperreflexive.

De novo acquisition of resistance to three antibiotics by Escherichia coli.

The acquisition of resistance to amoxicillin, tetracycline, and enrofloxacin by Escherichia coli MG 1655 was examined by exposing growing cells to constant or stepwise increasing concentrations of these compounds. The minimal inhibitory concentration (MIC) of E. coli for amoxicillin increased from 4-8 to 32 µg/ml after growth in the presence of 1.25 or 2.5 µg/ml. By stepwise increasing the exposure, an MIC of 512 µg/ml was reached. This high MIC was maintained after removal of the antibiotics, whereas the lesser increase after exposure to low levels was reversed, indicating that the high MIC was due to a genetic change, but the lower one to phenotypic adaptation only. The MIC for tetracycline increased from 2 µg/ml to maximally 32 µg/ml. The MIC decreased to control levels in the absence of tetracycline, so no genetic changes seem to have occurred. The MIC for enrofloxacin increased from 0.25 µg/ml to maximally 512 µg/ml depending on the concentration during growth. These data mostly support the "radical-based" theory that bactericidal antibiotics induce a common mechanism that contributes to cell killing. Our findings indicate that exposure to low levels of antibiotics causes an increase in MIC above the concentration that the cells were exposed to. The implication is that exposure to low levels of antibiotics should be prevented as much as possible, because this causes resistance far more than high concentrations that inhibit growth or kill the cell and thus prevent acquisition of resistance.

Relating reflex gain modulation in posture control to underlying neural network properties using a neuromusculoskeletal model.

During posture control, reflexive feedback allows humans to efficiently compensate for unpredictable mechanical disturbances. Although reflexes are involuntary, humans can adapt their reflexive settings to the characteristics of the disturbances. Reflex modulation is commonly studied by determining reflex gains: a set of parameters that quantify the contributions of Ia, Ib and II afferents to mechanical joint behavior. Many mechanisms, like presynaptic inhibition and fusimotor drive, can account for reflex gain modulations. The goal of this study was to investigate the effects of underlying neural and sensory mechanisms on mechanical joint behavior. A neuromusculoskeletal model was built, in which a pair of muscles actuated a limb, while being controlled by a model of 2,298 spiking neurons in six pairs of spinal populations. Identical to experiments, the endpoint of the limb was disturbed with force perturbations. System identification was used to quantify the control behavior with reflex gains. A sensitivity analysis was then performed on the neuromusculoskeletal model, determining the influence of the neural, sensory and synaptic parameters on the joint dynamics. The results showed that the lumped reflex gains positively correlate to their most direct neural substrates: the velocity gain with Ia afferent velocity feedback, the positional gain with muscle stretch over II afferents and the force feedback gain with Ib afferent feedback. However, position feedback and force feedback gains show strong interactions with other neural and sensory properties. These results give important insights in the effects of neural properties on joint dynamics and in the identifiability of reflex gains in experiments.

Tizanidine does not affect the linear relation of stretch duration to the long latency M2 response of m. flexor carpi radialis.

The long latency M2 electromyographic response of a suddenly stretched active muscle is stretch duration dependent of which the nature is unclear. We investigated the influence of the group II afferent blocker tizanidine on M2 response characteristics of the m. flexor carpi radialis (FCR). M2 response magnitude and eliciting probability in a group of subjects receiving 4 mg of tizanidine orally were found to be significantly depressed by tizanidine while tizanidine did not affect the significant linear relation of the M2 response to stretch duration. The effect of tizanidine on the M2 response of FCR is supportive of a group II afferent contribution to a compound response of which the stretch duration dependency originates from a different mechanism, e.g., rebound Ia firing.

Sensory weighting of force and position feedback in human motor control tasks.

In daily life humans integrate force and position feedback from mechanoreceptors, proprioception, and vision. With handling relatively soft, elastic objects, force and position are related and can be integrated to improve the accuracy of an estimate of either one. Sensory weighting between different sensory systems (e.g., vision and proprioception) has been extensively studied. This study investigated whether similar weighting can be found within the proprioceptive sensory system, more specifically between the modalities force and position. We hypothesized that sensory weighting is governed by object stiffness: position feedback is weighted heavier on soft objects (large deflections), while force feedback is weighted heavier on stiff objects (small deflections). Subjects were instructed to blindly reproduce either position or force while holding a one degree of freedom haptic manipulator that simulated a linear spring with one of four predetermined stiffnesses. In catch trials the spring was covertly replaced by a nonlinear spring. The difference in force (DeltaF) and position (DeltaX) between the regular and the catch trials revealed the sensory weighting between force and position feedback. A maximum likelihood estimation model predicted that: (1) task instruction did not affect the outcome measures, and (2) force feedback is weighted heavier with increasing object stiffness as was hypothesized. Both effects were found experimentally, and the subjects' sensory weighting closely resembled the optimal model predictions. To conclude, this study successfully demonstrated sensory weighting within the proprioceptive system.

The monosynaptic Ia afferent pathway can largely explain the stretch duration effect of the long latency M2 response.

Sudden stretch of active muscle typically results in two characteristic electromyographic responses: the short latency M1 and the long latency M2. The M1 response originates from the monosynaptic Ia afferent reflex pathway. The M2 response is less well understood and is likely a compound response to different afferent inputs mediated by spinal and transcortical pathways. In this study the possible contribution of the Ia afferent pathway to the M2 response was investigated. A mechanism was hypothesized in which the M1 response synchronizes the motoneurons, and therewith their refractory periods. Stretch perturbation experiments were performed on the wrist and results were compared with a computational model of a pool of motoneurons receiving tonic and Ia afferent input. The simulations showed the same stretch amplitude, velocity, and duration-dependent characteristics on the M2 as found experimentally. It was concluded that the stretch duration effect of the M2 likely originates from the proposed Ia afferent mediated mechanism.

Effect of hxk2 deletion and HAP4 overexpression on fermentative capacity in Saccharomyces cerevisiae.

To describe the fermentative potential of a yeast cell, the fermentative capacity (FC) has been defined as the specific rate of ethanol and CO2 production under anaerobic conditions. The effect of growth rate on FC of glucose-limited grown Saccharomyces cerevisiae strains with altered expression of two major glycolytic regulators, Hap4p and Hxk2p, was compared with their parent strain. Whereas overproduction of Hap4p behaved similar to the wild-type strain, deletion of hxk2 resulted in a very different FC profile. Most importantly, with maltose as the carbon and energy source, the latter strain expressed an FC twofold that of the wild type. Further analysis at the level of gene expression showed large changes in ADH2 transcripts and to a lesser extent in hexose transporters and genes involved in the glyoxylate cycle. With respect to primary glucose metabolism, a shift in the type of hexose transport to one with high affinity was induced. In accordance with the phenotype of the mutant strain, the maltose transporter was constitutively expressed under glucose-limited conditions and synthesis increased in the presence of maltose.

Analysis of reflex modulation with a biologically realistic neural network.

In this study, a neuromusculoskeletal model was built to give insight into the mechanisms behind the modulation of reflexive feedback strength as experimentally identified in the human shoulder joint. The model is an integration of a biologically realistic neural network consisting of motoneurons and interneurons, modeling 12 populations of spinal neurons, and a one degree-of-freedom musculoskeletal model, including proprioceptors. The model could mimic the findings of human postural experiments, using presynaptic inhibition of the Ia afferents to modulate the feedback gains. In a pathological case, disabling one specific neural connection between the inhibitory interneurons and the motoneurons could mimic the experimental findings in complex regional pain syndrome patients. It is concluded that the model is a valuable tool to gain insight into the spinal contributions to human motor control. Applications lay in the fields of human motor control and neurological disorders, where hypotheses on motor dysfunction can be tested, like spasticity, clonus, and tremor.