Hydrogen Abstraction by Alkoxyl Radicals: Computational Studies of Thermodynamic and Polarity Effects on Reactivities and Selectivities.

Density functional theory calculations (ωB97X-D) are reported for the reactions of methoxy, tert-butoxy, trichloroethoxy, and trifluoroethoxy radicals with a series of 26 C-H bonds in different environments characteristic of a variety of hydrocarbons and substituted derivatives. The variations in activation barriers are analyzed with modified Evans-Polanyi treatments to account for polarity and unsaturation effects. The treatments by Roberts and Steel and by Mayer have inspired the development of a simple treatment involving the thermodynamics of reactions, the difference between the reactant radical and product radical electronegativities, and the absence or presence of α-unsaturation. The three-parameter equation (ΔH⧧ = 0.52ΔHrxn(1 - d) - 0.35ΔχAB2 + 10.0, where d = 0.44 when there is α-unsaturation to the reacting C-H bond), correlates well with quantum mechanically computed barriers and shows the quantitative importance of the thermodynamics of reactions (dictated by the reactant and the product bond dissociation energies) and polar effects.

Research on the Specificity of Electrophysiological Signals of Human Acupoints Based on the 90-Day Simulated Weightlessness Experiment on the Ground.

Acupoint specificity for diseases has consistently been the focus of acupuncture research owing to its excellent prospects for clinical diagnosis and treatment. However, the specificity of cardiovascular and sleep functions in terms of electrical signals at acupoints remains unclear. In this study, five volunteers were recruited and their electrophysiological signals of GV20 (baihui), RN17 (danzhong), PC6 (neiguan), and SP6 (sanyinjiao) and the corresponding sham points, Pittsburgh sleep quality index, blood pressure, and echocardiography were monitored over four periods of 90-day head-down bed rest (HDBR). The results demonstrated that the power and characteristic amplitude of the acupoints were more significant than those of the sham points under normal conditions. And along with the altered physiological condition of the body after HDBR, the differential signal characteristic amplitude (DSCA) and the power of the acupoints were decreased to a larger extent than those of the sham points. In addition, the difference between the power of acupuncture and sham points was also reduced. During the recovery period, except for GV20, the power and DSCA of other acupoints did not return to normal. In terms of DSCA, GV20 is related to human sleep function and other acupoints are related to cardiovascular function. The above results show that the electrophysiological signals of acupoints are disease-specific and more accurately reflect the changes of physiological homeostasis. The research conduces to the development of acupuncture-based disease diagnosis and treatment integrated methods, and the realization of the portable and accurate diagnosis and regulation of diseases in space medicine.

PtNPt/MWCNT-PEDOT:PSS-Modified Microelectrode Arrays for the Synchronous Dopamine and Neural Spike Detection in Rat Models of Sleep Deprivation.

In this study, a biosensor assembly based on microelectrode arrays (MEAs) modified with PtNPt/MWCNT-PEDOT:PSS nanocomposites is presented to synchronously detect the dopamine (DA) and electrophysiological activities in rat brains. Different morphological and electrochemical characterizations were conducted to show the excellent mechanical and electrical properties of the as-prepared probes. The developed biosensors realized the sensitive and selective detection of DA with the existence of significant interferences such as uric acid (UA), ascorbic acid (AA), glutamate (Glu), and 3,4-dihydroxyphenylacetic acid (DOPAC). Calibration curve for the DA response was linear with the concentration from 0.05 µM to 79 µM (R = 0.999), with a sensitivity of 30.561 pA/µM and detection limit as low as 50 nM. Finally, the proposed microelectrode was applied to be implanted into the cortex and caudate putamen (CPU) of rats, which was demonstrated to stably measure the synchronous neurochemical and neurophysiological changes caused by 72 h sleep deprivation. The in vivo measuring results showed that the sleep deprivation increased the DA release and neural spike activity in both cortex and CPU. The local field potential (LFP) power in the delta and theta band was significantly increased as well. These changes in brain may reflect the brain's adaptive reaction toward the side effects induced by sleep deprivation and may partially explain the mechanism of forced wakefulness in the presence of accumulated sleep pressure.

Cellular-Scale Microelectrode Arrays to Monitor Movement-Related Neuron Activities in the Epileptic Hippocampus of Awake Mice.

OBJECTIVE: Epilepsy affects 50 million people worldwide and its pathogenesis is still unknown. In particular, the movement-related neural activities involving glutamate (Glu) and electrophysiological signals at cellular level remains unclear. METHODS: A cellular-scale implantable microelectrode array (MEA) was fabricated to detect the movement-related neural activities involving Glu concentration and electrophysiological signals. Platinum and reduced graphene oxide nanocomposites were deposited to enhance the surface area. Glu oxidase (Gluox) were coated to effectively recognize Glu molecule. RESULTS: Neural activities in the hippocampus of normal and epileptic mice is different, and the changes are closely connected with movement. Glu concentration and spike firing rate in the epileptic mice were much higher than those in the normal ones. And the neural activities with significant synchronization were detected in the epileptic mice even without seizure occurrence. Meanwhile, the spikes fire more intensively and Glu level became much higher during the movement of the mice compared to the stationary state. CONCLUSION: The existing abnormality of neural activities in the epileptic mice are potential factors to induce a seizure. Movement may impact the neural activities and the duration of seizure. SIGNIFICANCE: The MEA can monitor changes of movement, Glu and neuron discharges synchronously and provides us an effective technology to understand the neuronal disease.

Implanted multichannel microelectrode array for simultaneous electrophysiological signal detection of hippocampal CA1 and DG neurons of simulated microgravity rats.

Microgravity can cause body fluids to accumulate in the brain, resulting in brain damage. There are few studies that focus on the detection of electrophysiological signals in simulated microgravity rats, and the precise mechanisms are unknown. In this study, a new device was established to investigate the influence of microgravity on hippocampal neurons. A 16-channel microelectrode array was fabricated for in vivo multichannel electrophysiological recordings. In these experiments, microelectrode array was inserted into normal, 28-day tail suspension model, and 3-day recovered after modulation rats to record electrophysiological signals in the CA1 and DG regions of the hippocampus. Through analysis of electrophysiological signals, we obtained the following results: (1) spike signals of model rats sporadically showed brief periods of suspension involving most of the recorded neurons, which corresponded to slow and smooth peaks in local field potentials. For model rats, the firing rate was reduced, and the power in the frequency spectrum was concentrated in the slow frequency band (0-1 Hz); (2) after the detected hippocampal cells divided into pyramidal cells and interneurons, the spike duration of pyramidal cells showed remarkable latency, and their average firing rates showed a more significant decrease compared to interneurons. These results demonstrate that the hippocampal neurons were impaired after modulation in the cellular dimension, and pyramidal cells were more susceptible than interneurons.

Series of Highly Luminescent Macrocyclic Sm(III) Complexes: Functional Group Modifications Together with Luminescence Performances in Solid-State, Solution, and Doped Poly(methylmethacrylate) Film.

Here, we report our trials to regulate the luminescence performance of the macrocyclic samarium(III) complex and prepare four excellent luminescent Sm(III) complex-doped poly(methylmethacrylate) (PMMA) composites. Four 23-membered [1 + 1] Schiff-base macrocyclic mononuclear Sm(III) complexes, Sm-2 a -Sm-2 d , originating from dialdehydes with different pendant arms and 1,2-bis(2-aminoethoxy)ethane, have been constructed by the template method. Crystal structures reveal that every Sm(III) ion with the coordination geometry of a distorted bicapped square antiprism is capsulated by the macrocyclic cavity environment forming the "lasso-type" protection. Relative photophysical properties of macrocyclic Sm(III) complexes are carefully investigated in solid-state, methanol solution, and doped PMMA film, and all these show characteristic emissions of the Sm(III) ion associated with satisfactory lifetimes and quantum yields in all media, which could be comparable to reported outstanding examples. Especially, the luminescence performance for this type of Sm(III) complex could be regulated in the solid state by the use of different functional groups in the pendant arm while it is not achieved in solution and the doped PMMA composite. High emitting and air-stable plastic materials could be obtained when these Sm(III) complexes are doped in PMMA with 0.1 wt % mixing ratio, and the corresponding maximum lifetime and quantum yield are 61.2 µs and 0.63% in the case of complex Sm-2 a , respectively. We believe that these highly luminescent "lasso-type" Sm(III) complexes and doped PMMA composites are valuable references in the design of luminescent lanthanide(III) hybrid materials.

An excellent colorimetric and "turn off" fluorescent probe for tetrahydrofuran based on a luminescent macrocyclic samarium(iii) complex.

In this paper we report a novel probe based on a luminescent 23-membered [1 + 1] Schiff-base macrocyclic mononuclear Sm(iii) complex Sm-2e, originating from the dialdehyde H2Qe and 1,2-bis(2-aminoethoxy)ethane precursors, which is synthesized by the Sm(iii) ion template method. X-ray structural analyses confirm that each ten-coordinate Sm(iii) center with the coordination geometry of a distorted bicapped square antiprism is fully encapsulated by a flexible macrocyclic ligand H2L2e to form a "lasso-type" architecture, and this architecture could enable efficient energy transfer in various solvents confirmed by long lifetimes (33.5-65.2 µs) and high quantum yields (0.23-0.76%) of the Sm(iii) ion. Simultaneously, complex Sm-2e could serve as a probe for sensing organic solvents. Particularly, this complex probe Sm-2e exhibits a highly selective, rapid and sensitive response to tetrahydrofuran (THF), which is easily distinguished by a large absorption shift, even visible to the naked eye, and complete fluorescence quenching. Moreover, the limit of detection for THF is about 0.20% determined by titration experiments, and good selectivity for THF could still be realized in mixture solvents. Consequently, this colorimetric and "turn off" fluorescent probe Sm-2e could be a valuable candidate as a sensor material for sensing THF which has been rarely reported.