Design Strategies toward High-Utilization Zinc Anodes for Practical Zinc-Metal Batteries.

Aqueous Zn-metal batteries (AZMBs) hold a promise as the next-generation energy storage devices due to their low cost and high specific energy. However, the actual energy density falls far below the requirements of commercial AZMBs due to the use of excessive Zn as anode and the associated issues including dendritic growth and side reactions. Reducing the N/P ratio (negative capacity/positive capacity) is an effective approach to achieve high energy density. A significant amount of research has been devoted to increasing the cathode loading and specific capacity or tuning the Zn anode utilization to achieve low N/P ratio batteries. Nevertheless, there is currently a lack of comprehensive overview regarding how to enhance the utilization of the Zn anode to balance the cycle life and energy density of AZMBs. In this review, we summarize the challenges faced in achieving high-utilization Zn anodes and elaborate on the modifying strategies for the Zn anode to lower the N/P ratio. The current research status and future prospects for the practical application of high-performance AZMBs are proposed at the end of the review.

Fast Independent Component Analysis Algorithm-Based Diagnosis of L5 Nerve Root Compression and Changes of Brain Functional Areas Using 3D Functional Magnetic Resonance Imaging.

In this paper, the application of 3-dimensional (3D) functional magnetic resonance imaging (FMRI) in the diagnosis of the 5th lumbar (L5) nerve root compression and brain functional areas in patients with lumbar disc herniation (LDH) was analyzed. The traditional fast independent component analysis (Fast ICA) algorithm was optimized based on the modified whitening matrix to establish a new type of Modified-Fast ICA (M-Fast ICA) algorithm that was compared with the introduced traditional Fast ICA and ICA. M-Fast ICA was applied to the 3D FMRI diffusion tensor imaging (DTI) evaluation of 65 patients with L5 nerve root pain due to LDH (group A) and 50 healthy volunteers (group B). The values of fractional anisotropy (FA) and apparent diffusion coefficient (ADC) in the lumbar nerve roots (L3, L4, L5, and the 1st sacral vertebra (S1)) were recorded among subjects from the two groups. Besides, the score of edema degree in the lumbar nerve roots (L5 and S1) and activity of brain functional areas were also recorded among all subjects of the two groups. The results showed that the mean square error of M-Fast ICA was smaller than that of traditional Fast ICA and ICA, while its signal-to-noise ratio (SNR) was greater than that of Fast ICA and ICA (P < 0.05). The FA of L5 and S1 nerve roots in patients of group A was sharply lower than the values of group B, while the ADC of patients in group A was greater than that of the control group (P < 0.05). Besides, the score of edema in L5 and S1 nerve roots of patients in group A increased in contrast to group B (P < 0.05). The brain areas were activated after surgery including bilateral temporal lobe, left thalamus, splenium of corpus callosum, and right internal capsule. In conclusion, the 3D image denoising performance of M-Fast ICA optimized and constructed in this study was superior to that of the traditional Fast ICA and ICA. The FA of patients with L5 nerve root pain due to LDH decreased steeply, while the ADC increased dramatically. L5 nerve root pain caused by LDH resulted in changes in brain functional areas of the patients to inhibit the resting state default network activity, and the corresponding brain functional areas could be activated through treatment.

Comparative Study on the Flame Retardancy and Retarding Mechanism of Rare Earth (La, Ce, and Y)-Based Organic Frameworks on Epoxy Resin.

In this work, a series of rare earth-based metal-organic frameworks (RE-MOFs) with the same organic ligand were synthesized and studied as flame retardants on epoxy. Through thermogravimetric analysis, limiting oxide index, UL-94, and cone calorimeter tests, a Y-based MOF (Y-MOF) showed the best flame retardancy compared with a La-based MOF (La-MOF) and Ce-based MOF (Ce-MOF). Further research with Raman, X-ray photoelectron spectroscopy, and theoretical calculation revealed that the reasons for the different flame retardance performances of RE-MOFs resulted from the catalytic carbonizing abilities and the radical-trapping abilities of La, Ce, and Y.

Metal-Organic Framework-Derived Strategy for Improving Catalytic Performance of a Chromia-Based Catalyst in the Chlorine/Fluorine Exchange Reactions for Unsaturated Fluorocarbons.

Hydrofluoroolefins (HFOs) and cyclic hydrofluorocarbons (c-HFCs) have been the most favored alternatives of the ozone depletion substances; however, because of the poor performance of the present chlorine/fluorine (Cl/F) exchange catalysts, the development and production of HFOs and c-HFCs are hindered. Here, we first report a novel and facile route to fabricate high-performance Cl/F exchange catalysts via a metal-organic framework (MOF) carbonization method. The MOF-derived catalyst not only has high selectivity but also can significantly lower the reaction temperature. Moreover, benefiting from the stable structure and coke-inhibiting ability, the MOF-derived catalyst has a long service life compared with the traditional precipitation method. Furthermore, the nanoscopic MOF-derived catalyst can greatly reduce the Cr dosage, which would help to minimize the risk of Cr contamination.

Construction of MnO nanoparticles anchored on SiC whiskers for superior electromagnetic wave absorption.

MnO nanoparticles (MnONP) decorated SiC whiskers (SiCw) with superior electromagnetic (EM) wave absorption performances were successfully synthesized by combining a hydrothermal and thermal annealing process. The microstructural feature and the content of MnONP of these MnONP/SiCw composites could be effectively controlled by the hydrothermal temperature, resulting in the adjustable EM wave absorption capacity. Compared with the poor EM wave absorption property of pristine SiCw (-10.48 dB), the MnONP/SiCw heterostructures achieve substantially enhanced microwave absorption performances, attributing to the suitable impedance matching and improved loss ability arose from the synergetic effect between MnO and SiC, whose minimum reflection loss (RLmin) is improved to -15.84 dB for MnONP/SiCw obtained at 80 °C (S-80), to -15.17 dB for MnONP/SiCw obtained at 100 °C (S-100), and to -55.10 dB for MnONP/SiCw obtained at 120 °C (S-120), respectively. The MnONP/SiCw composite not only exhibits enhanced microwave absorption property, but also presents wider effective absorption bandwidth (EAB), reaching up to 5.4 GHz for S-80, 3.6 GHz for S-100 and 5.2 GHz for S-120 in comparison with pristine SiC (1.5 GHz). This work is expected to provide an effective approach to enhance EM wave absorption property of dielectric materials by incorporation of MnO and the MnONP/SiCw composites could be as a promising candidate for EM wave absorption applications.

Isoelectronic analogues of graphene: the BCN monolayers with visible-light absorption and high carrier mobility.

By employing particle-swarm optimization (PSO) and first-principles computations, we theoretically predicted five stable phases of graphene-like borocarbonitrides (g-BCN) with the stoichiometric ratio of 1:1:1 and uniformly distributed B, C, N atoms, which are the isoelectronic analogues of graphene. These g-BCN monolayers are effectively stabilized by their relatively high proportion of robust C-C or B-N bonds and strong partial ionic-covalent B-C and C-N bonds within them, leading to pronounced thermal and kinetic stability. The visible-light absorption and high carrier mobility of the investigated g-BCN monolayers indicate their possible applications in high-efficiency photochemical processes and electronic devices. Our computations could provide some guidance for designing the graphene-like materials with earth-abundant elements, as well as some clues for the experimental synthesis and practical applications of ternary BCN nanosheets.

From metal-organic framework to morphology- and size-controlled 3D mesoporous Cr2O3 toward a high surface area and enhanced volatile organic compound oxidation catalyst.

Morphology- and size-controlled 3D mesoporous Cr2O3 have always been a research hotspot due to their wide applications. Herein, we for the first time report that the carbonized Cr-MOFs can ignite spontaneously at room temperature and form the corresponding 3D mesoporous Cr2O3 with high specific surface areas (219.25 to 303.44 cm2 g-1). More importantly, the shape and size of 3D mesoporous Cr2O3 can be well controlled by a facile adjustment of the Cr-MOF synthesis conditions. Furthermore, these materials showed an exceptionally high catalytic performance in formaldehyde oxidation. These results are predicted to offer a novel method in the design and synthesis of 3D porous Cr2O3.

Prediction of Kinetic Isotope Effects for Various Hydride Transfer Reactions Using a New Kinetic Model.

In this work, kinetic isotope effect (KIEself) values of 68 hydride self-exchange reactions, XH(D) + X(+) → X(+) + XH(D), in acetonitrile at 298 K were determined using a new experimental method. KIE values of 4556 hydride cross transfer reactions, XH(D) + Y(+) → X(+) + YH(D), in acetonitrile were estimated from the 68 determined KIEself values of hydride self-exchange reactions using a new KIE relation formula derived from Zhu's kinetic equation and the reliability of the estimations was verified using different experimental methods. A new KIE kinetic model to explain and predict KIE values was developed according to Zhu's kinetic model using two different Morse free energy curves instead of one Morse free energy curve in the traditional KIE theories to describe the free energy changes of X-H bond and X-D bond dissociation in chemical reactions. The most significant contribution of this paper to KIE theory is to build a new KIE kinetic model, which can be used to not only uniformly explain the various (normal, enormous and inverse) KIE values but also safely prodict KIE values of various chemical reactions.

A classical but new kinetic equation for hydride transfer reactions.

A classical but new kinetic equation to estimate activation energies of various hydride transfer reactions was developed according to transition state theory using the Morse-type free energy curves of hydride donors to release a hydride anion and hydride acceptors to capture a hydride anion and by which the activation energies of 187 typical hydride self-exchange reactions and more than thirty thousand hydride cross transfer reactions in acetonitrile were safely estimated in this work. Since the development of the kinetic equation is only on the basis of the related chemical bond changes of the hydride transfer reactants, the kinetic equation should be also suitable for proton transfer reactions, hydrogen atom transfer reactions and all the other chemical reactions involved with breaking and formation of chemical bonds. One of the most important contributions of this work is to have achieved the perfect unity of the kinetic equation and thermodynamic equation for hydride transfer reactions.

Enzyme-mimetic catalyst-modified nanoporous SiO2-cellulose hybrid composites with high specific surface area for rapid H2O2 detection.

Mesoporous silica-cellulose hybrid composites were prepared by surface sol-gel coating process on nature cellulose substance. The template CTAB (hexadecyl trimethyl ammonium Bromide) in the silica film can be removed by extraction to obtain high specific surface area (80.7 m(2) g(-1)), which is 2 orders of magnitude higher than that of raw cellulose. In the following, the enzyme-mimetic catalyst and chromogenic agent were introduced onto the hybrid system. Just as the peroxidase, the resultant hybrid material exhibits extraordinary sensitivity for the H2O2 and shows an immediate and obvious color change. The detection limit is about 1 µmol L(-1) by the naked eye.

Conversion and origin of normal and abnormal temperature dependences of kinetic isotope effect in hydride transfer reactions.

The effects of substituents on the temperature dependences of kinetic isotope effect (KIE) for the reactions of the hydride transfer from the substituted 5-methyl-6-phenyl-5,6-dihydrophenanthridine (G-PDH) to thioxanthylium (TX(+)) in acetonitrile were examined, and the results show that the temperature dependences of KIE for the hydride transfer reactions can be converted by adjusting the nature of the substituents in the molecule of the hydride donor. In general, electron-withdrawing groups can make the KIE to have normal temperature dependence, but electron-donating groups can make the KIE to have abnormal temperature dependence. Thermodynamic analysis on the possible pathways of the hydride transfer from G-PDH to TX(+) in acetonitrile suggests that the transfers of the hydride anion in the reactions are all carried out by the concerted one-step mechanism whether the substituent is an electron-withdrawing group or an electron-donating group. But the examination of Hammett-type free energy analysis on the hydride transfer reactions supports that the concerted one-step hydride transfer is not due to an elementary chemical reaction. The experimental values of KIE at different temperatures for the hydride transfer reactions were modeled by using a kinetic equation formed according to a multistage mechanism of the hydride transfer including a returnable charge-transfer complex as the reaction intermediate; the real mechanism of the hydride transfer and the root that why the temperature dependences of KIE can be converted as the nature of the substituents are changed were discovered.

What are the differences between ascorbic acid and NADH as hydride and electron sources in vivo on thermodynamics, kinetics, and mechanism?

Ascorbic acid (AscH(2)) and dihydronicotinamide adenine dinucleotide (NADH) are two very important natural redox cofactors, which can be used as hydride, electron, and hydrogen atom sources to take part in many important bioreduction processes in vivo. The differences of the two natural reducing agents as hydride, hydrogen atom, and electron donors in thermodynamics, kinetics, and mechanisms were examined by using 5,6-isopropylidene ascorbate (iAscH(-)) and ß-D-glucopyranosyl-1,4-dihydronicotinamide acetate (GluNAH) as their models, respectively. The results show that the hydride-donating ability of iAscH(-) is smaller than that of GluNAH by 6.0 kcal/mol, but the electron-donating ability and hydrogen-donating ability of iAscH(-) are larger than those of GluNAH by 20.8 and 8.4 kcal/mol, respectively, which indicates that iAscH(-) is a good electron donor and a good hydrogen atom donor, but GluNAH is a good hydride donor. The kinetic intrinsic barrier energy of iAscH(-) to release hydride anion in acetonitrile is larger than that of GluNAH to release hydride anion in acetonitrile by 6.9 kcal/mol. The mechanisms of hydride transfer from iAscH(-) and GluNAH to phenylxanthium perchlorate (PhXn(+)), a well-known hydride acceptor, were examined, and the results show that hydride transfer from GluNAH adopted a one-step mechanism, but the hydride transfer from iAscH(-) adopted a two-step mechanism (e-H(•)). The thermodynamic relation charts (TRC) of the iAscH(-) family (including iAscH(-), iAscH(•), iAsc(•-), and iAsc) and of the GluNAH family (including GluNAH, GluNAH(•+), GluNA(•), and GluNA(+)) in acetonitrile were constructed as Molecule ID Cards of iAscH(-) and of GluNAH in acetonitrile. By using the Molecule ID Cards of iAscH(-) and GluNAH, the character chemical properties not only of iAscH(-) and GluNAH but also of the various reaction intermediates of iAscH(-) and GluNAH all have been quantitatively diagnosed and compared. It is clear that these comparisons of the thermodynamics, kinetics, and mechanisms between iAscH(-) and GluNAH as hydride and electron donors in acetonitrile should be quite important and valuable to diagnose and understand the different roles and functions of ascorbic acid and NADH as hydride, hydrogen atom, and electron sources in vivo.

Actual structure, thermodynamic driving force, and mechanism of benzofuranone-typical compounds as antioxidants in solution.

5,7-Ditert-butyl-3-(3,4-dimethylphenyl)benzofuran-2(3H)-one (HP-136) (1H) and its 30 analogues (2H-5H) as benzofuranone-typical antioxidants were synthesized. The structures of the benzofuranones in solid and solution were examined by using experimental and theoretical methods. The results show that the dominant structure is the lactone form rather than the enol form both in solid and solution. The thermodynamic driving forces of the 31 benzofuranone-typical compounds to release protons [ΔG(PD)(XH)], hydrogen atoms [ΔG(HD)(XH)], and electrons [E(ox)(XH)] and the thermodynamic driving forces of the anions (X(-)) of the benzofuranones to release electrons [E(ox)(X(-))] were determined for the first time in DMSO. The ΔG(HD)(XH) scale of these compounds in DMSO ranges from 65.2 to 74.1 (kcal/mol) for 1H-4H and from 73.8 to 75.0 (kcal/mol) for 5H, respectively, which are all smaller than that of the most widely used commercial antioxidant BHT (2,6-ditert-butyl-4-methylphenol, 81.6 kcal/mol), suggesting that the 31 XH could be used as good hydrogen-atom-donating antioxidants. The ΔG(PD)(XH) were observed to range from 11.5 to 16.0 (kcal/mol) for 1H-4H and from 18.6 to 22.4 (kcal/mol) for 5H, indicating that benzofuranones (1H-4H) are good proton donors, and their analogues (5H) should belong to middle-strong proton donors. E(ox)(XH) of the 31 XH to release an electron vary from 1.346 to 1.962 (V versus Fc(+/0)), implying that the 31 XH are weak electron donors, whereas the quite negative E(ox)(X(-)) show that X(-) are good electron donors. The Gibbs free-energy changes of the radical cations (XH(+•)) to release protons [ΔG(PD)(XH(+•))] were evaluated according to the corresponding thermodynamic cycle, and the results reveal that XH(+•) are good proton donors. Further inspection of our experimental results showed the ΔG(HD)(XH), ΔG(PD)(XH), ΔG(PD)(XH(+•)), E(ox)(XH), and E(ox)(X(-)) of the five chemical and electrochemical processes are all linearly dependent on the sum of Hammett substituent parameters σ with very good correlation coefficients, indicating that for any one- or multisubstituted species at the para- and/or meta-position of benzofuranones and their various reaction intermediates, the five thermodynamic driving force parameters all can be easily and safely estimated from the corresponding Hammett substituent parameters. The rates of hydrogen atom transfer from XH to DPPH(•) were determined by using the UV-vis absorption spectroscopy technique. Combining these important thermodynamic parameters and dynamic determination results, the mechanism of hydrogen transfer from HP-136 and its analogues to DPPH(•) was studied. The results suggest that the hydrogen transfer from HP-136 and its analogues 2H to DPPH(•) actually includes two steps, proton transfer and the following electron transfer, but the proton transfer is rate-determined.

Immobilization of penicillin G acylase on poly[(glycidyl methacrylate)-co-(glycerol monomethacrylate)]-grafted magnetic microspheres.

Poly[(glycidyl methacrylate)-co-(glycerol monomethacrylate)]-grafted magnetic microspheres were prepared by graft random copolymerization via ATRP from polymer microspheres with dispersed Fe(3)O(4) nanoparticles. Penicillin G acylase (PGA) was immobilized onto the polymer brush-grafted magnetic microspheres. The immobilized PGA prepared with initial glycidyl methacrylate/glycerol monomethacrylate ratios of 40/60 to 60/40 possessed higher catalytic activity than that prepared with higher proportions of glycidyl methacrylate in the initial monomer mixture. The immobilized PGA showed high thermal stability and enhanced tolerability to the pH variance.