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CDK2 is a critical regulator of the cell cycle. For a variety of human cancers, the dysregulation of CDK2/cyclin E1 can lead to tumor growth and proliferation. Historically, early efforts to develop CDK2 inhibitors with clinical applications proved unsuccessful due to challenges in achieving selectivity over off-target CDK isoforms with associated toxicity. In this report, we describe the discovery of (4-pyrazolyl)-2-aminopyrimidines as a potent class of CDK2 inhibitors that display selectivity over CDKs 1, 4, 6, 7, and 9. SAR studies led to the identification of compound 17 , a kinase selective and highly potent CDK2 inhibitor (IC 50 = 0.29 nM). The evaluation of 17 in CCNE1 -amplified mouse models shows the pharmacodynamic inhibition of CDK2, measured by reduced Rb phosphorylation, and antitumor activity.

As the global marketplace for lithium-ion batteries (LIBs) proliferates, technologies for efficient and environmentally friendly recycling, i.e., direct recycling, of spent LIBs are urgently required. In this contribution, we elucidated the mechanisms underlying the degradation that occurs during the cycling of a Li/LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM622) cell. The results provided fundamental insights into the optimum procedures for direct recycling using a recently developed, state-of-the-art positive electrode material. Capacity fade in NCM622 was induced by cycling at high voltages above 4.6 V vs Li + /Li, during which the rhombohedral symmetry approached cubic symmetry. The selective line broadening and peak shifts that appeared in the X-ray diffraction patterns after cycling indicated the formation of stacking faults along the c h -axis. In addition, high-resolution transmission electron microscopy clarified that rock-salt domains were located on the NCM622 surface before and after cycling. These structural analyses confirmed that the NCM622 particles degrade not at their surfaces but rather in the bulk, contradicting previous reports where degradation during cycling is mainly caused by rock-salt domains on the surface. Material regeneration processes involving the restoration of the original stacking sequence are essential for effective direct recycling., Competing Interests: The author declares no competing financial interest., (© 2023 The Author. Published by American Chemical Society.)

A series of Li 4/3-2 x /3 Zn x Ti 5/3- x /3 O 4 (LZTO) with 0 ≤ x ≤ 0.5 have received considerable interest as a negative electrode material for long-cycle-life lithium-ion batteries. However, their dynamic structural transformations under operating conditions have remained unknown, making an in-depth understanding essential for further improving the electrochemical performance. We, thus, performed almost simultaneous operando X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) studies on x = 0.125, 0.375, and 0.5. The x = 0.5 sample, Li 2 ZnTi 3 O 8 , indicated differences in the cubic lattice parameter between the discharge and charge reactions ( δa c s), corresponding to the reversible movement of Zn 2+ ions between the tetrahedral and octahedral sites. δa c was also observed for x = 0.125 and 0.375, although the capacity region exhibiting δa c decreased with a decrease in x . For all of the samples, there is no significant difference in the nearest-neighbor distance of the Ti-O bond ( d Ti-O ) between the discharge and charge reactions. We also demonstrated different structural transformations between the micro- (XRD) and atomic (XAS) scales. In the case for x = 0.5, for instance, the maximum microscale change in a c was within +0.29(3)%, whereas at the atomic scale, d Ti-O changed by up to +4.8(3)%. Combined with our previous results for ex situ XRD and operando XRD/XAS measurements on other x compositions, the whole structural nature of LZTO, such as correspondence between a c and d Ti-O , origins for voltage hysteresis, and zero-strain reaction mechanisms, has been unveiled.

Negative electrode materials with high thermal stability are a key strategy for improving the safety of lithium-ion batteries for electric vehicles without requiring built-in safety devices. To search for crucial clues into increasing the thermal stability of these materials, we performed differential scanning calorimetry (DSC) and in situ high-temperature (HT)-X-ray diffraction (XRD)/X-ray absorption (XAS) up to 450 °C with respect to a solid-solution compound of Li 4/3-2 x /3 Zn x Ti 5/3- x /3 O 4 with 0 ≤ x ≤ 0.5. The DSC profile of fully discharged x = 0.5 (Li 2 ZnTi 3 O 8 ) with a LiPF 6 -based electrolyte could be divided into three temperature ( T ) regions: (i) T ≤ 250 °C for Δ H accum i , (ii) 250 °C < T ≤ 350 °C for Δ H accum ii , and (iii) T > 350 °C for Δ H accum iii , where Δ H accum n is the accumulated change in enthalpy in region n . The HT-XRD/XAS analyses clarified that Δ H accum i and Δ H accum ii originated from the decomposition of solid electrolyte interphase (SEI) films and the formation of a LiF phase, respectively. Comparison of the DSC profiles with x = 0 (Li[Li 1/3 Ti 5/3 ]O 4 ) and graphite revealed the operating voltage, i.e., amount of SEI films, and stability of the crystal lattice play significant roles in the thermal stability of negative electrode materials. Indeed, the highest thermal stability was attained at x = 0.25 using this approach.

An in-depth understanding of the thermal behavior of lithium-ion battery materials is valuable for two reasons: one is to devise strategies for inhibiting the risk of catastrophic thermal runaway and the other is to respond to the increasing demand for sustainable batteries using a direct regeneration method. Li 1+ x [Li 1/3 Ti 5/3 ]O 4 (LTO) is regarded as a suitable negative electrode under the type of severe conditions that cause this thermal runaway, such as in ignition systems for automobiles. Thus, in this study, we used differential scanning calorimetry to systematically analyze lithiated LTO combined with ex situ and in situ high-temperature X-ray diffraction measurements. The observed thermal reactions with a LiPF 6 -based electrolyte were divided into three processes: (i) the decomposition of the initially formed solid electrolyte interphase below 200 °C, (ii) the formation of a LiF phase at 200 °C ≤ T ≤ 340 °C, and (iii) the formation of a TiO 2 phase at T > 340 °C. Because the enthalpy change in process (ii) mainly contributed to the total heat generation, fluorine-free Li salts and/or stabilization of the LTO lattice may be effective in coping with the thermal runaway. Even in various lithiated states, a direct regeneration method returned the discharge capacity of LTO to ∼90% of its initial value, if we ignore the contributions from the electrochemically inactive LiF and TiO 2 rutile phases. Hence, it can be concluded that the recycling performance of LTO is far superior to those of lithium transition metal oxides for a positive electrode, whose delithiated states easily convert into electrochemical-inactive phases at high temperatures.

"Zero-strain" insertion materials are essential for high-performance Li-ion batteries, but the experimental determination of changes in their local structures remains challenging. In this study, we successfully visualized the reaction scheme of a perfect zero-strain material, (Li 0.75 Zn 0.25 )[Li 0.417 Ti 1.583 ]O 4 with a spinel framework, using operando X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS). The operando XRD/XAS technique, which provided a series of XRD, Ti K-edge XAS, and Zn K-edge XAS data, can be employed owing to a recently developed tapered undulator and monochromator system. Although previous ex situ XRD measurements indicated the immutable cubic lattice parameter ( a c ) during the discharge process, these studies unveiled drastic structural variations occurring on the atomic scale between the charge and discharge reactions, such as differences in the a c , bond distances, and occupancies of the Zn 2+ ions. This dynamic information obtained under operating conditions could be useful not only for understanding the zero-strain reaction scheme but also for designing advanced zero-strain insertion materials with enhanced energy density.

Lithium overstoichiometric cobalt oxide, Li(Li δ Co 1-δ )O 2-δ , still occupies a privileged position as a positive electrode material for lithium-ion batteries. However, despite its widespread applications in commercial lithium-ion batteries, little is known about its reaction mechanisms and the effects of δ on cyclability at deep charge. We herein revisited this material through a recently developed in operando technique, i.e., rapid, alternating measurements of X-ray diffraction and X-ray absorption spectroscopy. The cyclability degraded when the charge cutoff voltage was >4.4 V versus Li + /Li, which corresponds to the Li composition exhibiting a minimum (maximum) lattice parameter along the a h ( c h ) axis. Differences in the structural parameters such as lattice parameters and bond distances clearly appeared between the charge and discharge reactions at a capacity below ∼220 mAh g -1 . These changes occurred because deep charge and/or increasing the amount of δ induced a local distortion in the CoO 6 octahedra. We found a critical Li extraction content that satisfied the need for both high capacity and cyclability for Li(Li δ Co 1-δ )O 2-δ , which can be applied to other layered materials.

The demand for eco-friendly materials for secondary batteries has stimulated the exploration of a wide variety of Fe oxides, but their potential as electrode materials remains unknown. In this contribution, ϵ-FeOOH was synthesized using a high-pressure/high-temperature method and examined for the first time in nonaqueous Li and Na cells. Under a pressure of 8 GPa, α-FeOOH transformed into ϵ-FeOOH at 400 °C and then decomposed into α-Fe 2 O 3 and H 2 O above 500 °C. Here, FeO 6 octahedra form [2 × 1] tunnels in α-FeOOH or [1 × 1] tunnels in ϵ-FeOOH. The ϵ-FeOOH/Li cell exhibited a rechargeable capacity ( Q recha ) of ∼700 mA h·g -1 at 0.02-3.0 V, whereas the ϵ-FeOOH/Na cell indicated a Q recha of less than 30 mA h·g -1 at 0.02-2.7 V. The discharge and charge profiles of ϵ-FeOOH and α-FeOOH were similar, but the rate capability of ϵ-FeOOH was superior to that of α-FeOOH., Competing Interests: The authors declare no competing financial interest., (Copyright © 2020 American Chemical Society.)

Negative electrode materials with lower operating voltages are urgently required to increase the energy density of lithium-ion batteries. In this study, LiMgVO 4 with a Na 2 CrO 4 -type structure, LiZnVO 4 with a phenacite structure, and their mixture were treated under a high pressure of 12 GPa and a high temperature of 1273 K, and their electrochemical reactivities were examined in a nonaqueous lithium cell. Synchrotron X-ray diffraction (XRD) measurements and Raman spectroscopy revealed that the LiMg 1- x Zn x VO 4 samples with 0 ≤ x ≤ 1 are in a single phase of the inverse spinel structure that forms a solid solution compound over the whole x range. All of the samples were brown or light black due to the presence of a small amount of V 4+ ions with S = 1/2 and oxygen deficiencies. Since the majority of the vanadium ions are located at the route of the Li + ion conduction pathway, no rechargeable capacity ( Q recha ) would be expected. Nevertheless, all LiMg 1- x Zn x VO 4 samples exhibited a Q recha value of more than 200 mAh g -1 with an operating voltage of ∼0.8 V. This operating voltage is ∼1.6 V lower than that of LiV 2 O 4 with a normal spinel structure. Furthermore, the x = 0.5 sample demonstrated an extremely stable cycle performance over 1 month. Ex situ XRD measurements clarified that the reversible electrochemical reaction can be attributed to the movement of vanadium ions from the tetrahedral 8a to octahedral 16c sites during the initial discharge reaction. Details regarding the crystal structure, magnetism, and electrochemistry of LiMg 1- x Zn x VO 4 are presented.

The understanding of polymer dewetting on solid surfaces is significant in both fundamental polymer physics and practical film technologies. When liquid crystalline (LC) polymers are dewetted, LC ordering is involved in the dewetting process. Here, we report on the characteristic dewetting processes of a diblock copolymer composed of a cyanobiphenyl side chain liquid crystalline polymer (SCLCP) block connected with polystyrene (PS) taking place on a PS base film. Thin films of the block copolymer were prepared by the water-floating method onto the PS film, and the dewetting process is observed in a softened state above the glass transition temperature of the PS. At the smectic A phase temperature of the SCLCP block, the dewetted surface layer generated a flat unique fingering pattern leading to a monolayered (two-dimensional) high-density LC polymer brush through the LC ordering. The important role of the anchoring PS block on the base PS film surface is suggested for the formation of highly stretched LC polymer brush. Above the isotropization temperature, in contrast, ordinary three-dimensional droplet morphologies with smooth round edges were observed. By photo-cross-linking the base PS film, the lateral diffusion rate was significantly reduced. This can be applied to an entropy-driven morphology patterning via dewetting. The polymer brush formation and its spatial controls are expected to provide new opportunities for the modification strategies of polymer surfaces.

Lithium zinc titanate spinel, Li 2 ZnTi 3 O 8 , has received significant attention as a negative electrode material for lithium-ion batteries (LIBs). However, its reaction mechanism has not been fully clarified yet, particularly for the large voltage hysteresis between discharge and charge curves. We hence closely examined (Li 1- x Zn x )[Li 1/3+ x /3 Ti 5/3- x /3 ]O 4 (LZTO) with 0 < x ≤ 0.5 by measuring its open-circuit voltage (OCV) and recording synchrotron radiation X-ray diffraction (XRD) patterns. Here, LZTO is a solid solution of Li[Li 1/3 Ti 5/3 ]O 4 ( x = 0) and Li 2 ZnTi 3 O 8 ( x = 0.5), both of which have a spinel-framework structure. For the x = 0.5 sample, the OCV of the discharge reaction differed from that of the charge reaction, particularly at a capacity above 50 mAh·g -1 . This difference was due to the migration of Zn 2+ ions from tetrahedral sites to octahedral sites, and the Zn 2+ ions moved back to tetrahedral sites during the charge reaction. Despite these drastic movements of Zn 2+ ions, the cubic lattice parameter of the spinel was maintained during the whole reaction, i.e., zero strain. Perfect zero strain, which has never been reported for any LIB materials, was achieved with the x = 0.25 sample. The reaction mechanism with x = 0.5 and the contributions of the amount of Zn ions are discussed in detail.

Lithium transition metal (M) oxides with a rhombohedral structure, r-LiMO 2 , have attracted a great deal of attention as a positive electrode material for lithium-ion batteries. Despite intensive studies thus far, Mn-rich r-LiMO 2 compounds have remained unattainable, due to a cooperative Jahn-Teller distortion of Mn 3+ ions in the MnO 6 octahedra. We employed a high-pressure method for synthesizing r-LiCo x Mn 1- x O 2 ( r-LCMO) with x = 0.5 and examined its electrochemical properties in a nonaqueous lithium cell. The high-pressure method successfully suppressed the Jahn-Teller distortion of Mn 3+ ions, and the r-LCMO phase was observed in a wide temperature-pressure region when using a LiOH·H 2 O precursor. The rechargeable capacity of the sample synthesized at 600 °C and 12 GPa reached 126 mAh g -1 , although the r-LCMO phase was contaminated with electrochemically inactive rock-salt LCMO and hexagonal LCMO phases. Compositional and structural analyses clarified that the actual Co/Mn ratio of the r-LCMO phase was 64/36, which deviated slightly from the initial composition (50/50). The high-pressure method was found to be effective for synthesizing Mn-rich r-LiMO 2 compounds, although their electrochemical properties should be improved.

Lithium manganese oxides have received much attention as positive electrode materials for lithium-ion batteries. In this study, a post-spinel material, CaFe 2 O 4 -type LiMn 2 O 4 (CF-LMO), was synthesized at high pressures above 6 GPa, and its crystal structure and electrochemical properties were examined. CF-LMO exhibits a one-dimensional (1D) conduction pathway for Li ions, which is predicted to be superior to the three-dimensional conduction pathway for these ions. The stoichiometric LiMn 2 O 4 spinel (SP-LMO) was decomposed into three phases of Li 2 MnO 3 , MnO 2 , and Mn 2 O 3 at 600 °C and then started to transform into the CF-LMO structure above 800 °C. The rechargeable capacity ( Q recha ) of the sample synthesized at 1000 °C was limited to ∼40 mA h·g -1 in the voltage range between 1.5 and 5.3 V because of the presence of a small amount of Li 2 MnO 3 phase in the sample (=9.1 wt %). In addition, the Li-rich spinels, Li[Li x Mn 2- x ]O 4 with x = 0.1, 0.2, and 0.333, were also employed for the synthesis of CF-LMO. The sample prepared from x = 0.2 exhibited a Q recha value exceeding 120 mA h·g -1 with a stable cycling performance, despite the presence of large amounts of the phases Li 2 MnO 3 , MnO 2 , and Mn 2 O 3 . Details of the structural transformation from SP-LMO to CF-LMO and the effect of Mn ions on the 1D conduction pathway are discussed., Competing Interests: The authors declare no competing financial interest.

Azaspirene and related congeners, which possess various biological activities, have a unique spirocyclic core structure. However, there are few studies on the chemical properties of (-)-azaspirene, despite the fact that it may provide important insights into unveiling the biosynthetic pathway. Here, we report a nine-step chemical synthesis of an azaspirene analogue with a new finding that the natural (-)-azaspirene skeleton easily racemizes in neutral aqueous media.

Cardenolides comprise an important family of natural steroids with a wide spectrum of biological activities. Although 19-hydroxysarmentogenin-3- O-α-l-rhamnoside (1a) and trewianin (1b) were structurally determined to have cardenolide structures, their biological activities have not been evaluated. The 6/6/6/5-membered ABCD-ring systems of both 1a and 1b are decorated by a β-oriented C17-butenolide, three C11,14,19-hydroxy groups, and a C3-O-l-rhamnoside moiety. On the other hand, 1a and 1b are epimeric at the C5-position. The structures of 1a and 1b were assembled from four simple fragments by applying a convergent and unified strategy. The AB-ring 10a/b and the D-ring 8/9 were tentatively tethered at the acetal moiety, and a subsequent stereoselective 6- exo radical reaction linked the two fragments. Next, an aldol reaction enabled simultaneous introduction of three new stereocenters of the C-rings of 5aa and 54. Attachment of the C17-butenolide led to aglycons 2a and 2b. l-Rhamnose was then installed into 2a and 2b to yield the targets 1a and 1b, respectively. Finally, the growth inhibitory activity of 1a, 1b, 2a, and 2b was assessed against MCF-7 human breast carcinoma cells. The significantly higher activities of 1a and 1b in comparison to 2a and 2b demonstrated the biological importance of the monosaccharide substructure.

Developments in subcellular fractionation strategies have provided the means to analyze the protein and lipid composition of organelles by proteomics. Here, we developed ultrasmall magnetic-plasmonic hybrid nanobeads and applied them to the isolation of autophagosomes by applying a magnetic field. The beads were chemically synthesized and comprised an Ag/FeCo/Ag core/shell/shell structure with a mean diameter of 15 nm. The Ag core and the FeCo shell conferred imaging and magnetic separation capabilities, respectively. The nanobeads were transfected into mammalian cells by lipofection. Thirty minutes after lipofection, the nanobeads colocalized with Vps26 and subsequently with LC3. Cell lysates were prepared at the appropriate time points and were subjected to magnetic separation. The separated fraction contained LC3-II, transferrin receptor, and LAMP2, but not LC3-I, suggesting that autophagosomes engulfing endosomal origin had been isolated. The magnetic separation process was completed in less than 30 min, providing a rapid method for isolation of autophagosomes. The present organelle isolation technique using the hybrid nanobeads with imaging and magnetic separation capabilities is highly promising for isolation of other types of organelles such as endosomes and endosome-related organelles., Competing Interests: The authors declare no competing financial interest.

To obtain positive electrode materials with higher energy densities ( W s), we performed systematic structural and electrochemical analyses for LiCo x Mn 2- x O 4 (LCMO) with 0 ≤ x ≤ 1. X-ray diffraction measurements and Raman spectroscopy clarified that the samples with x ≤ 0.5 are in the single-phase of a spinel structure with the Fd 3̅ m space group, whereas the samples with x ≥ 0.75 are in a mixture of the spinel-phase and Li 2 MnO 3 phase with the C 2/ m space group. The x -dependence of the discharge capacity ( Q dis ) indicated a broad maximum at x = 0.5, although the average operating voltage ( E ave ) monotonically increased with x . Thus, the W value obtained by Q dis × E ave reached the maximum (=627 mW h·g -1 ) at x = 0.5, which is greater than that for Li[Ni 1/2 Mn 3/2 ]O 4 . Furthermore, the change in the lattice volume (Δ V ) during charge and discharge reactions approached 0%, that is, zero-strain, at x = 1. Because Δ V for x = 0.5 was smaller than that for Li[Ni 1/2 Mn 3/2 ]O 4 , the x = 0.5 sample is found to be an alternative positive electrode material for Li[Ni 1/2 Mn 3/2 ]O 4 with a high W ., Competing Interests: The authors declare no competing financial interest.

A kinetic study of the reaction between an aroxyl radical (ArO • ) and fatty acid esters (LHs 1-5, ethyl stearate 1, ethyl oleate 2, ethyl linoleate 3, ethyl linolenate 4, and ethyl arachidonate 5) has been undertaken. The second-order rate constants (k s ) for the reaction of ArO • with LHs 1-5 in toluene at 25.0 °C have been determined spectrophotometrically. The k s values obtained increased in the order of LH 1 < 2 < 3 < 4 < 5, that is, with increasing the number of double bonds included in LHs 1-5. The k s value for LH 5 was 2.93 × 10 -3 M -1 s -1 . From the result, it has been clarified that the reaction of ArO • with LHs 1-5 was explained by an allylic hydrogen abstraction reaction. A similar kinetic study was performed for the reaction of ArO • with six carotenoids (Car-Hs 1-6, astaxanthin 1, β-carotene 2, lycopene 3, capsanthin 4, zeaxanthin 5, and lutein 6). The k s values obtained increased in the order of Car-H 1 < 2 < 3 < 4 < 5 < 6. The k s value for Car-H 6 was 8.4 × 10 -4 M -1 s -1 . The k s values obtained for Car-Hs 1-6 are in the same order as that of the values for LHs 1-5. The results of detailed analyses of the k s values for the above reaction indicated that the reaction was also explained by an allylic hydrogen abstraction reaction. Furthermore, the structure-activity relationship for the reaction was discussed by taking the result of density functional theory calculation reported by Martinez and Barbosa into account.

The most simple and clear advantage of Na-ion batteries (NIBs) over Li-ion batteries (LIBs) is the natural abundance of Na, which allows inexpensive production of NIBs for large-scale applications. However, although strenuous research efforts have been devoted to NIBs particularly since 2010, certain other advantages of NIBs have been largely overlooked, for example, their low-temperature power and cycle performances. Herein, we present a comparative study of spirally wound full-cells consisting of Li 0.1 Na 0.7 Co 0.5 Mn 0.5 O 2 (or Li 0.8 Co 0.5 Mn 0.5 O 2 ) and hard carbon and report that the power of NIB at -30 °C is ∼21% higher than that of LIB. Moreover, the capacity retention in cycle testing at 0 °C is ∼53% for NIB but only ∼29% for LIB. Raman spectroscopy and density functional theory calculations revealed that the superior performance of NIB is due to the relatively weak interaction between Na + ions and aprotic polar solvents., Competing Interests: The authors declare no competing financial interest.

Recently, a new assay method for the quantification of the singlet oxygen absorption capacity (SOAC) of antioxidants (AOs) and food extracts in homogeneous organic solvents was proposed. In this study, second-order rate constants (k Q ) for the reaction of singlet oxygen ( 1 O 2 ) with eight different carotenoids (Cars) and α-tocopherol (α-Toc) were measured in an aqueous Triton X-100 (5.0 wt %) micellar solution (pH 7.4, 35 °C), which was used as a simple model of biomembranes. The k Q and relative SOAC values were measured using ultraviolet-visible (UV-vis) spectroscopy. The UV-vis absorption spectra of Cars and α-Toc were measured in both a micellar solution and chloroform, to investigate the effect of solvent on the k Q and SOAC values. Furthermore, decay rates (k d ) of 1 O 2 were measured in 0.0, 1.0, 3.0, and 5.0 wt % micellar solutions (pH 7.4), using time-resolved near-infrared fluorescence spectroscopy, to determine the absolute k Q values of the AOs. The results obtained demonstrate that the k Q values of AOs in homogeneous and heterogeneous solutions vary notably depending on (i) the polarity [dielectric constant (ε)] of the reaction field between AOs and 1 O 2 , (ii) the local concentration of AOs, and (iii) the mobility of AOs in solution. In addition, the k Q and relative SOAC values obtained for the Cars in a heterogeneous micellar solution differ remarkably from those in homogeneous organic solvents. Measurements of k Q and SOAC values in a micellar solution may be useful for evaluating the 1 O 2 quenching activity of AOs in biological systems.

Although all-solid-state lithium-ion batteries (ALIBs) have been believed as the ultimate safe battery, their true character has been an enigma so far. In this paper, we developed an all-inclusive-microcell (AIM) for differential scanning calorimetry (DSC) analysis to clarify the degree of safety (DOS) of ALIBs. Here AIM possesses all the battery components to work as a battery by itself, and DOS is determined by the total heat generation ratio (ΔH) of ALIB compared with the conventional LIB. When DOS = 100%, the safety of ALIB is exactly the same as that of LIB; when DOS = 0%, ALIB reaches the ultimate safety. We investigated two types of LIB-AIM and three types of ALIB-AIM. Surprisingly, all the ALIBs exhibit one or two exothermic peaks above 250 °C with 20-30% of DOS. The exothermic peak is attributed to the reaction between the released oxygen from the positive electrode and the Li metal in the negative electrode. Hence, ALIBs are found to be flammable as in the case of LIBs. We also attempted to improve the safety of ALIBs and succeeded in decreasing the DOS down to ∼16% by incorporating Ketjenblack into the positive electrode as an oxygen scavenger. Based on ΔH as a function of voltage window, a safety map for LIBs and ALIBs is proposed.

Detailed kinetic studies have been performed for reactions of aroxyl (ArO(•)) and α-tocopheroxyl (α-Toc(•)) radicals with five catecholamines (CAs) (dopamine (DA), norepinephrine (NE), epinephrine (EN), and 5- and 6-hydroxydopamine (5- and 6-OHDA)) and two catechins (epicatechin (EC) and epigallocatechin gallate (EGCG)) to clarify the free-radical-scavenging activity of CAs. Second-order rate constants (ks and kr) for reactions of ArO(•) and α-Toc(•) radicals with the above antioxidants were measured in 2-propanol/water (5:1, v/v) solution at 25.0 °C, using single- and double-mixing stopped-flow spectrophotometries, respectively. Both the rate constants (ks and kr) increased in the order NE < EN < DA < EC < 5-OHDA < EGCG < 6-OHDA. The ks and kr values of 6-OHDA are large and comparable to the corresponding values of ubiquinol-10 and sodium ascorbate, which show high free-radical-scavenging activity. The ultraviolet-visible absorption of α-Toc(•) (λmax = 428 nm), which was produced by the reaction of α-tocopherol (α-TocH) with ArO(•), disappeared under the coexistence of CAs due to the α-TocH-regeneration reaction. The results suggest that the CAs may contribute to the protection from oxidative damage in nervous systems, by scavenging free radicals (such as lipid peroxyl radical) and regenerating α-TocH from the α-Toc(•) radical.

The Li+-ion conductivity (σLi) in an electrolyte is an important parameter with respect to the performance of all-solid-state lithium-ion batteries (LIBs). However, little is known about how σLi in a porous electrolyte differs from that in a highly dense electrolyte. In this study, the relationship between the bulk density (dbulk) and apparent σLi (σLiapp) in a porous electrolyte of Li[Li1/3Ti5/3]O4 (LTO) was examined by theoretical and experimental approaches. The theoretical calculations demonstrated that dbulk and σLi have a simple relationship irrespective of the radius of the spherical pores in the electrolyte; i.e., σLi increases almost linearly with increasing ζ,where ζ is the ratio of d bulk to the theoretical density. In fact, the observed σLiapp of LTO, which was determined by four-probe alternating-current impedance measurements, increased with increasing ζ. Hence, with this relationship, σLiapp can be estimated by ζ and intrinsic σLi (σLiint) and vice versa; such estimations provide critical information for determining the optimum compositions of composite electrodes for all-solid-state LIBs. The temperature dependence of σLiapp in LTO and differences between the calculated and experimental results are also discussed.

Recently, a new assay method that can quantify the aroxyl radical (ArO•) absorption capacity (ARAC) of antioxidants (AOHs) was proposed. In the present work, the second-order rate constants (ks(Extract)) and ARAC values for the reaction of ArO• with seven kinds of rice bran extracts 1-7, which contain different concentrations of α-, β-, γ-, and δ-tocopherols and -tocotrienols (α-, β-, γ-, and δ-Tocs and -Toc-3s) and γ-oryzanol, were measured in ethanol at 25 °C using stopped-flow spectrophotometry. The ks(Extract) value (1.26 × 10(-2) M(-1) s(-1)) of Nipponbare (extract 1) with the highest activity was 1.5 times larger than that (8.29 × 10(-3)) of Milyang-23 (extract 7) with the lowest activity. The concentrations (in mg/100 g) of α-, β-, γ-, and δ-Tocs and -Toc-3s and γ-oryzanol found in the seven extracts 1-7 were determined using HPLC-MS/MS and UV-vis absorption spectroscopy, respectively. From the results, it has been clarified that the ArO•-scavenging rates (ks(Extract)) (that is, the relative ARAC value) obtained for the seven extracts 1-7 may be approximately explained as the sum of the product {Σ ks(AOH-i) [AOH-i]/10(5)} of the rate constant (ks(AOH-i)) and the concentration ([AOH-i]/10(5)) of AOH-i (Tocs, Toc-3s, and γ-oryzanol) included in rice bran extracts. The contribution of γ-oryzanol to the ks(Extract) value was estimated to be between 3.0-4.7% for each extract. Taken together, these results suggest that the ARAC assay method is applicable to general food extracts.

Measurements of aroxyl radical (ArO•)-scavenging rate constants (k(s)(AOH)) of antioxidants (AOHs) [α-, β-, γ-, and δ-tocopherols (TocHs) and -tocotrienols (Toc-3Hs)] were performed in ethanol solution via stopped-flow spectrophotometry. k(s)(AOH) values of α-, β-, γ-, and δ-Toc-3Hs showed good agreement with those of the corresponding α-, β-, γ-, and δ- TocHs. k(s)(AOH) values were measured not only for each antioxidant but also for mixtures of two antioxidants: (i) α-TocH with β-, γ-, or δ-TocH and (ii) α-TocH with α-, β-, γ-, or δ-Toc-3H. A synergistic effect in which the k(s)(AOH) value increases by 12% for γ-TocH (or by 12% for γ-Toc-3H) was observed for solutions including α-TocH and γ-TocH (or γ-Toc-3H). On the other hand, a cancel effect in which the k(s)(AOH) value decreases (a) by 7% for β-TocH (or 11% for β-Toc-3H) and (b) by 24% for δ-TocH (or 25% for δ-Toc-3H) was observed for solutions including two kinds of antioxidants. However, only a synergistic effect may function in edible oils, because contents of β- and δ-TocHs (and β- and δ-Toc-3Hs) are much less than those of α- and γ-TocHs (and α- and γ-Toc-3Hs) in many edible oils. UV-vis absorption of α-Toc•, which was produced by reaction of α-TocH with ArO•, decreased remarkably for coexistence of α-TocH with β-, γ-, or δ-TocH (or β-, γ-, or δ-Toc-3H), indicating that the prooxidant effect of α-Toc• is suppressed by the coexistence of other TocHs and Toc-3Hs.

Volumetric capacity Qvol (mAh cm(–3)), more correctly, volumetric energy density Wvol (mWh cm(–3)), is a crucial property of lithium-ion battery (LIB) materials, because LIBs are devices that operate in a limited space. The actual value of Wvol (Wvol(act)) is currently limited to 40–60% of the maximum (theoretical) value of Wvol (Wvol(max)), for reasons that have not yet been fully clarified. Thus, to gain information that will enable an increase in Wvol(act) such that it is closer to Wvol(max), systematic studies of the values for Qvol, Wvol, true density (dXRD), and particle density (dp) obtained using gas pycnometry were undertaken for LiCo1–xNixO2 samples with 0 ≤ x ≤ 1. Here, dp is the density that includes the volume of the closed pores in the particles, and consequently is less than dXRD, which is determined by X-ray diffraction (XRD) measurement. DXRD monotonically decreased from 5.062(1) g cm(–3) for x = 0 to 4.779(1) g cm(–3) for x = 1, as expected. On the contrary, dp decreased almost linearly from 4.98(2) g cm(–3) for x = 0 to 4.80(2) g cm(–3) for x = 0.5, then suddenly dropped to 4.63(2) g cm(–3) for x = 0.667, and finally leveled off to a constant value (~4.6 g cm(–3)) at larger values of x. The cross-sectional observations using a Focused Ion Beam system revealed that the significantly smaller values for dp compared with those for dXRD, particularly when x > 0.5, is due to the presence of closed pores in agglomerated secondary particles. This indicates that the closed pores in the secondary particles play an important role in determining the value of Wvol(act) for LIBs. The formation of well-developed primary particles as a mean for increasing the value of dp was also investigated.

Measurements of aroxyl radical (ArO•)-scavenging rate constants (ks AOH) of antioxidants (AOHs: pyrroloquinolinequinol (PQQH2), α-tocopherol (α-TocH), ubiquinol-10 (UQ10H2), epicatechin, epigallocatechin, epigallocatechin gallate, and caffeic acid) were performed in dimethyl sulfoxide (DMSO) solution, using stopped-flow spectrophotometry. The ks AOH values were measured not only for each AOH but also for the mixtures of two AOHs ((i) α-TocH and PQQH2 and (ii) α-TocH and UQ10H2). A notable synergistic effect that the ks AOH values increase 1.72, 2.42, and 2.50 times for α-TocH, PQQH2, and UQ10H2, respectively, was observed for the solutions including two kinds of AOHs. Measurements of the regeneration rates of α-tocopheroxyl radical (α-Toc•) to α-TocH by PQQH2 and UQ10H2 were performed in DMSO, using double-mixing stopped-flow spectrophotometry. Second-order rate constants (kr) obtained for PQQH2 and UQ10H2 were 1.08 × 105 and 3.57 × 104 M−1 s−1, respectively, indicating that the kr value of PQQH2 is 3.0 times larger than that of UQ10H2. It has been clarified that PQQH2 and UQ10H2 having two HO groups within a molecule may rapidly regenerate two molecules of α-Toc• to α-TocH. The result indicates that the prooxidant effect of α-Toc• is suppressed by the coexistence of PQQH2 or UQ10H2.

A new free radical absorption capacity assay method is proposed with use of an aroxyl radical (2,6-di-tert-butyl-4-(4'-methoxyphenyl)phenoxyl radical) and stopped-flow spectroscopy and is named the aroxyl radical absorption capacity (ARAC) assay method. The free radical absorption capacity (ARAC value) of each tocopherol was determined through measurement of the radical-scavenging rate constant in ethanol. The ARAC value could also be evaluated through measurement of the half-life of the aroxyl radical during the scavenging reaction. For the estimation of the free radical absorption capacity, the aroxyl radical was more suitable than the DPPH radical, galvinoxyl, and p-nitrophenyl nitronyl nitroxide. The ARAC value in tocopherols showed the same tendency as the free radical absorption capacities reported previously, and the tendency was independent of an oxygen radical participating in the scavenging reaction and of a medium surrounding the tocopherol and oxygen radical. The ARAC value can be directly connected to the free radical-scavenging rate constant, and the ARAC method has the advantage of treating a stable and isolable radical (aroxyl radical) in a user-friendly organic solvent (ethanol). The ARAC method was also successfully applied to a palm oil extract. Accordingly, the ARAC method would be useful in free radical absorption capacity assay of antioxidative reagents and foods.

Measurements of aroxyl radical (ArO(•))-scavenging rate constants (ks(AOH)) of antioxidants (AOHs) (α-tocopherol (α-TocH), ubiquinol-10 (UQ10H2), and sodium ascorbate (Na(+)AsH(-))) were performed in 2-propanol/water (2-PrOH/H2O, 5/1, v/v) solution using stopped-flow spectrophotometry. ks(AOH) values were measured not only for each AOH but also for the mixtures of two AOHs ((i) α-TocH and UQ10H2 and (ii) α-TocH and Na(+)AsH(-)). A notable synergistic effect that the ks(AOH) values increase 1.6, 2.5, and 6.8 times for α-TocH, UQ10H2, and Na(+)AsH(-), respectively, was observed for the solutions including two kinds of AOHs. Furthermore, measurements of the regeneration rates of α-tocopheroxyl radical (α-Toc(•)) to α-TocH by UQ10H2 and Na(+)AsH(-) were performed in 2-PrOH/H2O using double-mixing stopped-flow spectrophotometry. Second-order rate constants (kr) obtained for UQ10H2 and Na(+)AsH(-) were 2.01 × 10(5) and 1.19 × 10(6) M(-1) s(-1), respectively. In fact, UV-vis absorption of α-Toc(•) (λmax = 428 nm), which had been produced by reaction of α-TocH with ArO(•), disappeared under the existence of UQ10H2 or Na(+)AsH(-) due to the above fast regeneration reaction. The result indicates that the prooxidant effect of α-Toc(•) is suppressed by the coexistence of UQ10H2 or Na(+)AsH(-). As α-TocH, UQ10H2, and ascorbate monoanion (AsH(-)) coexist in relatively high concentrations in plasma, blood, and various tissues, the above synergistic effect, that is, the increase of the free-radical-scavenging rate and suppression of the prooxidant reaction, may function in biological systems.

Measurements of the singlet oxygen ((1)O(2)) quenching rates (k(Q) (S)) and the relative singlet oxygen absortpion capacity (SOAC) values were performed for 16 phenolic antioxidants (tocopherol derivatives, ubiquinol-10, caffeic acids, and catechins) and vitamin C in ethanol/chloroform/D(2)O (50:50:1, v/v/v) solution at 35 °C. It has been clarified that the SOAC method is useful to evaluate the (1)O(2)-quenching activity of lipophilic and hydrophilic antioxidants having 5 orders of magnitude different rate constants from 1.38 × 10(10) M(-1) s(-1) for lycopene to 2.71 × 10(5) for ferulic acid. The logarithms of the k(Q) (S) and the SOAC values for phenolic antioxidants were found to correlate well with their peak oxidation potentials (E(p)); the antioxidants that have smaller E(p) values show higher reactivities. In previous works, measurements of the k(Q) (S) values for many phenolic antioxidants were performed in ethanol. Consequently, measurements of the k(Q) (S) and relative SOAC values were performed for eight carotenoids in ethanol to investigate the effect of solvent on the (1)O(2)-quenching rate. The k(Q) (S) values for phenolic antioxidants and carotenoids in ethanol were found to correlate linearly with the k(Q) (S) values in ethanol/chloroform/D(2)O solution with a gradient of 1.79, except for two catechins. As the relative rate constants (k(Q)(AO) (S)/k(Q)(α-Toc) (S)) of antioxidants (AO) are equal to the relative SOAC values, the SOAC values do not depend on the kinds of solvent used, if α-tocopherol is used as a standard compound. In fact, the SOAC values obtained for carotenoids in mixed solvent agreed well with the corresponding ones in ethanol.

The measurements of the UV-vis absorption spectra of α-, β-, γ-, and δ-tocopheroxyl (α-, β-, γ-, and δ-Toc(•)) radicals were performed by reacting aroxyl (ArO(•)) radical with α-, β-, γ-, and δ-tocopherol (α-, β-, γ-, and δ-TocH), respectively, in acetonitrile solution including three kinds of alkali and alkaline earth metal salts (LiClO(4), NaClO(4), and Mg(ClO(4))(2)) (MX or MX(2)), using stopped-flow spectrophotometry. The maximum wavelengths (λ(max)) of the absorption spectra of the α-, β-, γ-, and δ-Toc(•) located at 425-428 nm without metal salts increased with increasing concentrations of metal salts (0-0.500 M) in acetonitrile and approached some constant values, suggesting (Toc(•)···M(+) (or M(2+))) complex formations. Similarly, the values of the apparent molar extinction coefficient (ε(max)) increased drastically with increasing concentrations of metal salts in acetonitrile and approached some constant values. The result suggests that the formations of Toc(•) dimers were suppressed by the metal ion complex formations of Toc(•) radicals. The stability constants (K) were determined for Li(+), Na(+), and Mg(2+) complexes of α-, β-, γ-, and δ-Toc(•). The K values increased in the order of NaClO(4) < LiClO(4) < Mg(ClO(4))(2), being independent of the kinds of Toc(•) radicals. Furthermore, the K values increased in the order of δ- < γ- < β- < α-Toc(•) radicals for each metal salt. The alkali and alkaline earth metal salts having a smaller ionic radius of the cation and a larger charge of the cation gave a larger shift of the λ(max) value, a larger ε(max) value, and a larger K value. The result of the DFT molecular orbital calculations indicated that the α-, β-, γ-, and δ-Toc(•) radicals were stabilized by the (1:1) complex formation with metal cations (Li(+), Na(+), and Mg(2+)). Stabilization energy (E(S)) due to the complex formation increased in the order of Na(+) < Li(+) < Mg(2+) complexes, being independent of the kinds of Toc(•) radicals. The calculated result also indicated that the metal cations coordinate to the O atom at the sixth position of α-, β-, γ-, and δ-Toc(•) radicals.

A kinetic study of regeneration reaction of α-tocopherol (α-TocH) by ubiquinol-10 has been performed in the presence of four kinds of alkali and alkaline earth metal salts (LiClO(4), NaClO(4), NaI, and Mg(ClO(4))(2)) in methanol and acetonitrile solutions, using double-mixing stopped-flow spectrophotometry. The second-order rate constants (k(r)'s) for the reaction of α-tocopheroxyl (α-Toc•) radical with ubiquinol-10 increased and decreased notably with increasing concentrations of metal salts in methanol and acetonitrile, respectively. The k(r) values increased in the order of no metal salt < NaClO(4) ~ NaI < LiClO(4) < Mg(ClO(4))(2) at the same concentration of metal salts in methanol. On the other hand, in acetonitrile, the k(r) values decreased in the order of no metal salt > NaClO(4) ~ NaI > LiClO(4) > Mg(ClO(4))(2) at the same concentration of metal salts. The metal salts having a smaller ionic radius of cation and a larger charge of cation gave a larger k(r) value in methanol, and a smaller k(r) value in acetonitrile. The effect of anion was almost negligible in both the solvents. Notable effects of metal cations on the UV-vis absorption spectrum of α-Toc• radical were observed in aprotic acetonitrile solution, suggesting complex formation between α-Toc• and metal cations. On the other hand, effects of metal cations were negligible in protic methanol, suggesting that the complex formation between α-Toc• and metal cations is hindered by the hydrogen bond between α-Toc• and methanol molecules. The difference between the reaction mechanisms in methanol and acetonitrile solutions was discussed on the basis of the results obtained. High concentrations of alkali and alkaline earth metal salts coexist with α-TocH and ubiquinol-10 in plasma, blood, and many tissues, suggesting the contribution of the metal salts to the above regeneration reaction in biological systems.

The carotenoid β-cryptoxanthin (β-CRX) is abundant in Satsuma mandarins (Citrus unshiu Marc). Several studies have shown a relationship between Satsuma mandarin consumption and a low risk of several diseases, for example, diabetes, gout, and hypertension, suggesting β-CRX involvement in disease prevention. We investigated the effect of β-CRX on mildly obese males. β-CRX administration reduced visceral adipose tissue, body weight, and abdominal circumference. However, the detailed mechanism by which β-CRX mediates these changes remains unknown. To identify this mechanism, we used an obese model mouse (TSOD). Oral β-CRX administration repressed body weight, abdominal adipose tissue weight, and serum lipid concentrations in TSOD; these results are identical to previous human trial results. β-CRX administration significantly repressed adipocyte hypertrophy. Gene expression analysis strongly indicated that β-CRX can alter cytokine secretion and cell proliferation. These results suggest that β-CRX derived from Satsuma mandarins can help prevent obesity by repressing hypertrophy of abdominal adipocytes.

The measurement of the UV-vis absorption spectrum of α-tocopheroxyl (α-Toc(•)) radical was performed by reacting aroxyl (ArO(•)) radical with α-tocopherol (α-TocH) in acetonitrile solution including four kinds of alkali and alkaline earth metal salts (MX or MX(2)) (LiClO(4), LiI, NaClO(4), and Mg(ClO(4))(2)), using stopped-flow spectrophotometry. The maximum wavelength (λ(max)) of the absorption spectrum of the α-Toc(•) at 425.0 nm increased with increasing concentration of metal salts (0-0.500 M) in acetonitrile, and it approached constant values, suggesting an [α-Toc(•)-M(+) (or M(2+))] complex formation. The stability constants (K) were determined to be 9.2, 2.8, and 45 M(-1) for LiClO(4), NaClO(4), and Mg(ClO(4))(2), respectively. By reacting ArO(•) with α-TocH in acetonitrile, the absorption of ArO(•) disappeared rapidly, while that of α-Toc(•) appeared and then decreased gradually as a result of the bimolecular self-reaction of α-Toc(•) after passing through the maximum. The second-order rate constants (k(s)) obtained for the reaction of α-TocH with ArO(•) increased linearly with an increasing concentration of metal salts. The results indicate that the hydrogen transfer reaction of α-TocH proceeds via an electron transfer intermediate from α-TocH to ArO(•) radicals followed by proton transfer. Both the coordination of metal cations to the one-electron reduced anions of ArO(•) (ArO:(-)) and the coordination of counteranions to the one-electron oxidized cations of α-TocH (α-TocH(•)(+)) may stabilize the intermediate, resulting in the acceleration of electron transfer. A remarkable effect of metal salts on the rate of bimolecular self-reaction (2k(d)) of the α-Toc(•) radical was also observed. The rate constant (2k(d)) decreased rapidly with increasing concentrations of the metal salts. The 2k(d) value decreased at the same concentration of the metal salts in the following order: no metal salt > NaClO(4) > LiClO(4) > Mg(ClO(4))(2). The complex formation between α-Toc(•) and metal cations may stabilize the energy level of the reactants (α-Toc(•) + α-Toc(•)), resulting in the decrease of the rate constant (2k(d)). The alkali and alkaline earth metal salts having a smaller ionic radius of cation and a larger charge of cation gave larger K and k(s) values and a smaller 2k(d) value.

Recently a new assay method that can quantify the singlet oxygen absorption capacity (SOAC) of antioxidants was proposed. In the present work, kinetic study of the reaction of singlet oxygen ((1)O(2)) with carotenoids and vegetable extracts has been performed in ethanol/chloroform/D(2)O (50:50:1, v/v/v) solution at 35 °C. Measurements of the second-order rate constants (k(Q)(S)) and the SOAC values were performed for eight kinds of carotenoids and three kinds of vegetable extracts (red paprika, carrot, and tomato). Furthermore, measurements of the concentrations of the carotenoids included in vegetable extracts were performed, using a HPLC technique. From the results, it has been clarified that the total (1)O(2)-quenching activity (that is, the SOAC value) for vegetable extracts may be explained as the sum of the product {Σ k(Q)(Car-i)(S) [Car-i](i)} of the rate constant (k(Q)(Car-i)(S)) and the concentration ([Car (i)]) of carotenoids included in vegetable extracts.

A kinetic study of the quenching reaction of singlet oxygen ((1)O(2)) with pyrroloquinolinequinol (PQQH(2), a reduced form of pyrroloquinolinequinone (PQQ)), PQQNa(2) (disodium salt of PQQ), and seven kinds of natural antioxidants (vitamin C (Vit C), uric acid (UA), epicatechin (EC), epigallocatechin (EGC), α-tocopherol (α-Toc), ubiquinol-10 (UQ(10)H(2)), and β-carotene (β-Car)) has been performed. The second-order rate constants k(Q) (k(Q) = k(q) + k(r), physical quenching and chemical reaction) for the reaction of (1)O(2) with PQQH(2), PQQNa(2), and seven kinds of antioxidants were measured in 5.0 wt % Triton X-100 micellar solution (pH 7.4), using UV-visible spectrophotometry. The k(Q) values decreased in the order of β-Car > PQQH(2) > α-Toc > UA > UQ(10)H(2) > Vit C ∼ EGC > EC ≫ PQQNa(2). PQQH(2) is a water-soluble antioxidant. The singlet oxygen-quenching activity of PQQH(2) was found to be 6.3, 2.2, 6.1, and 22 times as large as the corresponding those of water-soluble antioxidants (Vit C, UA, EGC, and EC). Further, the activity of PQQH(2) was found to be 2.2 and 3.1 times as large as the corresponding activity of lipid-soluble antioxidants (α-Toc and UQ(10)H(2)). On the other hand, the activity of PQQH(2) is 6.4 times as small as that of β-Car. It was observed that the chemical reaction (k(r)) is almost negligible in the quenching reaction of (1)O(2) by PQQH(2). The result suggests that PQQH(2) may contribute to the protection of oxidative damage in biological systems, by quenching (1)O(2).

A kinetic study of the quenching reaction of singlet oxygen (1O2) with eight kinds of carotenoids and α-tocopherol was performed in ethanol/chloroform/D2O (50:50:1, v/v/v) solution at 35 °C. The overall rate constants, kQ (=kq+kr, physical quenching+chemical reaction), for the reaction of carotenoids with 1O2 were measured, using the competition reaction method, where endoperoxide was used as a singlet oxygen generator, 2,5-diphenyl-3,4-benzofuran (DPBF) as an UV-vis absorption prove, and α-tocopherol as a standard compound. The rate constants, kQ (S) and kQ (t1/2), were determined by analyzing the first-order rate constant (S) and the half-life (t1/2) of the decay curve of DPBF with carotenoids, respectively, showing good accordance with each other. Similar measurements were performed for tomato and carrot extracts. From the results, a new assay method that can quantify the singlet oxygen absorption capacity (SOAC) of antioxidants, including carotenoids, α-tocopherol, and vegetable extracts, has been proposed.

A kinetic study of the regeneration reaction of vitamin E by ubiquinol was carried out by means of double-mixing stopped-flow spectroscopy. A substantial deuterium kinetic-isotope effect was observed on the second-order rate constant and the activation energy. In the regeneration reaction of alpha-tocopherol, deuteration of ubiquinol increased and decreased the activation energy and the second-order rate constant by 6.1 kJ/mol and a factor of 18.3, respectively. From this result, it is considered that proton tunneling plays an important role in the regeneration reaction of vitamin E by ubiquinol. The conditions under which the tunneling effect becomes an important factor were discussed in conjunction of our experimental results.

A kinetic study of the aroxyl (ArO*) radical-scavenging reaction of alpha-tocopherol (alpha-TocH) has been performed in the presence of six kinds of alkali and alkaline earth metal salts (LiI, LiClO(4), NaI, NaClO(4), KI, and Mg(ClO(4))(2)) in methanol solution, using stopped-flow spectrophotometry. The decay rate of the ArO* for the reaction of alpha-TocH with ArO* increased linearly with increasing concentration of metal salts. The second-order rate constants (k(s)) for the reaction of alpha-TocH with ArO* increased in the order of no metal salt < KI approximately NaClO(4) approximately NaI

Kinetic study of the aroxyl radical-scavenging action of pyrroloquinolinequinol [PQQH(2), a reduced form of pyrroloquinolinequinone (PQQ)] and water-soluble antioxidants (vitamin C, cysteine, glutathione, and uric acid) has been performed. The second-order rate constants (k(s)) for the reaction of aroxyl radical with PQQH(2) and water-soluble antioxidants were measured in Triton X-100 micellar solution (5.0 wt %) (pH 7.4), using stopped-flow and UV-visible spectrophotometers. The k(s) values decreased in the order PQQH(2) > vitamin C >> cysteine > uric acid > glutathione. The aroxyl radical-scavenging activity of PQQH(2) was 7.4 times higher than that of vitamin C, which is well-known as the most active water-soluble antioxidant. Furthermore, PQQNa(2) (disodium salt of PQQ) was easily reduced to PQQH(2) by reaction of PQQNa(2) with glutathione and cysteine in buffer solution (pH 7.4) under nitrogen atmosphere. The result suggests that PQQ exists as a reduced form throughout the cell and plays a role as antioxidant.

Kinetic study of the aroxyl radical-scavenging action of catechins (epicatechin (EC), epicatechin gallate (ECG), epigallocatechin (EGC), and epigallocatechin gallate (EGCG)) and related compounds (methyl gallate (MG), 4-methylcatechol (MC), and 5-methoxyresorcinol (MR)) has been performed. The second-order rate constant ( k s) for the reaction of these antioxidants with aroxyl radical has been measured in ethanol and aqueous Triton X-100 micellar solution (5.0 wt %). The k s values decreased in the order of EGCG > EGC > MC > ECG > EC > MG >> MR in ethanol, indicating that the reactivity of the OH groups in catechins decreased in the order of pyrogallol B-ring > catechol B-ring > gallate G-ring > resorcinol A-ring. The structure-activity relationship in the free radical-scavenging reaction by catechins has been clarified by the detailed analyses of the pH dependence of k s values. From the results, the p K a values have been determined for catechins. The monoanion form at catechol B- and resorcinol A-rings and dianion form at pyrogallol B- and gallate G-rings show the highest activity for free radical scavenging. It was found that the free radical-scavenging activities of catechins are 3.2-13 times larger than that of vitamin C at pH 7.0.

The rate constants (kr) of the regeneration reaction of 7-t-butyl-5-isopropyltocopheroxyl with ubiquinol-10 (UQ10H2), ubiquinol-0 (UQ0H2), alpha-, beta-, and gamma-tocopherolhydroquinones (alpha-, beta-, gamma-TQH2), 2,3,5-trimethyl-1,4-hydroquinone (TMQH2), vitamin K3 hydroquinone (VK3H2), and vitamin C (Vit C) have been measured in 2-propanol/water and micellar solutions by a stopped-flow spectrophotometer. The kr values of these hydroquinones (HQs) in micellar solution remained constant at pHs of 6-9 and increased rapidly by increasing the pH value. The kr values decreased in the order of VK3H2 > gamma-TQH2 > or = alpha-TQH2 > beta-TQH2 > or = UQ10H2 > or = TMQH2 > UQ0H2 >> Vit C at pHs of 6-9. These HQs are dibasic acids and can exist in three different molecular forms, depending on pH. By comparing the kr values with the mole fraction of each molecular form of the HQs, the reaction rate kr1 for the undissociated form, kr2 for the monoanion, and kr3 for the dianion and the pKa1 and pKa2 values were determined. It has been found that the kr values of UQ10H2, alpha-TQH2, beta-TQH2, and gamma-TQH2 (plastoquinol model) are 460, 1430, 494, and 1530 times larger than that of Vit C at pH 7.0, respectively, although the values are similar to that of Vit C in 2-propanol/water. The biological HQs and Vit C coexist in many tissues of animals and plants, and thus, the relative antioxidant activities of HQs and Vit C have been tentatively discussed based on the products of kr values by concentrations in several tissues. The results suggest that these HQs show high activity for the tocopherol regeneration in biological systems.

The reaction rates ( k s) of tocopherol metabolites (alpha-, gamma-, and delta-CEHC) and Trolox with aroxyl radical have been measured in ethanol and micellar solution by a stopped-flow spectrophotometer, and the k s values obtained were compared with those reported for tocopherols (alpha-, beta-, gamma-, and delta-tocopherol, TocH) and tocol. The rate constants ( k s) increased in the order of Tocol < delta-CEHC < delta-TocH < gamma-CEHC < Trolox approximately gamma-TocH approximately beta-TocH < alpha-CEHC < alpha-TocH in ethanol. The antioxidants that have lower oxidation potentials ( E p) showed higher reactivities. The k s values of alpha-, beta-, gamma-, and delta-tocopherol and tocol in micelle remained constant between pH 4 and pH 10 and decreased rapidly at pH 11~12 by increasing pH value. On the other hand, the k s values of alpha-CEHC, gamma-CEHC, and Trolox showed notable pH dependence. As a result of the detailed analysis of the pH dependence of the rate constants ( k s), the structure-activity relationship in the free radical-scavenging action of the tocopherol metabolites and Trolox has been clarified.

The magnetic orientation has been studied for paramagnetic organic radical crystals 1,3,5-triphenyl-6-oxoverdazyl and 1,5-di-p-tolyl-3-phenyl-6-oxoverdazyl in magnetic fields of 2-80 kOe at temperatures of 77-343 K. The X-ray diffraction measurement has revealed that the crystals are oriented with the crystallographic c axis perpendicular to the field. The anisotropic diamagnetic susceptibility arising from the benzene rings has been estimated for the crystals along the principal magnetic chi 1, chi 2, and chi 3 axes. (The chi 1 axis is at a small angle to the a axis in the monoclinic ac plane, and the chi 3 axis is along the b axis.) Since the paramagnetic susceptibility originating from the verdazyl ring is isotropic (though a large absolute value), it is shown that the magnetic orientation occurs by the anisotropy of the diamagnetic susceptibility in the crystals. The diamagnetic susceptibility is found to have a relation of chi 2 < chi 1 < chi 3 < 0.

We investigated the adsorption states of 2-methylpropene and propene on Si(100)c(4 x 2) using low-temperature scanning tunneling microscopy. We have found that regioselective cycloaddition reactions (di-sigma bond formation) occur between the asymmetric alkene molecules and the asymmetric dimers on Si(100)c(4 x 2). First-principles calculations have elucidated that the regioselectivity is closely related to the structures of precursor species and these precursor species have carbocation-like features. Thus, we conclude that Markovnikov's rule is applicable for the cycloaddition of asymmetric alkene with the asymmetric dimer on Si(100)c(4 x 2).

The reaction rates (ks) of vitamin E (alpha-, beta-, gamma-, delta-tocopherols, TocH), ubiquinol-10, and related antioxidants (tocol, ubiquinol-0, and hydroquinone) with aroxyl (ArO(.-)) radical have been measured in micellar solution by stopped-flow spectrophotometer. The ks values increased in the order of hydroquinone < tocol < delta-TocH < ubiquinol-0 < gamma-TocH approximately beta-TocH < ubiquinol-10 < alpha-TocH at pH 4 approximately 8. The antioxidants which have lower oxidation potentials showed higher reactivities. The ks values of alpha-, beta-, gamma-, delta-tocopherol, and tocol remained constant between pH 4 and 10, and decreased rapidly at pH 11 approximately 12 by increasing pH value. From the pH dependence of ks values, the pKa values (= 13.1 approximately 12.6) have been determined for these tocopherols. The ks values of ubiquinol-10 also remained constant between pH 4 and 9, and increased rapidly at pH 9.5. Ubiquinol-10 is dibasic acid and can exist in three different molecular forms, depending on the pH value. By comparing the ks values with the mole fraction of each molecular form of ubiquinol-10, the reaction rate ks1 (= 1.21 x 10(5) M(-1)s(-1)) for the undissociated form, ks2 (= 1.04 x 10(6) M(-1)s(-1)) for monoanion and ks3 (= 0 M(-1)s(-1)) for dianion, and the pKa1 and pKa2 values (= 11.4 and 12.7) were determined. The ks2 value is 8.6 times as large as the ks1 value. Similar analyses were performed for ubiquinol-0 and hydroquinone. It was found that the relative ratio of ks values (100:21:20:2.9) of alpha-, beta-, gamma-, delta-tocopherols in micellar dispersion has good correlation with the relative biopotency ratios for rat fetal resorption, rat hemeolysis, and chicken muscle dystrophy. The relative antioxidant activities of alpha-tocopherol and ubiquinol-10 have been discussed based on the ks values obtained and their concentrations in serum and several tissues (heart, muscle, liver, kidney, and brain).

The adsorption of water (D(2)O) molecules on Rh(111) at 20 K was investigated using infrared reflection absorption spectroscopy (IRAS). At the initial stage of adsorption, water molecules exist as monomers on Rh(111). With increasing water coverage, monomers aggregate into dimers, larger clusters (n = 3-6), and two-dimensional (2D) islands. Further exposure of water molecules leads to the formation of three-dimensional (3D) water islands and finally to a bulk amorphous ice layer. Upon heating, the monomer and dimer species thermally migrate on the surface and aggregate to form larger clusters and 2D islands. Based on the temperature dependence of OD stretching peaks, we succeeded in distinguishing water molecules inside 2D islands from those at the edge of 2D islands. From the comparison with the previous vibrational spectra of water clusters on other metal surfaces, we conclude that the number of water molecules at the edge of 2D islands is comparable with that of water molecules inside 2D islands on the Rh(111) surface at 20 K. This indicates that the surface migration of water molecules on Rh(111) is hindered as compared with the cases on Pt(111) and Ni(111) and thus the size of 2D islands on Rh(111) is relatively small.

The quenching rate of singlet oxygen (1O2) by seven kinds of flavonoids (flavone, flavonol, chrysin, apigenin, rutin, quercetin, and myricetin) with 2,3-double bonds has been measured spectrophotometrically in ethanol at 35 degrees C. The overall rate constants kQ (= kq + kr, physical quenching + chemical reaction) increased as the number of OH groups substituted to the flavone skeleton (that is, the total electron-donating capacity of flavonoids) increases. The existence of catechol or pyrogallol structure in the B-ring is essential for the 1O2 quenching of flavonoids. Log kQ was found to correlate with their peak oxidation potentials, E(P); the flavonoids that have smaller E(P) values show higher reactivities. Similarly, log kQ values of flavonoids correlate with the energy level of the highest occupied molecular orbital (E(HOMO)), calculated by the PM3 MO method, and the longest wavelength pi pi* excitation energy (E(ex)). The contribution of the chemical reaction (kr) was found to be negligible in these flavonoids. The kQ values of rutin, quercetin, and myricetin [(1.21 approximately 5.12) x 10(8) M(-1) s(-1)] were found to be larger than those of lipids [(0.9 approximately 6.4) x 10(4) M(-1) s(-1)], amino acids (<3.7 x 10(7) M(-1) s(-1)), and DNA (5.1 x 10(5) M(-1) s(-1)). The result suggests that these flavonoids may contribute to the protection of oxidative damage in foods and plants, by quenching 1O2.

We report the direct observation of a precursor state for the cycloaddition reaction (the di-sigma bond formation) of ethylene on Si(100)c(4 x 2) using high-resolution electron energy loss spectroscopy at low temperature, and the meta-stable precursor state is identified as a weakly bonded pi-complex type. The activation energy from the pi-complex precursor to the di-sigma bonded species is experimentally estimated to be 0.2 eV. First-principles calculations support the pi-complex precursor mediated cycloaddition reaction of ethylene on Si(100)c(4 x 2).