Recent Advances in NIR-Switchable Multi-Redox Systems Based on Organic Molecules.

In recent years, near-infrared (NIR) dyes, exhibiting absorption in the NIR region (750-2500 nm), have been applied to various optical applications such as security marking, photovoltaic cells and chemotherapy of deep tissues in vivo. Electrochromic systems capable of switching NIR absorption are attractive from the viewpoint of applications for material and life science, and thus several examples have been reported to date. The development of organic-based materials is needed to reduce the environmental impact and improve biocompatibility, however, the switching of NIR absorption based on redox interconversion is still a challenging issue regarding reversibility and durability during interconversion. To overcome this potential instability, several studies on organic electrochromic systems that allow ON/OFF switching of NIR absorption have been developed in recent years. In this review, we focus on redox-active well-defined small molecules that enable ON/OFF switching of NIR absorption, and present recent studies on their intrinsic electrochemical and spectroscopic properties and/or structural characterization of their charged states. We also address more sophisticated electrochromic systems that can modulate their properties in response to external stimuli such as light, heat, and electric potential.

Heterogeneous precipitation behavior and mechanism during the adsorption of cationic heavy metals by biochar: Roles of inorganic components.

Heavy metals are commonly adsorbed by biochar in contaminated water and soil. However, the behaviour and underlying mechanisms of heterogeneous precipitation between the inorganic components of biochar and cationic heavy metals remain poorly understood. In this study, we comprehensively investigated the nucleation, growth, and aggregation of precipitates, ion exchange-coupled precipitation behaviour, adsorption-precipitation correlation, and the influence of environmental factors (e.g., anion content, pH, initial concentration, type of heavy metals, and biochar size). The kinetic results indicated that the generation of precipitates was accompanied by an adsorption reaction with a gradual increase in crystal size and aggregation behaviour. Moreover, precipitation includes both surface and solution precipitation. The increasing local concentration of Pb(II) around the biochar at high initial concentrations increased the supersaturation of the nucleating substance, which decreased the potential for heterogeneous nucleation and facilitated heterogeneous precipitation. Correlation analysis revealed the presence of a coupling mechanism between precipitation and cation exchange. The enhanced electrostatic attraction at high pH could lower the heterogeneous nucleation potential barrier, thus promoting heterogeneous precipitation. The small biochar size extended the induction time, which was unfavourable for heterogeneous nucleation. This study provides a deeper understanding of the heterogeneous precipitation behaviour of the inorganic components of biochar and cationic heavy metals.

Borenium Ion Equivalents Stabilized by BICAAC and Their Implementation as Catalysts in Hydrosilylation of Carbonyls.

Hydride abstraction from the borane adduct, (BICAAC)‧BH3 afforded the hydride bridged dinuclear borenium ion equivalent complexes 1 and 2 that have been characterized by various spectroscopic and spectrometric techniques followed by the assessment of Lewis acidity using the Gutmann-Beckett method. The single crystal X-ray structure of complex 2 revealed the presence of discrete ions in the solid state. The complex (BICAAC)‧BH2(OTf) (3), obtained from the reaction of (BICAAC)‧BH3 with MeOTf, forms the corresponding boronium cations [(BICAAC)‧BH2(L)]+(OTf)- on reaction with Lewis bases (L = pyridine (4) and DMAP (5)). Complexes 1 and 2 demonstrated notable catalytic activity in the hydrosilylation of a diverse array of carbonyls using 1.0 mol% catalyst loading (achieving the highest turnover frequency (TOFmax) of up to 1200 h-1 with benzaldehyde. A broad substrate scope has been presented for aldehydes and ketones decorated with various electron-donating and withdrawing substituents along with this the hydrosilylation of a few para-quinone methides has also been presented.

Rapid evaluation of vegetable oil varieties and geographical origins by ambient corona discharge ionization mass spectrometry.

The composition and ratio of unsaturated fatty acids in vegetable oils play a crucial role in determining their overall quality. In this study, we present a corona discharge ionization mass spectrometry (MS) method for the rapid differentiation of vegetable oil varieties and their geographical origins under environmental conditions. Abundant water dimer radical cations, (H2O)2+•, were generated by the ionization setup, which effectively activated carbon­carbon double bonds (C=C) to form epoxidized products. These epoxidation products were analyzed using tandem MS, generating diagnostic fragment ions that precisely identified CC bond positions. Statistical analysis models were subsequently developed using the resulting MS fingerprint data, revealing significant differences between various vegetable oils and olive oils from different origins. Key advantages of this method include minimal sample preparation, rapid analysis, and easily interpretable spectra. This study provides a new MS-based strategy for food quality assessment and offers a promising tool for identifying CC positional isomers in complex systems.

Characterization of varietal effects on the acidity and pH of grape berries for selection of varieties better adapted to climate change.

Climate change is drastically modifying berry composition and wine quality across the world. Most wine regions with a history of winemaking are suffering from a loss of typicity and terroir expression because of climate change impact on berry components at harvest, including wine acidity, with total acidity decreasing and pH increasing. Such changes can have a major impact on wine stability and quality. One important option for adaptation is the selection of grapevine varieties better adapted to warmer and drier conditions. Weekly measurement of tartaric acid, malic acid, pH and titratable acidity from veraison until maturity were carried out on 51 varieties over seven years in two experimental plots. Varietal differences were shown for the rate of malic acid degradation during the ripening period, with some varieties metabolizing malic acid faster per unit of thermal time than others. Some varietal differences were also noticed regarding tartaric acid modulation, which can occur under exceptionally high temperatures. Differences in the dynamics of pH evolution in grape must over the growing season were evaluated and varieties characterized with regard to organic acids (tartaric acid and malic acid), inorganic compounds (cations) as well as pH levels and stability. This multi-trait approach allows the selection of grapevine varieties based on parameters linked to their acidity, which is of particular importance in the context of climate change.

Developing Rapid-Charging Li-S Batteries via "Target Catalysis" of Cations and Anions Modified Electrocatalyst.

The shuttle effect and sluggish sulfur reduction reaction have resulted in significantly low efficiency and poor high current cycling stability in lithium-sulfur batteries, impeding their practical applications. To address these challenges, the introduction of Ni cations into MoS2 grown on reduced graphene oxide (MoS2/rGO) induces the formation of impurity energy levels between the conduction and valence bands of MoS2. Additionally, the introduction of anionic Se expands the interlayer spacing, enhances intrinsic conductivity, and improves ion diffusion rates. Simultaneously introducing anionic and cationic species into the MoS2/rGO causes the center of the d-band to shift upward, reducing the occupancy of electrons in antibonding orbitals. This modification leads to a rearrangement of the electronic structure of Mo, accelerating the redox reactions of lithium polysulfides. It particularly enhances the binding energy and lowers the conversion energy barrier of Li2S4. Consequently, the Li||S coin cell with the Ni-MoSSe/rGO cathode demonstrates an initial capacity of 446 mAh g-1 at 20 C, with a remarkable capacity retention of ≈96.7% after 200 cycles. Moreover, even under high sulfur loading conditions (6.45 mg cm-2) and a low electrolyte/sulfur ratio (5.4 µL mg-2), it maintains a high areal capacity of 6.42 mAh cm-2.

Impacts of shifting from single-species pine forests to distinct agroforestry models on soil fertility, exchangeable cations, and microbial functions.

The transition from monoculture to mixed-species agroforestry systems affects soil organic matter and microbial activity. However, the specific dynamics of these changes, particularly within medicinal plant-based agroforestry, remain underexplored. This study investigates the impact of monoculture Pine (Pinus massoniana) forests and four agroforestry models: (M1) Pinus massoniana and Alpina oxyphylla, (M2) Pinus massoniana and Ficus simplicissima, (M3) Pinus massoniana and Amomum villosum, and (M4) Pinus massoniana and Curcuma longa on soil properties and microbial activity in rhizosphere and non-rhizosphere environments. Our results showed significantly higher pH (4.80) and total nitrogen (N) content (1.77 g kg-1) in the rhizosphere of model (M4) compared to (CK). Total organic carbon (TOC) and carbon fractions (POC, DOC, and MBC) also differed significantly across monoculture and agroforestry models, with highest TOC concentrations (31.70 g kg⁻1) in rhizosphere of CK. Exchangeable cations, including Ca2⁺, and Mg2⁺ were significantly higher in the rhizosphere of agroforestry models compared to CK, particularly in M4, where Ca2⁺ was recorded at 12.03 cmol kg-1 with the highest percent base saturation (PBS) at 90.17%. Enzymes leucine aminopeptidase and polyphenol oxidase varied significantly, with higher activity in the rhizosphere of agroforestry models and greater activity in non-rhizosphere of monoculture. Soil microbial respiration (MRes) revealed substantial differences, with an average 17% decrease in rhizosphere soil for models M2 and M4 and a 20.83% reduction in non-rhizosphere soil for model M1 compared to CK. Generalized Linear Model (GLM) demonstrated a significant positive correlation between TOC and MRes (R2 = 0.885, p < 0.01), indicating that higher TOC levels are linked with increased MRes. In conclusion, model M4 most effectively enhanced soil fertility and nutrient availability followed by the other agroforestry models tested. This suggests that integrating medicinal plants into agroforestry systems is a viable strategy for improving ecosystem functioning compared to monoculture practices.

Preparation, structure, reactivity, Lewis acidic and fluorescence properties of arylpyridine based boron C,N-chelates featuring weakly coordinating anions.

Herein, we present the preparation of a series of electronically and/or sterically distinct borenium-type species based on a simple 2-arylpyridine scaffold. Corresponding arylpyridine was firstly subjected to electrophilic borylation (BBr3 / i-Pr2NEt) and formed BBr2 chelate was reduced with LiAlH4 to yield arylpyridine boron dihydride. Elimination of one hydride led to Lewis acidic borenium-like products. Four methods of hydride elimination were evaluated and influence of counterions on reactivity, Lewis acidic and luminescent properties was assessed both experimentally and computationally. Arylpyridine chelates featuring weakly coordinating counterions exhibit fluorescent properties upon UV irradiation. Several general trends were inferred to modulate emission wavelength and fluorescence quantum yield. Based on our observations, we have devised and prepared borenium-type fluorophores with yellow-green fluorescence and quantum yields up to 93%.

Design and synthesis of novel mitochondria-targeted ergosterol peroxide derivatives as potential anti-cancer agents.

Ergosterol peroxide (EP) is a natural steroid compound that has been reported to have significant antitumor activity. However, its poor water solubility and cellular uptake mean that it has weak efficacy against tumor cells. Herein, we designed and synthesized a series of EP derivatives with mitochondrial targeting properties. Of these, compound 15a showed an IC50 value of 0.32 µM against MCF-7 cells, which was 67-fold higher than that of the parental EP (IC50 = 21.46 µM), and was better than cisplatin (IC50 = 4.23 µM), had a selectivity index of 25.28 (IC50MCF-10A/IC50MCF-7). Additionally, compound 15a promoted an increase in intracellular reactive oxygen species levels and a decrease in mitochondrial membrane potential, and blocked the cell cycle in the G0/G1 phase. In a mouse model of breast cancer, 15a showed 89.85 % tumor inhibition at a dose of 20 mg/kg, which is similar to the therapeutic effect of the cisplatin. On the basis of these results, 15a could be considered for further preclinical evaluation for cancer therapy.

Unimolecular isomerizations of C6H6•+ radical cations: a computational study.

CONCEPT: Eighteen concerted isomerization reactions of various C6H6•+ radical cation (RC) species are studied and found to proceed via well-defined transition states, whose relative positions along the reaction pathway generally agree with Hammond's postulate. From the barrier heights, the rate coefficients of these reactions are estimated by using transition state theory, and the activation energies are computed. Through combination among themselves, these 18 isomerizations yielded 15 multi-step conversion routes of various C6H6•+ species to the lowest energy benzene radical cation isomer 1, which routes are compared. METHODS: Use is made of DFT with the B3LYP and M06-2X functionals, along with the CBS-QB3 approach to arrive at better energies. From the barrier heights for each of the concerted reactions, canonical transition state theory was applied to evaluate rate coefficients k over the temperature range 200-500 K. The Arrhenius activation energies were computed using the plot of ln k vs. 1/T.

The effects of Carpinus betulus expansion on soil properties under changing climatic conditions.

Carpinus betulus (CB) is becoming increasingly important in the forests of Central Europe and is significantly increasing its proportion in various habitat types. We have analysed how the increase in CB affects soil properties. The study was conducted in the Bialowieza Forest (BF). We monitored the changes in CB cover between 1962 and 2013 on 56 permanent plots and collected samples of the litter sub-horizons and the content of the underlying A horizons for laboratory analyses in 2014. During the study period, there was a significant increase in CB cover in the second tree layer by an average of 17.4 % (±1.8) and in the shrub layer by 3.8 % (±1.0), as well as an increase in species diversity from 41 % in the past to 59 % currently. The C/N ratio of the Oi sub-horizon was 32.0 (±0.9), and NH4+ compounds predominated over NO3-, with all nitrogen forms most closely associated with the C/N ratio. In the Oea sub-horizon, the C/N ratio was 23.4 (±0.4), and the sum of mineralised nitrogen reached 8%, with a clear predominance of NO3-. The characteristic most strongly associated with the increase in CB coverage was the NO3- content in the Oea sub-horizon. The MID analysis confirmed that the change in CB cover was not only significant, but also ecologically important. We suggest that there is a feedback loop in which the generally observed climate changes lead to trees occupying new habitats that supply the forest floor with high quality litter, which in turn affects the soil and promotes the persistence of changes in the species composition of the forest.

Increased rainfall frequency enhances dry seasonal soil mineral-associated organic carbon in a subtropical forest.

Climate models predict longer and more severe droughts, and alterations in the frequency and intensity of rainfall events. However, how changing precipitation patterns affect soil organic carbon (SOC), particulate organic carbon (POC), and mineral-associated organic carbon (MAOC) remains unclear. Here, we conducted a three-year rainfall manipulation experiment with ambient rainfall as the control, removal of half the total rainfall amount with unaltered frequency (DRA), and increased rainfall frequency with the total amounts unchanged (IRF) in a subtropical forest. The results showed that the rainfall treatments did not change SOC content or fractions during the wet season. In the dry season, DRA significantly increased topsoil POC but did not change SOC or MAOC. IRF significantly increased POC and MAOC levels. The increased MAOC was associated with the newly formed binary complexes of Fe3+, Al3+, and Ca2+, and the adsorption/precipitation of reduced short-range-ordered Fe oxides, likely derived from the enhanced reductive dissolution in the IRF treatment. Our results suggest that changes in rainfall frequency affect organo-mineral interactions more profoundly relative to the rainfall amount and that these effects are season-dependent. Therefore, moisture-sensitive geochemical processes play an essential role in SOC stabilization in subtropical forests.

Mechanical and Ionic Characterization for Organic Semiconductor-Incorporated Perovskites for Stable 2D/3D Heterostructure Perovskite Solar Cells.

Hybrid metal halide perovskite (MHP) materials, while being promising for photovoltaic technology, also encounter challenges related to material stability. Combining 2D MHPs with 3D MHPs offers a viable solution, yet there is a gap in the understanding of the stability among various 2D materials. The mechanical, ionic, and environmental stability of various 2D MHP ligands are reported, and an improvement with the use of a quater-thiophene-based organic cation (4TmI) that forms an organic-semiconductor incorporated MHP structure is demonstrated. It is shown that the best balance of mechanical robustness, environmental stability, ion activation energy, and reduced mobile ion concentration under accelerated aging is achieved with the usage of 4TmI. It is believed that by addressing mechanical and ion-based degradation modes using this built-in barrier concept with a material system that also shows improvements in charge extraction and device performance, MHP solar devices can be designed for both reliability and efficiency.

Design, synthesis and antitumor effects of lupeol quaternary phosphonium salt derivatives.

Lupeol is a natural pentacyclic triterpenoid with a wide range of biological activities. To improve the water solubility and targeting of lupeol, in the following study, we synthesized 27 lupeol derivatives in the first series by introducing lipophilic cations with lupeol as the lead compound. Through the screening of different cancer cells, we found that some of the derivatives showed better activity than cisplatin against human non-small cell lung cancer A549 cells, among which compound 6c was found to have an IC50 value of 1.83 µM and a selectivity index of 21.02 (IC50MRC-5/IC50A549) against A549 cells. To further improve the antiproliferative activity of the compounds, we replaced the ester linkage of the linker with a carbamate linkage and synthesized a second series of five lupeol derivatives which were screened for activity, among which compound 14f was found to have an IC50 value of 1.36 µM and a selectivity index of 15.60 (IC50MRC-5/IC50A549) against A549 cells. We further evaluated the bioactivity of compounds 6c and 14f and found that both compounds induced apoptosis in A549 cells, promoted an increase in intracellular reactive oxygen species and decrease in mitochondrial membrane potential, and inhibited the cell cycle in the S phase. Of the compounds, compound 14f showed stronger bioactivity than compound 6c. We then selected compound 14f for molecular-level Western blot evaluation and in vivo evaluation in the zebrafish xenograft A549 tumor cell model. Compound 14f was found to significantly downregulate Bcl-2 protein expression and upregulate Bax, Cyt C, cleaved caspase-9, and cleaved caspase-3 protein expression, and 14f was found to be able to inhibit the proliferation of A549 cells in the zebrafish xenograft model. The above results suggest that compound 14f has great potential in the development of antitumor drugs targeting mitochondria.

Heavier Diferrocenylpnictogenium Ions.

The synthesis, characterization and reactivity of the diferrocenylphosphenium ion [Fc2P]+ was extended to the heavier diferrocenylpnictogenium ions, [Fc2E]+ (E = As, Sb, Bi). The lighter diferrocenylnitrenium ion, [Fc2N]+, was detected by mass spectrometry, but could not be isolated. The molecular structures of [Fc2E]+ (E = P, As, Sb, Bi) reveal intramolecular coordination of the iron atoms, which counterbalance the electron deficiency of the pnictogens without affecting the strong Lewis acidities, which were determined according to the method of Gutmann and Beckett. The (electro-)chemical oxidation and reduction afforded the dications [Fc2E]2+ (E = P (unstable), As) and the neutral dipnictogens Fc2EEFc2 (E = P, As).

Synergistic Cationic Shielding and Anionic Chemistry of Potassium Hydrogen Phthalate for Ultrastable Zn─I2 Full Batteries.

Electrolyte additives are investigated to resolve dendrite growth, hydrogen evolution reaction, and corrosion of Zn metal. In particular, the electrostatic shielding cationic strategy is considered an effective method to regulate deposition morphology. However, it is very difficult for such a simple cationic modification to avoid competitive hydrogen evolution reactions, corrosion, and interfacial pH fluctuations. Herein, multifunctional additives of potassium hydrogen phthalate (KHP) based on the synergistic design of cationic shielding and anionic chemistry for ultrastable Zn||I2 full batteries are demonstrated. K cations, acting as electrostatic shielding cations, constructed the smooth deposition morphology. HP anions can enter the first solvation shell of Zn2+ for the reduced activities of H2O, while they remain in the primary solvation shell and are finally involved in the formation of SEI, thus accelerating the charge transfer kinetics. Furthermore, by in situ monitoring the near-surface pH of the Zn electrode, the KHP additives can effectively inhibit the accumulation of OH- and the formation of by-products. Consequently, the symmetric cells achieve a high stripping-plating reversibility of over 4500 and 2600 h at 1.0 and 5 mA cm-2, respectively. The Zn||I2 full cells deliver an ultralong term stability of over 1400 cycles with a high-capacity retention of 78.5%.

Guest Cation Functionalized Metal Organic Framework for Highly Efficient C2H2/CO2 Separation.

The removal of carbon dioxide (CO2) from acetylene (C2H2) production is critical yet difficult due to their similar physicochemical properties. Despite extensive research has been conducted on metal-organic frameworks (MOFs) for C2H2/CO2 separation, approaches to designing functionalized MOFs remain limited. Enhancing gas adsorption through simple pore modification holds great promise in molecular recognition and industrial separation processes. This study proposes a guest cation functionalization strategy using the anionic framework SU-102 as the prototype material. Specifically, the guest cation Li+ is introduced into the skeleton by ion exchange to obtain SU-102-Li+. This strategy generates strong interactions between Li+ and gas molecules, thereby elevating C2H2 uptake to 49.18 cm3 g-1 and CO2 uptake to 29.88 cm3 g-1, marking 20.3% and 36.9% improvements over the parent material, respectively. In addition, ideal adsorbed solution theory selectivity calculations and dynamic breakthrough experiments confirmed the superior and stable separation performance of SU-102-Li+ for C2H2/CO2 (25 min g-1) and C2H2 productivity (1.55 mmol g-1). Theoretical calculations further reveals the unique molecular recognition mechanism between gas molecules and guest cations.

Novel Br-doped Bi2WO6 photocatalyst for high-efficiency removal of norfloxacin: mechanism and photocatalytic activity.

In this work, the bismuth tungstate (Bi2WO6) photocatalyst was successfully prepared, and the pure Bi2WO6 was modified with Br (Br-Bi2WO6). The effects of different experimental conditions on the degradation of norfloxacin (NOR) solution under visible light were investigated. The Br-Bi2WO6 photocatalyst was characterized by FTIR, XRD, SEM, BET, XPS, DRS, EIS, and EPR. The results show that the Br-modified Bi2WO6 photocatalyst can effectively improve the photocatalytic performance. The best photocatalytic performance of Br-Bi2WO6 was observed when the doping amount of Br was 3%. The degradation percentage of norfloxacin can reach 94.67%. The presence of anions and cations (Cl-, SO42-, Ag+, and Cu2+) in the solution significantly inhibited the photocatalytic activity of 3%Br-Bi2WO6. The photocatalytic degradation of norfloxacin by 3%Br-Bi2WO6 was not greatly affected in the presence of HCO3- and NO3-. The characterization analysis showed that Br was successfully doped on the Bi2WO6 photocatalyst, and the original structure of Bi2WO6 was not destroyed by the addition of Br. Br doping increased the specific surface area of Bi2WO6 and decreased the band gap of Bi2WO6 resulting in a broader visible light absorption range. In addition, Br doping promoted the migration rate of photogenerated electron-hole pairs. The ·O2- and h+ played a major role in the photodegradation of norfloxacin, and the mechanism of photocatalytic degradation of norfloxacin by Br-Bi2WO6 was proposed.

Colorimetric and Fluorimetric Detection of Fe(III) Using a Rhodamine-Imidazole Hydrazone Based Chemosensor: Photophysical Properties, DFT, TGA, and DSC Studies.

Rhodamine-imidazole hydrazones (RIH-1 & RIH-2) based chemosensors have been synthesized. These are characterised and evaluated by FT-IR spectroscopy, 1H-NMR, 13C-NMR, LCMS, absorption and fluorescence spectroscopy. These chemosensors exhibit enhanced sensitivity and selectivity in detecting the biologically significant Fe3+ metal ion through both colorimetric and fluorescence changes. The optical properties have been investigated using binary acetonitrile-water (7:3 v/v) semi-aqueous solution. The probe RIH-1 can be deployed as a fluorescent and colorimetric probe for the detection of Fe3+ ion. It shows an absorption band at 559 nm and an intensity band at 579 nm increasing up to 50-fold with the increase in the concentration of Fe3+ with the detection limit as low as 11nM. In the visible light, RIH-1 helps in the detection of Fe3+ ion through the naked eye, while the addition of Fe3+ to the probe RIH-1 results in a colour change from colourless to pink. This is primarily due to the opening of the lactone ring in RIH-1. Notably, RIH-1 probe displays a high quantum yield of 0.51, after binding with Fe3+ ions. Indeed, it has been found that sensor RIH-1 is very effective in sensing Fe3+ ions through both fluorescence based and visual detection methods. Additionally, DFT studies of these chemosensors have been evaluated, TGA and DSC analysis showed good thermal stability.

Gelation of gellan induced by trivalent cations and coexisting trivalent with monovalent cations studied by rheological and DSC measurements.

The effect of trivalent cation Fe3+ on the gelation process of a sodium salt form of gellan (DG, deacylated gellan gum) was investigated by rheology and DSC studies. On addition of a fairly low concentration of Fe3+ (1 mM), both the complex modulus (G*) of a 1.0 % DG solution in gel state and the sol-gel transition temperature (Tgel) slightly decreased. At higher Fe3+ concentrations (2 and 3 mM), however, a slight increase in the G* and Tgel was observed. In the coexisting monovalent cation (K+) solutions, addition of Fe3+ always improved the G* in gel state and the Tgel in a concentration-dependent manner. Moreover, for all Fe3+ DG solutions, the ordered structure formation temperature (Torder) was always lower than Tgel and increased with increasing Fe3+ concentration. This finding indicates that the network formation in the DG solutions should occur in advance of the ordered structure formation of the DG chains and that the presence of Fe3+ unfavorably affected the conformational transition of DG. In coexisting cation solution, the presence of K+ ion made a favorable contribution to the binding of Fe3+ to the disordered DG chains and to the subsequent ordered structure formation of the DG chains.