Oxidation State Research Articles

A Triply Linked Copper(III) Dicarbacorrole Dimer.

A triply linked dicarbacorrole dimer (7) was synthesized from a new meso-meso singly linked dicarbacorrole dimer precursor (6) via an oxidative fusion reaction by 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) in the presence of trifluoromethanesulfonic acid (TfOH). Single crystal X-ray structure of 7 adopts a flat conformation with a length as ca. 15.946 Å and a width as 6.903 Å, which can be regarded as a short carbaporphyrinoid tape. Two coordinated Cu ions keeps the +3 oxidation state in 7, as confirmed by NMR spectroscopy, single crystal X-ray diffraction and X-ray photoelectron spectroscopy (XPS). This is in sharp contrast to the Osuka's triply linked tetrapyrrolic corrole dimers, where the inner 3NH form is not stable and thus can only act as a divalent ligand. Due to the non-aromatic nature of dicarbacorrole macrocycle, the largely decreased HOMO-LUMO gap and red-shifted absorption of 7 are best ascribed to the strong electronic interaction between two dipyrromethene-type chromophores. To our knowledge, this is the first fully fused carbaporphyrinoid dimer with β-β, meso-meso, β-β triply linkages prepared to date.

Unveiling Dynamic Structure and Bond Evolutions in BiOIO3 Photocatalysts during CO2 Reduction.

We have established a correlation between photocatalytic activity and dynamic structure/bond evolutions of BiOIO3-based photocatalysts during CO2 reduction by combining operando X-ray diffraction with photoelectron spectroscopy. More specifically, the selective photo-deposition of PtOx species on BiOIO3 (010) facets could effectively promote the electron enrichment on Bi active sites of (100) facets for facilitating the adsorption/activation of CO2 molecules, leading to the formation of Bi sites with high oxidation state and the shrink of crystalline structures. With introducing light irradiation to drive CO2 reduction, the Bi active sites with high oxidation states transformed into normal Bi3+ state, accompanying with the expansion of crystalline structures. Owing to the dynamic structure, bond, and chemical-state evolutions, a significant improvement of photocatalytic activity for CO evolution has been achieved on PtOx-BiOIO3 (195.0 μmol g-1 ⋅ h-1), much higher than the pristine (61.9 μmol g-1 ⋅ h-1) as well as metal-Pt decorated BiOIO3 (70.3 μmol g-1 ⋅ h-1) samples. This work provides new insights to correlate the intrinsically dynamic structure/bond evolutions with CO2 reduction activity, which may help to guide future photocatalyst design.

Essential oil mediated synthesis and application of highly stable copper nanoparticles as coatings on textiles and surfaces for rapid and sustained disinfection of microorganisms

Rampant pathogenesis induced by communicable microbes has necessitated development of technologies for rapid and sustained disinfection of surfaces. Copper nanoparticles (CuNPs) have been widely reported for their antimicrobial properties. However, nanostructured copper is prone to oxidative dissolution in the oil phase limiting its sustained use on surfaces and coatings. The current study reports a systematic investigation of a simple synthesis protocol using fatty acid stabilizers (particularly essential oils) for synthesis of copper nanoparticles in the oil phase. Of the various formulations synthesized, rosemary oil stabilized copper nanoparticles (RMO CuNPs) were noted to have the best inactivation kinetics and were also most stable. Upon morphological characterization by TEM and EELS, these were found to be monodispersed (φ 5–8 nm) with copper coexisting in all three oxidation states on the surface of the nanoparticles. The nanoparticles were drop cast on woven fabric of around 500 threads per inch and exposed to gram positive bacteria (Staphylococcus aureus), gram negative bacteria (Escherichia coli and Pseudomonas aeruginosa), enveloped RNA virus (phi6), non-enveloped RNA virus (MS2) and non-enveloped DNA virus (T4) to encompass the commonly encountered groups of pathogens. It was possible to completely disinfect 107 copies of all microorganisms within 40 min of exposure. Further, this formulation was incorporated with polyurethane as thinners and used to coat non-woven fabrics. These also exhibited antimicrobial properties. Sustained disinfection with less than 9% cumulative copper loss for upto 14 washes with soap water was observed while the antioxidant activity was also preserved. Based on the studies conducted, RMO CuNP in oil phase was found to have excellent potential of integration on surface coatings, paints and polymers for rapid and sustained disinfection of microbes on surfaces.

Understanding Ligand Effects on Bielectronic Transitions: Chemo- and Electroreduction of Rhodium Bis(Diphosphine) Complexes to Low Oxidation States.

Rhodium complexes in the -I and 0 oxidation states are of great potential interest in catalytic applications. In contrast to their rhodium +I congeners, however, the structural and electronic parameters governing their access and stability are far less understood. Herein, we investigate the two-electron reduction of a parameterized series of bis(diphosphine) Rh complexes [Rh(dxpy)2]NTf2 (x = P-substituent, y = alkanediyl bridging P atoms). Through (electro)reductions from the RhI parents, Rh-Id10-complexes were obtained and characterized spectroscopically, including 103Rh NMR data. The reductive steps convolute with structural rearrangements from square planar to tetrahedral coordination. We found that the extent of these reorganisations defines whether the first E0(RhI/0) and second E0(Rh0/-I) reduction potentials are normally ordered, leading to monoelectronic stepwise events, or inverted, giving bielectronic transitions. Reductionist approaches based on Hammett parameters or the P-Rh-P bite angles provide only partial correlations with the redox potentials. However, we identified the C-O stretch of analogue diphosphine complexes as an expedient computational parameter that enables these correlations through both electronic and geometric features, even in a predictive manner. Gaining control over two-electron reduction behaviors through rationalized ligand effects has potential impact beyond Rh complexes, for molecular and enzymatic metal sites commonly exhibiting bielectronic transitions.

Alternatively Connected Corrole‐Porphyrin Multimetallic Complexes: Synthesis, Structure, and Properties

AbstractSynthetic multimetallic porphyrinoids are potential candidates in catalysis, molecular magnetism and as modern optoelectronic materials. Introducing electronic heterogenity in these multi‐porphyrinoids shall bring in novel electronic and redox characteristics. In this direction, herein we report four discrete Corrole‐Porphyrin‐Corrole C[10] ⋅ P[5,15] ⋅ C[10] hybrids that have both corrole and porphyrin units covalently connected together. Metal ions in diverse oxidation states have been incorporated into respective cores to achieve homo and heterotrinuclear metal complexes. Selective metalation at the porphyrin and corrole cores was achieved by step‐wise insertion of Zn(II)/Cu(II), Zn(II)/Ga(III) and Cu(II)/Cu(II) ions to suit the dianionic and trianionic pockets, respectively. Single crystal X‐ray diffraction studies reveal the solid‐state structural evidence for both homo‐, and hetero‐trinuclear metal complexes. The Zn(II) and Ga(III) moieties have two distinct geometries in the molecular assembly. The geometry of Zn(II) at the porphyrin core is a perfect square planar, whereas the Ga(III) geometry at the corrole is square pyramidal with pyridine as an axial ligand. In case of homotrinuclear Cu(II) complex, the Cu(II) ions adopt square planar geometry irrespective of the core. Similar to all porphyrin trimers, C[10] ⋅ P[5,15] ⋅ C[10] trimers exhibit significant excitonic coupling between corrole and porphyrin units in the absorption spectra. The cyclic voltametric investigations also reveal electronic coupling between the individual chromophores despite the non‐coplanar arrangement amongst the individual macrocycles.

Intramolecular Disulfide Bridges in Voltage-Dependent Anion Channel 2 (VDAC2) Protein from Rattus norvegicus Revealed by High-Resolution Mass Spectrometry.

Voltage-Dependent Anion Channel isoforms (VDAC1, VDAC2, and VDAC3) are relevant components of the outer mitochondrial membrane (OMM) and play a crucial role in regulation of metabolism and in survival pathways. As major players in the regulation of cellular metabolism and apoptosis, VDACs can be considered at the crossroads between two broad families of pathologies, namely, cancer and neurodegeneration, the former being associated with elevated glycolytic rate and suppression of apoptosis in cancer cells, the latter characterized by mitochondrial dysfunction and increased cell death. Recently, we reported the characterization of the oxidation pattern of methionine and cysteines in rat and human VDACs showing that each cysteine in these proteins is present with a preferred oxidation state, ranging from the reduced to the trioxidized form, and such an oxidation state is remarkably conserved between rat and human VDACs. However, the presence and localization of disulfide bonds in VDACs, a key point for their structural characterization, have so far remained undetermined. Herein we have investigated by nanoUHPLC/High-Resolution nanoESI-MS/MS the position of intramolecular disulfide bonds in rat VDAC2 (rVDAC2), a protein that contains 11 cysteines. To this purpose, extraction, purification, and enzymatic digestions were carried out at slightly acidic or neutral pH in order to minimize disulfide bond interchange. The presence of six disulfide bridges was unequivocally determined, including a disulfide bridge linking the two adjacent cysteines 4 and 5, a disulfide bridge linking cysteines 9 and 14, and the alternative disulfide bridges between cysteines 48, 77, and 104. A disulfide bond, which is very resistant to reduction, between cysteines 134 and 139 was also detected. In addition to the previous findings, these results significantly extend the characterization of the oxidation state of cysteines in rVDAC2 and show that it is highly complex and presents unusual features. Data are available via ProteomeXchange with the identifier PXD044041.

Leonardite humic acid activated carbon/MnO\(_{2}\) composite nanostructures for supercapacitors

Abstract This work reports the preparation and electrochemical studies of activated carbon derived from leonardite humic acid composited with MnO2 for supercapacitors. Activated carbon contains high conductivity, high specific surface area, and accommodates large volume expansion/contraction during charging/discharging process. Meanwhile, MnO2 has very high theoretical specific capacity (1370 F∙g‒1). Their composite could significantly improve both the storage performance and cycle stability of supercapacitors. Moreover, humic acid from leonardite was selected to add value to this waste and reduce environmental pollution. By varying the carbonization temperature (500℃ to 800℃), the prepared samples carbonized at 800℃ exhibited fascinating properties. The oxidation state of Mn ions was in the mixed state of Mn+2 (41.2%) and Mn+2, +3 (52.8%). A gravimetric capacitance of 329 F∙g‒1 and 294 F∙g‒1 were observed at 2 mVs-1 and 0.5 Ag-1, respectively. The remaining gravimetric capacitance of 193 F∙g‒1 was evaluated at 1000 cycles, indicating its high cycle performance. Moreover, the gravimetric energy of 37.51 Wh∙kg‒1 and gravimetric power of 272.96 W∙kg‒1 were observed. When combined, the interesting electrochemical properties of leonardite humic acid-activated carbon/MnO2 composite nanostructures make them important options for supercapacitor application.

Adaptive evolution of Clostridium thermocellum ATCC 27405 on alternate carbon sources leads to altered fermentation profiles.

Consolidated bioprocessing candidate, Clostridium thermocellum, is a cellulose hydrolysis specialist, with the ability to ferment the released sugars to produce bioethanol. C. thermocellum is generally studied with model substrates Avicel and cellobiose to understand the metabolic pathway leading to ethanol. In the present study, adaptive laboratory evolution, allowing C.thermocellum DSM 1237 to adapt to growth on glucose, fructose, and sorbitol, with the prospect that some strains will adapt their metabolism to yield more ethanol. Adaptive growth on glucose and sorbitol resulted in an approximately 1mM and 2mM increase in ethanol yield per millimolar glucose equivalent, respectively, accompanied by a shift in the production of the other expected fermentation end products. The increase in ethanol yield observed for sorbitol adapted cells was due to the carbon source being more reduced compared to cellobiose. Glucose and cellobiose have similar oxidation states thus the increase in ethanol yield is due to the rerouting of electrons from other reduced metabolic products excluding H2 which did not decrease in yield. There was no increase in ethanol yield observed for fructose adapted cells, but there was an unanticipated elimination of formate production, also observed in sorbitol adapted cells suggesting that fructose has regulatory implications on formate production either at the transcription or protein level.

Quantitative Kinetic Insights from Operando-UV-Vis Spectroscopy: An Application to NH3-SCR of NOx on Cu-CHA Catalysts.

We employ UV-Vis Diffuse Reflectance spectroscopy directly coupled with a packed bed flow reactor to extract quantitative kinetic information. We use as a show-case the CuII/CuI redox dynamics during the reduction half cycle of the NH3-Selective Catalytic Reduction (SCR) on Cu-CHA catalysts. Our measurements enable quantification of the fraction of oxidized Cu, reconstructed by Multivariate Curve Resolution (MCR) together with monitoring of the gas-phase evolution during the reaction. These data both on the dynamics of the gas-phase and of the active site oxidation state have been used to assess the reduction half cycle rate equation and estimate the rate constant. Our results in terms of reaction orders and kinetic constant are in line with previous findings in the literature. Overall, our results demonstrate that the combined analysis of the UV spectra and of the gas-phase dynamics provides converging and unparalleled kinetic insight: this approach effectively resolves ambiguities concerning RHC kinetics and mechanism. More in general, this work provides evidence that operando spectroscopy can be used to extract quantitative kinetic information on catalytic cycles.

Quantitative Kinetic Insights from Operando‐UV‐Vis Spectroscopy: An Application to NH3‐SCR of NOx on Cu‐CHA Catalysts

We employ UV‐Vis Diffuse Reflectance spectroscopy directly coupled with a packed bed flow reactor to extract quantitative kinetic information. We use as a show‐case the CuII/CuI redox dynamics during the reduction half cycle of the NH3‐Selective Catalytic Reduction (SCR) on Cu‐CHA catalysts. Our measurements enable quantification of the fraction of oxidized Cu, reconstructed by Multivariate Curve Resolution (MCR) together with monitoring of the gas‐phase evolution during the reaction. These data both on the dynamics of the gas‐phase and of the active site oxidation state have been used to assess the reduction half cycle rate equation and estimate the rate constant. Our results in terms of reaction orders and kinetic constant are in line with previous findings in the literature. Overall, our results demonstrate that the combined analysis of the UV spectra and of the gas‐phase dynamics provides converging and unparalleled kinetic insight: this approach effectively resolves ambiguities concerning RHC kinetics and mechanism. More in general, this work provides evidence that operando spectroscopy can be used to extract quantitative kinetic information on catalytic cycles.

Intrinsic flame-retardant epoxy resin based on phosphorus-containing liquid imidazole compound: Simultaneously improving fire safety, mechanical property and heat resistance

In this work, two phosphorus-containing liquid imidazole compounds with different phosphorus oxidation states (1,1′-(phenylphosphanediyl)bis(1H-imidazole) (DCPPI) with + 1 valence phosphorus, and imidazole-phenylphosphate (PPOAI) with + 3 valence phosphorus) were designed and synthesized. Both of DCPPI and PPOAI were used as curing agents to obtain intrinsic flame-retardant epoxy resin (EP-DCPPI and EP-PPOAI), in which the imidazole group was used as the curing group of EP, and the phosphorus-containing group was directly connected to the EP crosslinking network. On the one hand, the efficient flame-retardant groups containing + 1 or + 3 valence phosphorus were incorporated into the EP system to obtain excellent flame-retardant properties; on the other hand, the introduction of phenylphosphine or phenoxyphosphine groups in the molecular chain of EP greatly enhanced the interaction between molecular chains, adjusted crosslinking density and endowed EP with excellent tensile strength and toughness. Compared with imidazole cured EP (EP-MZ), the peak heat release rate (PHRR) of EP-15DCPPI and EP-15PPOAI decreased by 70 % and 68 %, and the total heat release rate (THR) decreased by 37 % and 36 %, respectively. Meanwhile, EP-15DCPPI passed UL-94 V-0 rating, and the limiting oxygen index (LOI) reached 36.1 %. EP-15PPOAI passed UL-94 V-1 rating and the LOI reached 29.1 %. The flame-retardant mechanism was analyzed and discussed. Compared with EP-MZ, the dynamic and static mechanical properties of EP-15DCPPI and EP-15PPOAI were enhanced simultaneously, and the glass transition temperature (Tg) was obviously increased.

Survey of Recent Trends of IB-IVB Metals and Their Compounds in Cancer Treatment

Metals from IB to IVB groups of the periodic table, because of their flexible oxidation states, natures of coordinated bioligands, and geometries upon complexation, display various properties and efficiency of metal-based cytotoxic drugs. Recent decades have witnessed remarkable progress in the synthesis and therapeutic application of numerous inorganic compounds in cancer investigations. The main potential therapeutic agents, such as the complexes of platinum group metals possessing antineoplastic activity have been broadly described previously in the literature and are beyond the space of this analysis. The key objective of the present study is to analyze the possible activity of IB-IVB group metals their coordination compounds against the cancer cell types. The increasing number of anticancer drug candidates among these metals proves this field offers a remarkably variation of novel opportunities for the synthesis of advanced new pharmaceutics with diverse and specific modes of action. Furthermore, the review provides forthcoming insights into prospective clinical scenarios for approaching treatment applications. That is why this field of research deserves more attention. It is expected that this review can serve as a guiding framework for future investigations in cancer chemotherapy.

Dimethylglycine and B-vitamins administration counteracts the inflammatory and oxidative state in autism spectrum disorders

Dimethylglycine and B-vitamins administration counteracts the inflammatory and oxidative state in autism spectrum disorders

The role of Cu doped Ba0.5Sr0.5Fe0.95Zr0.05O3-δ: Local structure distortion, conductivity, and magnetization

The composition Ba0.5Sr0.5Fe1-xCuxZr0.05O3-δ (BSFCZ-x, x = 0–0.20) was successfully synthesized by the sol-gel self-combustion method using citric acid as fuel combustion. Structure, local structure, electrical, and magnetic properties are investigated. The X-ray diffraction revealed the oxides exhibit a cubic structure (Pm3 m), and the lattice parameter increases with x. The X-ray absorption data are analyzed to determine the oxidation state of B site metal transition Fe and Cu through edge-energy E0 evaluation. Fe performs the oxidation states Fe3+ and Fe4+, similarly to Cu2+ and Cu3+. Furthermore, the pre-edge was analyzed to determine the spin state configuration of the 3d subshell. The local lattice distortion was evaluated through EXAFS, resulting in a distorted FeO6 octahedron elongated to the z-axis, inducing the Jahn-Teller effect. The nonstoichiometric δ-value (3-δ) measurement leads to oxygen vacancy VO⦁⦁ defect. The electrical conductivity of semiconducting behavior increases significantly after Cu is dissolved in BSFZ up to 60 S/cm at 500 °C, from initially 5 S/cm. Furthermore, the magnetic properties show a slight magnetic saturation Ms for BSFZ related to the low spin state configuration of Fe 3d subshell, then significantly increased on BSFCZ samples due to Cu provoking spin state dragged partly to high spin state configuration.

Experimental conditions for room temperature ferromagnetism in Fe-doped SnO2 via mechanochemical milling and thermal treatment

Identifying optimal experimental conditions, preferably through a simple and cost-effective method, for the fabrication of oxide-diluted magnetic semiconductors, such as Fe-doped SnO2, holds great significance in the quest for spintronic materials operating at room temperature (RT). While mechanochemical milling is a well-established technique meeting these requirements, its numerous milling variables necessitate careful consideration of restricted experimental conditions. In this study, we present some experimental mechanochemical milling conditions to prepare impurity-free iron-doped tin dioxide nanoparticles exhibiting RT ferromagnetic signal. To achieve this, we investigated the effects of milling time, the choice of the starting Sn reactant, and iron concentration on the purity of Sn1−xFexO2 (x = 0, 0.03, and 0.05) nanopowders obtained through mechanochemical milling followed by thermal treatment. Characterization through XRD, XANES, and EXAFS at the Fe K-edge, RT Raman spectroscopy, 119Sn and 57Fe Mössbauer spectroscopies, and magnetic measurements was conducted. Among the experimental techniques, micro-Raman spectroscopy proved the most effective in detecting the formation of hematite as an impurity phase. Our results indicate that extending the milling time to 12 h, as opposed to 3 h, employing anhydrous SnCl2, instead of SnCl2·2H2O and using the low iron concentration of x = 0.03, results in proper conditions for producing impurity-free samples with a robust RT ferromagnetic signal. The oxidation states for iron and tin ions were determined to be 3+ and 4+, respectively, with both occupying octahedral sites, suggesting iron’s replacement of tin. Our findings propose that both the bound magnetic polaron and RKKY models offer potential explanations for the origin of the ferromagnetic signal observed at room temperature in Sn0.97Fe0.03O2 sample milled for 12 h.

Defect Engineering in Composition and Valence Band Center of Y2(YxRu1-x)2O7-δ Pyrochlore Electrocatalysts for Oxygen Evolution Reaction.

Oxygen evolution reaction (OER) takes place in various types of electrochemical devices that are pivotal for the conversion and storage of renewable energy. This paper describes a strategy in the design of solid-state structures of OER electrocatalysts through controlling the cation substitution on the active metal site and consequently valence band center position of site-mixed Y2(YxRu1-x)2O7-δ pyrochlore to achieve high catalytic activity. We found that partially replacing the B-site Ru4+ cation with A-site Y3+ in pyrochlore-structured Y2Ru2O7-δ modifies the oxidation state of B-site Ru from 4+ to 5+, as observed by electron paramagnetic resonance (EPR) spectroscopy but does not continuously increase the oxygen vacancy concentration in these oxygen substoichiometric compositions, as quantified by thermogravimetric analysis (TGA) decomposition studies. We found the increased Ru oxidation state leads to a downshift in valence band center. X-ray photoelectron spectroscopy (XPS) analysis was performed to quantitatively determine the optimal band center to be ∼1.27 eV below the Fermi energy level based on the analysis of the valence band edge of these Ru-based Y2(YxRu1-x)2O7-δ OER electrocatalysts. This work highlights that defect engineering can be a practical, effective approach to the optimization of oxidation state and electronic band center for high OER catalytic performance in a quantitative manner.

Micrometric patterning of a borogermanate glass containing terbium by thermal poling to manage luminescence and second order optical properties

Borogermanate glasses containing terbium ions are interesting materials due to their luminescent and magnetic properties. Terbium can present two different oxidation states and the thermal poling technique can be a pertinent way to modulate spatially the oxidation state of these ions. In this work, we demonstrate using a thermo-electrical imprinting process the transfer of micro scaled motifs on the surface of a borogermanate glass containing Tb3+ resulting in a micrometric structuring of the oxidation state of Tb3+/Tb4+ ions. A large change in absorption and luminescence optical properties is observed, arising from the distinct properties of trivalent and tetravalent terbium ions. Correlative micro luminescence, Raman and second harmonic generation measurements were carried out on the patterned poled glass surface. This has demonstrated an accurate concomitant modification of the glass structure accompanying large luminescence changes and the appearance of a second order optical response which could be attributed to a localized space charge implantation. These original results demonstrate how a simple electrical process allows managing multi optical properties but also paves the way to induce static electrical functionalities in a magnetic optical glassy system.

Chemical Environment and Structural Variations in High Entropy Oxide Thin Film Probed with Electron Microscopy.

We employ analytical transmission electron microscopy (TEM) to correlate the structural and chemical environment variations within a stacked epitaxial thin film of the high entropy oxide (HEO) Mg0.2Co0.2Ni0.2Cu0.2Zn0.2O (J14), with two layers grown at different substrate temperatures (500 and 200 °C) using pulsed laser deposition (PLD). Electron diffraction and atomically resolved STEM imaging reveal the difference in out-of-plane lattice parameters in the stacked thin film, which is further quantified on a larger scale using four-dimensional STEM (4D-STEM). In the layer deposited at a lower temperature, electron energy loss spectroscopy (EELS) mapping indicates drastic changes in the oxidation states and bonding environment for Co ions, and energy-dispersive X-ray spectroscopy (EDX) mapping detects more significant cation deficiency. Ab initio density functional theory (DFT) calculations validate that vacancies on the cation sublattice of J14 result in significant electronic and structural changes. The experimental and computational analyses indicate that low temperatures during film growth result in cation deficiency, an altered chemical environment, and reduced lattice parameters while maintaining a single phase. Our results demonstrate that the complex correlation of configurational entropy, kinetics, and thermodynamics can be utilized for accessing a range of metastable configurations in HEO materials without altering cation proportions, enabling further engineering of functional properties of HEO materials.

A novel polysaccharide of Undaria pinnatifida: Structural characterization, carboxymethylation and hypoglycemic activity in vivo

A new polysaccharide (UPP) was isolated and purified from Undaria pinnatifida with a low molecular weight of 8.34 kDa. The UPP was modified to obtain carboxymethylated polysaccharide (CM-UPP). UPP and CM-UPP were characterized by FT-IR, Ion chromatography, Congo red, DSC, SEM and NMR, and their hypoglycemic activity in vivo was investigated using the STZ-induced diabetes mice model. UPP mainly contained Ara, Gal, Glc and Man at a molar ratio of 0.18: 0.13: 2.06: 1, and CM-UPP added two alduronic acids including GalA and GlcA. CM-UPP had been prepared successfully and the carboxymethylation reaction might occur partially at the C-2 and C-4 position. There were no triple helix structures in both UPP and CM-UPP. In vivo hypoglycemic activity studies showed that both UPP and CM-UPP could alleviate symptoms of high blood glucose, improve blood lipid level, oxidative stress state and liver glycolytic enzyme activity in diabetic mice. Under the same dose, CM-UPP showed a more significant effect than UPP. These results indicated that carboxymethylation was an effective way to enhance the hypoglycemic activitiy of polysaccharide. UPP and CM-UPP could be potential therapeutic agents of T2DM.

Modulating Heavy Atom Effect in Germylene for Persistent Room Temperature Phosphorescence.

It is worth but still challenging to develop the low-valent main group compounds with persistent room temperature phosphorescence (pRTP). Herein, we presented germylene-based persistent phosphors by introduction of low-valent Ge center into chromophore. A novel phosphors CzGe and its series of derivatives, namely CzGeS, CzGeSe, CzGeAu, and CzGeCu, were synthesized. Experiments and theoretical calculations reveal that the pRTP behavior were "turn on" due to the heavy atom effect of germylene. More importantly, the low-valent of oxidation state and structural traits propelled GeCz had a balance between the intersystem crossing and the shortening of lifetime caused by the heavy atoms, resulting the ultralong lifetime of 309 ms and phosphorescent quantum efficiency of 15.84 %, which is remarkable among heavy main group phosphors.This research provides valuable insights to the design of heavy atoms in phosphors and expand the applications of germylene chemistry.