Indirect Determination of Ascorbic Acid with Ammonium Sulfate and Isopropyl Alcohol by Extraction-flotation of Copper

A new method of indirect determination of ascorbic acid(Vc) with ammonium sulfateand isopropyl alcohol by extraction-flotation of copper is studied in this paper. It shows that asmall amount of Cu( II ) can be reduced to Cu( I ) by Vc, then Cu( I ) reacted with the SCN-,which precipitated on the interface of isopropyl alcohol and H2O. A good linear relationshin is observed between the flotation yield(E) of Cu( II ) and the amount of Vc. The detection limi(forVc is 1.76 μg/mL. The method is simple, rapid (5 rain), but suffers from little interference of common anions and cations. It has been successfully applied for the determination of Vc in fruits.     

Gold Nanoparticle-based Colorimetric Assay for Determination of Lead(Ⅱ) in Aqueous Media

The authors presented a simple colorimetric assay for the detection of toxic heavy metal lead(Ⅱ) ion(Pb2+).Pentapeptide,cysteine-alanine-leacine-asparagine-asparagine(CALNN),functionalized gold nanoparticles(GNPs) were aggregated in the presence of the divalent metal ion in solution by an ion-templated chelation process,which caused an easily measurable change in the absorption spectrum of the particles.Typically,mono-dispersing GNPs exhibit an absorption band at 522 nm,corresponding to a red color solution,while aggregated GNPs have it at longer wavelengths,corresponding to a purple or blue color solution.The chelation/aggregation process is reversible via the addition of a strong metal ion chelator such as EDTA.Highly selective and sensitive detection of Pb2+ in aqueous solution is thus provided.A detection limit of 0.1 μmol/L of Pb2+ was demonstrated.     

Effect of Solvents on Oxidation of 1, 1′-Bi-2-naphthol

A novel biomimetic catalyst of complex Cu (p-OTs)2/ethanolamine (1 : 1 ) was used to oxidize 1, 1′-bi-2naphthol into xanthene derivatives with a relative high yield in a mixed solvents of dimethyl sulfoxide (DMSO) and CH3OH. The studies on the effect of some solvents on the yield of xanthene derivatives indicates that the yield reduces dramatically with the increase of the content of H2O in the mixed solvents of H2O and DMSO. No product can be obtained when the content of H2O is up to 70%. The cyclic voltammetric study demonstrated that the copper ion in complex Cu(p-OTs)2/ethanolamine(1:1) is reduced via a twostep one-electron reduction process from Cu (Ⅱ) to Cu in the mixture of DMSO and H2O. Water as a poor solvent in respect to the reactants probably hampered the coordination of 1, 1′-bi-2-naphthol to copper/amine complex and led to the insufficient catalytic efficiency of complex Cu(p-OTs),/ethanolamine(1:1).     

Studies of Ce（Ⅲ）-ALC-F^- Interacting with Herring Sperm DNA by Electrochemical,Fluorimetric and UV-spectrophotometric Method

Ce(Ⅲ)-ALC-F^- complex can react with hsDNA to form an electrochemically non-active supermolecular complex Ce(Ⅲ)-ALC-F^--DNA in the buffer solution of (CH2)6N4(pH=4.9),which results in the decrease of the peak current of Ce(Ⅲ)-ALC-F^-.This method can be applied to determine DNA concentration.In addition,by using fluorimetric and UV-spectrophotometric methods with studies of denatured DNA and the effect of NaC1 solution,it is also found that the binding mode is intercalation.     

Colorimetric detection of D-amino acids based on anti-aggregation of gold nanoparticles

A new method has been proposed to realize the visual detection of D-amino acids(DAAs) via the antiaggregation of 4-mercaptobenzoic acid modified gold nanoparticles(AuNPs) in the presence of D-amino acid oxidase(DAAO). The negatively charged AuNPs were prepared using sodium citrate as a reducer and stabilizer. The presence of 4-mercaptobenzoic acid(4-MBA) and Cu2+induces the aggregation of AuNPs,resulting in a color change from ruby red to royal purple. However, DAAO could oxidize DAAs to generate H2O2. In the presence of H2O2, the mercapto(–SH) group in 4-mercaptobenzoic acid can be oxidized to form a disulfide(–S–S–) bond. Based on these facts, the pre-incubation of DAAs and 4-mercaptobenzoic acid with DAAO would significantly reduce the concentration of free 4-mercaptobenzoic acid molecules,thus the aggregation of AuNPs was interrupted since due to the lack of inducer. As the concentration of DAAs increases, the color of the AuNPs solution would progress from royal purple to ruby red.Consequently, DAAs could be monitored by the colorimetric response of AuNPs using a UV–vis spectrophotometer or even naked eyes. This DAAO mediated visual detection method could determine Dalanine(D-Ala) as a representative DAA with concentrations ranging from 1.5×10~(-7)mol L~(-1) to 3.0×10~(-5)mol L~(-1), and the detection limit was as low as 7.5×10~(-8)mol L~(-1). The proposed method is convenient, low-cost and free of complex equipment, making it feasible to analyze the concentration of D-Ala in real samples of b-amyloid peptide(Aβ1–42).     

Construction of J-and H-Aggregates of meso-Tetrakis （4-hydroxyphenyl） porphyrin Diacid （H4THPP^2＋）

UV-Vis spectrum was utilized to study the aggregation behaviors of H4THPP^2 in DMF-chloroform mixture and water. It was found that J-aggregation of H4THPP^2 was formed in DMF-chloroform mixture and H-aggregate was formed in aqueous solution with high ionic-strength, as indicated by different spectral characteristics of different H4THPP^2 aggregates.     

Synthesis, Crystal Structure, UV-vis and EPR Studies of（ NH3CH2CH2NH2 ） 2.5 [ Mo0.5^（V）W0.5^（VI）O2 （ OC6H4O ） 2]

Cis-dioxo-metal complex ( NH3CH2CH2NH2 ) 2.5 [ Mo0.5^(V)W0.5^(VI)O2 ( OC6H4O ) 2] 1 was obtained by the reaction of tetra-butyl ammonium hexamolybdotungstate with 1, 2-dihydroxybenzene in the mixed solvent of CH3OH, CH3CN and ethylenediamine,and characterized by X-ray diffraction, UV-vis and EPR analysis. Compared with its analogous complexes (NH3CH2CH2NH2)3[Mo^(V)O2(OC6H40)2] 2 and (NH3CH2CH2NH2)2[W^(VI)O2(OC6H4O)2] 3, the results show that tungsten(VI) is less active in redox than molybdenum (VI) and that the change of the valence induced by substitution of W(VI) for Mo(V) in EMO2(OC6H40)2]n- does not influence the coordination geometry of the complex anion in which the metal center exhibits distorted octahedral coordination with cis-dioxo catechol. The responses to EPR of complexes 1 and 2 are active but complex 3 is silent,and the UV-vis spectra exhibited by the three complexes are obvious different because of the different electronic configuration between the central Mo(V) and W(VI) ions in the complexes.It is noteworthy that complexes 1 and 2 have the similar EPR signal to flavoenzyme, suggesting that the three complexes have the same coordination geometry feature with the co-factor of flavoenzyme.     

Synthesis,Crystal Structure of Cis—dioxo—catecholatotungsten（VI） Complex and Its NMR Studies on the Interaction with ATP

Cis-dioxo-catecholatotungsten(VI) complex anion[W^(VI)O2-(OC6H4O)2]^2- was obtained with discrete protonated ethylenediamine (NH2CH2CH2NH3)^ cations by the reaction of tetrabutyl ammonium decatungstate with catechol in the mixed solvent of CH3OH,CH3CN and ethylenediamine,and compared with its molybdenum anaogue [Mo^(V) O2(OC6H4O)2]^3- by crystal structure,UV,EPR,The results of the UV and EPR spectra show that tungsten is less redox active than molybdenum since the molybdenum is reduced from Mo(VI) to Mo(V) but tungsten stays in the original highest oxidized state Mo(VI) when they are crystallized from the solution above.It is worthy to note that [W^(VI)O2(OC6H4O)]^2- shows the same coordination structure as its molybdenum analogue in which the metal center exhibits distorted octahedral coordination geometry with two cis-dioxocatecholate ligands and might have the related coordination structure feature with the cofactor of flavoenzyme because [Mo^(V)O2(OC6H4O)2]^3- presented essentially the same EPR spectra as flavoenzyme.The NMR studies on the interaction of the title complex with ATP reveal that the reduction of W(VI) to W(V) occurs when the title complex is dissolved in D2O and the W(V) is oxidized again when ATP solution is mixed with original solution and the hydrolysis of the catecholato ligand take places at mean time being monitored by ^1H NMR and ^13C NMR spectra.     

Monitoring the Aggregation of Dansyl Chloride in Acetone through Fluorescence Measurements

The aggregation of dansyl chloride (DNS-Cl) in acetone has been studied in detail by steady-state fluorescence techniques.It has been demonstrated that DNS-Cl is stable in acetone during purification and aggregation study processes.The aggregates are not solvolyzed in acetone,and do not take part n any chemical reactions either.It has been found that DNS-Cl tends to aggregate even when its concentration is much lower than its solubility in acetone.The aggregation is reversible,and both the aggregation and the deaggregation are very slow processes.Introduction of SDS has a positive effect upon the formation and stabilization of the aggregates.     

RETENTION RULE IN THE LIQUID CHROMATOGRAPHY——SELECTION OF THE OPTIMUM ELUTION COMPOSITION OF SOME PTH AMINO ACIDS ON SILICA GEL

The minimal relative retention α' and the required relative retention α'_(min) of the pair of substances being most difficult to separate in a multicomponent mixture have been discussed on the basis of the fundametal retention equation ln k'=b_0 b_1C_B b_2ln C_B and resolution criterion. The selection principle to optimize elution composition means that selected a value must be greater than α'_(min) and that the capacity factor of last peak should be held to a minimum. A rapid method to select optimum elution composition has been established in which it is necessary to do a few experiments. An example for the 5 pairs of phenylthiohydantion amino acids (PTH-AA) using the ternary mobile phase of methanol, ether and hexane is also demonstrated in this paper. The results show that theoretical prediction is good in agreement with the experiments.     

The Concentration of Hydrogen Peroxide Generated during Aggregation of a-Synuclein in vitro Is Lower than 5 nmol/L

Introduction a-Syn is a major component of Lewy bodies and Lewy neurites in the brains of patients with neurode-generative diseases, such as Parkinson抯 disease, the Lewy body variant of Alzheimer抯 disease, dementia with Lewy bodies and multiple system atrophy.1,2 a-Syn is prone to aggregate in vitro and the aggregates appear to be toxic to neurons, though the reason for the cyto-toxicity remains unclear.3-6 Previous studies by electron spin resonance (ESR) showed that a-Syn could liberat…     

Conformational analysis of the disaccharide methyl α‐d‐mannopyranosyl‐(1→3)‐2‐O‐acetyl‐β‐d‐mannopyranoside monohydrate

The crystal structure of methyl α‐d ‐mannopyranosyl‐(1→3)‐2‐O‐acetyl‐β‐d ‐mannopyranoside monohydrate, C₁₅H₂₆O₁₂·H₂O, ( II ), has been determined and the structural parameters for its constituent α‐d ‐mannopyranosyl residue compared with those for methyl α‐d ‐mannopyranoside. Mono‐O‐acetylation appears to promote the crystallization of ( II ), inferred from the difficulty in crystallizing methyl α‐d ‐mannopyranosyl‐(1→3)‐β‐d ‐mannopyranoside despite repeated attempts. The conformational properties of the O‐acetyl side chain in ( II ) are similar to those observed in recent studies of peracetylated mannose‐containing oligosaccharides, having a preferred geometry in which the C2—H2 bond eclipses the C=O bond of the acetyl group. The C2—O2 bond in ( II ) elongates by ～0.02 Å upon O‐acetylation. The phi (?) and psi (ψ) torsion angles that dictate the conformation of the internal O‐glycosidic linkage in ( II ) are similar to those determined recently in aqueous solution by NMR spectroscopy for unacetylated ( II ) using the statistical program MA′AT, with a greater disparity found for ψ (Δ = ～16°) than for ? (Δ = ～6°).     

From α‐carbamoyl‐α‐cyano­oxiranes to 3‐halogenopyruv­amides

The crystal structures of the first stable α‐diol from the α‐halogenopyruv­amide series, 3‐chloro‐2,2‐di­hydroxy‐3‐phenyl­propan­amide, C₉H₁₀­ClNO₃, and three products [3‐(4‐chloro­phenyl)‐2‐cyano‐2,3‐epoxy­propan­amide, C₁₀H₇­ClN₂O₂, 3‐bromo‐2‐cyano‐2‐hydroxy‐3‐p‐tolyl­propan­amide, C₁₁H₁₁Br­N₂O₂, 3‐bromo‐2‐oxo‐3‐p‐tolyl­propan­amide, C₁₀H₁₀­BrNO₂] obtained during the systematic synthesis of α‐halogenopyruv­amides are reported. The crystal structures are dominated by hydrogen bonds involving an amide group. The stability of the geminal diol could be ascribed to hydrogen bonds which involve both hydroxyl groups.     

Quantitative Aspects of Electrochemical Detection of Amyloid‐β Aggregation

The tyrosine based electrochemical analysis of synthetic amyloid‐β (Aβ) peptide – an analog of natural peptide implicated in Alzheimer's disease pathogenesis – was applied for a quantitative estimation of peptide aggregation in vitro. The analysis was carried out by square wave voltammetry (SWV) on carbon screen printed electrodes (SPE). The electrooxidation peak current (I_p) for Aβ42 peptide in different aggregation states was directly compared with the size and structure of Aβ42 aggregates occurring in the analyzed sample. Dynamic light scattering (DLS) and thioflavin T (ThT) based fluorescence assay were employed to estimate the size and structure of Aβ42 aggregates. The I_p was found to decrease in a linear fashion when the average diameter of aggregates and the relative ThT fluorescence in Aβ42 solutions exceeded 35 nm and 3, respectively, while being nearly constant below these values. It was suggested that the electrooxidation current is mostly generated by peptide monomers and that a depletion of the monomer pool due to inclusion of Aβ42 molecules in aggregates is responsible for the decrease of electrooxidation current. The direct electrochemistry is emerging as a method complementary to methods based on aggregates’ detection and commonly employed for monitoring Aβ aggregation. The work further enlarges the basis for application of the cost‐effective and rapid electrochemical techniques, such as SWV on carbon SPE, to in vitro studies of Aβ aggregation.     

A 3,7‐Dihydroxyphenoxazine‐based Fluorescent Probe for Selective Detection of Intracellular Hydrogen Peroxide

A novel N‐borylbenzyloxycarbonyl‐3,7‐dihydroxyphenoxazine fluorescent probe (NBCD) for detecting H₂O₂ in living cells is described. The probe could achieve high selectivity for detecting H₂O₂ over other biological reactive oxygen species (ROS). In addition, upon addition of H₂O₂, NBCD exhibited color change from colorless to pink, which makes it a “naked‐eye” probe for H₂O₂ detection. NBCD could not only be used to detect enzymatically generated H₂O₂ but also to detect H₂O₂ in living systems by using fluorescence spectroscopy, with a detection limit of 2 μm . Importantly, NBCD enabled the visualization of epidermal growth factor (EGF)‐stimulated H₂O₂ generation inside the cells.     

Dual Mechanism of an Intramolecular Charge Transfer (ICT)–FRET‐Based Fluorescent Probe for the Selective Detection of Hydrogen Peroxide

A dual‐mechanism intramolecular charge transfer (ICT)–FRET fluorescent probe for the selective detection of H₂O₂ in living cells has been designed and synthesized. This probe used a coumarin–naphthalimide hybrid as the FRET platform and a boronate moiety as the recognition group. Upon the addition of H₂O₂, the probe exhibited a redshifted (73 nm) fluorescence emission, and the ratio of fluorescence intensities at λ =558 and 485 nm (F ₅₅₈/F ₄₈₅) shifted notably (up to 100‐fold). Moreover, there was a good linearity (R ²=0.9911) between the ratio and concentration of H₂O₂ in the range of 0 to 60 μm , with a limit of detection of 0.28 μm (signal to noise ratio (S/N)=3). This probe could also detect enzymatically generated H₂O₂. Importantly, it could be used to visualize endogenous H₂O₂ produced by stimulation from epidermal growth factor.     

Label‐Free,Non‐Derivatization CRET Detection Platform for 6‐Mercaptopurine Based on the Distance‐Dependent Optical Properties of Gold Nanoparticles

A label‐free, non‐derivatization chemiluminescence resonance energy transfer (CRET) detection platform has been developed for the detection of the non‐fluorescent small molecule 6‐mercaptopurine. This CRET process arose from a chemiluminescent (CL) donor–acceptor system in which the reaction of bis(2,4,6‐trichlorophenyl)oxalate (TCPO)–H₂O₂–fluorescein (maximum emission at 521.6 nm) served as the donor and gold nanoparticles (AuNPs, maximum absorption at 520.0 nm) served as the acceptor. This process caused a significant decrease in the CL signal of the TCPO–H₂O₂–fluorescein reaction. The presence of 6‐mercaptopurine induced an aggregation of AuNPs with the assistance of Cu²⁺ ions through cooperative metal–ligand interactions that was accompanied by a distinct change in color and optical properties. The maximum absorption band of the AuNPs was red‐shifted to 721.0 nm and no longer overlapped with the CL spectrum of the reaction; as a result, the CL signal was restored. This CRET system exhibited a wide linear range, from 9.0 nmol L^?1 to 18.0 μmol L^?1, and a low detection limit (0.62 nmol L^?1) for 6‐mercaptopurine. The applicability of the proposed CRET system was evaluated by analysis of 6‐mercaptopurine in spiked human plasma samples.     

Inhibition of α‐Synuclein Amyloid Fibril Elongation by Blocking Fibril Ends

Misfolding of the protein α‐synuclein (αSyn) into amyloid fibrils plays a central role in the development of Parkinson's disease. Most approaches for the inhibition of αSyn fibril formation are based on stabilizing the native monomeric form of the protein or destabilizing the fibrillized misfolded form. They require high concentrations of inhibitor and therefore cannot be easily used for therapies. In this work, we designed an inhibitor (Inh‐β) that selectively binds the growing ends of αSyn fibrils and creates steric hindrance for the binding of monomeric αSyn. This approach permits the inhibition of fibril formation at Inh‐β concentrations (IC₅₀=850 nm ) much lower than the concentration of monomeric αSyn. We studied its kinetic mechanism in vitro and identified the reactions that limit inhibition efficiency. It is shown that blocking of αSyn fibril ends is an effective approach to inhibiting fibril growth and provides insights for the development of effective inhibitors of αSyn aggregation.     

α‐Fe2O3 Film with Highly Photoactivity for Non‐enzymatic Photoelectrochemical Detection of Glucose

A non‐enzyme photoelectrochemical (PEC) glucose sensor based on α‐Fe₂O₃ film is investigated. The α‐Fe₂O₃ film was fabricated via a simple spin coating method. The proposed glucose sensor exhibits good selectivity, a fast response time of <5 s, a linear range of 0.05 to 6.0 mM, sensitivity of 17.23 μA mM^?1 cm^?2 and a detection limit of 0.05 μM. Meanwhile, the excellent performances of the α‐Fe₂O₃ sensor were obtained in reproducibility and the long‐term stability under ambient condition. The linear amperometric response of the sensor covers the glucose levels in physiological and clinical for diabetic patients. Therefore, this non‐enzyme PEC sensor based on α‐Fe₂O₃ film has a great potential application in the development of glucose sensors.     

The Electrochemical Behavior of α‐Ketoglutarate at the Hanging Mercury Drop Electrode in Acidic Aqueous Solution and Its Practical Application in Environmental and Biological Samples

The voltammetric behavior of α‐ketoglutarate (α‐KG) at the hanging mercury drop electrode (HMDE) has been investigated in acetate buffer solution. Under the optimum experimental conditions (pH 4.5, 0.2 M NaAc‐HAc buffer solution), a sensitive reductive wave of α‐KG was obtained by linear scan voltammetry (LSV) and the peak potential was ?1.18 V (vs. SCE), which was an irreversible adsorption wave. The kinetic parameters of the electrode process were α=0.3 and k_s=0.72 1/s. There was a linear relationship between peak current i_{p, α‐KG} and α‐KG concentration in the range of 2×10^?6–8×10^?4 M α‐KG. The detection limit was 8×10^?7 M and the relative standard deviation was 2.0% (C_α‐KG=8×10^?4 M, n=10). Applications of the reductive wave of α‐KG for practical analysis were addressed as follows: (1) It can be used for the quantitative analysis of α‐KG in biological samples and the results agree well with those obtained from the established ultraviolet spectrophotometric method. (2) Utilizing the complexing effect between α‐KG and aluminum, a linear relationship holds between the decrease of peak current of α‐KG Δi_p and the added Al concentration Cequation/tex2gif-inf-5.gif in the range of 5.0×10^?6–2.5×10^?4 M. The detection limit was 2.2×10^?6 M and the relative standard deviation was 3.1% (Cequation/tex2gif-inf-6.gif=4×10^?5 M, n=10). It was successfully applied to the detection of aluminum in water and synthetic biological samples with satisfactory results, which were consistent with those of ICP‐AES. (3) It was also applied to study the effect of Al^III on the glutamate dehydrogenase (GDH) activity in the catalytically reaction of α‐KG+NH +NADH?L ‐glutamate+NAD⁺+H₂O by differential pulse polarography (DPP) technique. By monitoring DPP reductive currents of NAD⁺ and α‐KG, an elementary important result was found that Al could greatly affect the activity of GDH. This study could be attributed to intrinsic understanding of the aluminum's toxicity in enzyme reaction processes.