Formation of the Inclusion Complex of Orange Ⅱ with β-Cyclodextrin and Its Photostability

0　IntroductionCyclodextrins (CD)arenon reducingcyclicmaltooligosaccharidesproducedfromstarchbycyclodextringlycosyltransferaseandarecom posedofahydrophilicoutersurfaceandahy drophobicinnercavity .β cyclodextrinsarecom posedofsevenD glucopyranoseunits.Theringshapedstructureandhydrophobicinnercavityal lowthemtohousevariousguestmoleculesandtoformhost/ guestinclusioncomplexes.Cyclodex trinswereusedtoforminclusioncomplexwithdrugstoincreasewatersolubilityandbioavailabili tyofpoorlywater solubledru…     

Studies on the inclusion complex reaction and fluorescent analytical application of β-cyclodextrin with hymecromone

The inclusion complex reaction condition and the mechanism of β-cyclodextrin with hymecromone have been studied by fluorescent spectrum. The fluorescent intensity and the stability of the system can be qreatly increased in qiven condition, and the formation constant of the inclusion complex reaction has been determined too. The system can be applied to the determination of trace amounts of hymecromone, the maximum fluorescent intensity is obtained with excitation and emission wavelength at 362 nm and 452 nm, respectively. The linear range for hymecromone is 8.0×10⁻⁹ mol·L⁻¹ to 1.0×10⁻⁵ mol·L⁻¹. The detection limit is 1.8×10⁻⁹ mol·L⁻¹. A simple, rapid and highly sensitive fluorimetric method is proposed for the determination of hymecromone. The results obtained are in agreement with those given by an official method. Foundation item: Supported by the National Natural Science Foundation of China (G1999046703) Biography: Luo Zhao-fu(1947-), female, Associate professor.     

Photoelectrochemical synergetic degradation of Acid Orange II with TiO_2 modified β-PbO_2 electrode

Advanced oxidation processes (AOPs) have been paid increasing attention recently due to their effective degradation of organic pollutants into environmentally friendly chemicals even resulting in complete mineralization, among which TiO2 heterogeneous photocatalysis appears to be the most emerging destructive technology. Surfactants, pesticides, dyes and a wide range of organic pollutants can be effectively reduced when TiO2 particles are used in photocatalytic degradation process. However, …     

Synthesis of a symmetrical tetrasubstituted cucurbit[6]uril and its host-guest inclusion complex with 2,2′-bipyridine

Synthesis of a symmetrical tetrasubstituted cucurbit[6]uril has been achieved by using the diether of dimethylglycoluril (1) and the dimmer of glycoluril (2). The structure of the symmetrical tetramethylcucurbit[6]uril (TMeQ[6]) has been determined by single crystal X-ray diffraction, ^1H NMR spectroscopy and ESMS. The ^1H NMR spectra of 2,2‘-bipyridine added to TMeQ[6] reveal that the host-guest inclusion complex was easily formed.     

Synthesis of a symmetrical tetrasubstituted cucurbit[6]uril and its host-guest inclusion complex with 2,2′-bipyridine

Since the structure of the first cucurbituril, a cyclic oligomer of 6 units of glycoluril linked by 12 methylene bridges was determined by Freeman et al. in 1981[1,2], considerable interest has emerged inspired by this new receptor. The receptor properties have been examined in a variety of ways such as polyrotaxanes, molecular neck-laces, rotaxane dendrimers, cyclo-addition reactions which occur more rapidly inside the cavity, and the treatment of effluent from the dye industry[2—12]. Almost…     

Study on the Synthesis and Adsorption Properties of KH-560 Modified PalygorskiteSupported β-Cyclodextrin

1 Results Palygorskite (PGS) is a chain-layer magnesium-aluminum silicate mineral. Because of its developed interior channels and large specific surface area, and thus considerable adsorption capacity, it has been studied for the application as one of environmental mineral adsorbents[1-3]. Cyclodextrins (CD) possess a hydrophilic exterior and a hydrophobic interior into which a variety of hydrophobic organic molecules maybe introduced. The CD molecule not only affects a hydrophilic cavity on the nanometer scale, generally smaller than the zeolitic cavities, but also possesses hydrophilic hydroxyl groups outside the cavity, which contribute to the solubility of CD in water[4-5].     

Development of the model of pancreatic β-cell membrane chromatography and its chromatographic characteristics

A new model of pancreatic β-cell membrane chromatography has been established by using a β-cell membrane stationary phase （β-CMSP） prepared by immobilizing the β-cell membrane onto the surface of silica carrier. The protein level and K^＋, Na^＋-ATP enzymatic activity of the β-CMSP were detected respectively. The surface characteristics of the β-CMSP were tested by using the scanning electron microscope and surface energy spectrometer. In this model, the column （10 mm × 2 mm, I.D.） packed with β-CMSP, 25 mmol/ammonium sulfate buffer solution （pH 7.4） as mobile phase with the flow rate of 0.2 mL/min at 37 ± 0.5℃ were used in the following studies. The retention characteristics of the sulfonylureas （gliquidone, glibenclamide, gliclazide and glipizide） were investigated under the chromatographic conditions above. The affinities of the sulfonylureas on β-cell membrane and receptor will be expressed by using the logk＇ values （the logarithm of capacity factor of a solute） in the model. The correlation of the affinity with the pharmacological effect of the sulfonylureas was analyzed also.     

Formation of the Yazi Spring Stream and its significance on tectonics-climate on the northern slope of Kunlun Mountains

The sequences of fluvial terraces in the Yazi Spring Stream are signs of the stepwise uplift of the Kunlun Mountains in the northern part of the Tibetan Plateau since the Late Pleistocene. Geomorphic and sedimentary features of the terraces reveal that they have resulted from the phased tectonic uplift and the consequent river incision in the northern plateau. Using the method of Single-aliquot Regenerative-dose （SAR） Protocol and Radiocarbon ^14C dating, the deposit ages of three-grade terraces were obtained, which are 57.5, 12.8 and 5.7 kaBP, respectively. The features and ages of terraces reveal that the incision rate of the stream accelerated at the beginning of the Holocene. The incision rate changed suddenly at 12.8 KaBP, from 0.43±0.07 mm/a to 1.59±0.55 mm/a. This implicates that uplift of the Kunlun Mountains is intensive at the first onset of the Holocene, corresponding to the obvious change of slip-rate on the AItyn Tagh Fault. But its uplift rate is much lower than that of the latter, which suggests that growth of the northern margin of the Tibetan Plateau is stronger than its interior.     

Strengthening of the boreal winter Hadley circulation and its connection with ENSO

Empirical orthogonal function (EOF) analysis is carried out for the year-to-year variability of the boreal winter (DJF) mass stream function of the mean meridional circulation (MMC) during the period 1948—2005. The results demonstrate that it is dominated by the equatorially asymmetric and symmetric modes. Further analysis shows that the former mode is linked with the boreal winter Hadley cell mainly on the decadal time-scale, and the latter on the interannual time-scale. The asymmetric mode index (AMI) with a clear upward trend contributes to the decadal strengthening of the boreal Hadley circulation, and is closely correlated with the tropical SST warming, especially in the region of Indo-west Pacific warm pool (INWP). Furthermore, the AMI also contributes to the abrupt change of the correlation coefficient between the boreal Hadley circulation and ENSO after 1976. The symmetric mode index (SMI) with robust and stable linkage with ENSO shows a significant interannual variability, suggesting that the variability of the Hadley circulation is mainly associated with ENSO on the interannual time-scale.     

SHRIMP U-Pb zircon dating for the dacite of the Sangxiu Formation in the central segment of Tethyan Himalaya and its implications

The Tethyan Himalaya is located between the In-dus-Yarlung Zangbo suture zone to the north and HigherHimalayan crystallines to the south, paleogeographicallybelonging to the northern margin of “Greater India”. TheSangxiu Formation is used to define a series of specialstrata with rich volcanic interbeds, and is only distributedto the southeast of Yangzuoyong Co within 200 km×50 km along the eastern part of central Tethyan Hima-laya[1]. Based on overlapped relationships of strata andfos…     

Crystal structure of the β2 adrenergic receptor-Gs protein complex

G protein-coupled receptors (GPCRs) are responsible for the majority of cellular responses to hormones and neurotransmitters as well as the senses of sight, olfaction and taste. The paradigm of GPCR signalling is the activation of a heterotrimeric GTP binding protein (G protein) by an agonist-occupied receptor. The β(2) adrenergic receptor (β(2)AR) activation of Gs, the stimulatory G protein for adenylyl cyclase, has long been a model system for GPCR signalling. Here we present the crystal structure of the active state ternary complex composed of agonist-occupied monomeric β(2)AR and nucleotide-free Gs heterotrimer. The principal interactions between the β(2)AR and Gs involve the amino- and carboxy-terminal α-helices of Gs, with conformational changes propagating to the nucleotide-binding pocket. The largest conformational changes in the β(2)AR include a 14 ? outward movement at the cytoplasmic end of transmembrane segment 6 (TM6) and an α-helical extension of the cytoplasmic end of TM5. The most surprising observation is a major displacement of the α-helical domain of Gαs relative to the Ras-like GTPase domain. This crystal structure represents the first high-resolution view of transmembrane signalling by a GPCR.     

Photoelectrochemical synergetic degradation of Acid Orange II with TiO2 modified β-PbO2 electrode

Electrochemically assisted photocatalysis is an effective approach to improve photocatalytic efficiency. In this paper, modified β-PbO2 electrode was prepared by TiO2 co-deposition and characterized by SEM and XRD. Then 2.0g TiO2 modified β-PbO2 electrode (2.0 g TiO2 involved in the 200 mL co-deposition solution) was used in electrochemically assisted photocatalytic degradation of Acid Orange II and the influence of initial pH values was investigated when the potential applied across the electrodes was 1.5 V. When the potential applied was 2.5 V, the difference of the degradation process and the final products were studied. The results indicated that 2.0 g TiO2 modified β-PbO2 electrode was different from the unmodified one in that the β-PbO2 crystals became finer and the electrode became more compact and more uniform. The synergetic effect in electrochemically assisted photocatalytic degradation of Acid Orange Ⅱ was observed and degradation efficiency and TOC removal were the highest at initial solution pH 2.0. By UV-visible spectral analysis, it was proved that photoelectrochemical synergetic degradation of Acid Orange Ⅱ went through the step of producing main product maleic acid for the solution at the initial pH 2.0 within 2 h, but the degradation was slow for the solution at the initial pH 12.0.     

Research of Inclusion Complexation of 4,4'-Thiodiphenol Effected by β-Cyclodextrin in Aqueous Solutions and the Effect on Photodegradation

The inclusion behavior of 4,4′ -Thiodiphenol (TDP),a typical bisphenol and endocrine disruptor,reacts with β-cyclodextrin (β-CD) in aqueous solutions has been investigated by means of UV absorption spectrum and quantum-chemical calculation with Gaussian 98 software. The results show that the inclusion behavior of TDP is quite different in acidic solutions (pH 5.9) from that in alkaline solutions (pH 10.0). This behavior difference is attributed to the different formula structures in aqueous solutions at acidic and alkaline pH values that are demonstrated by quantumchemical modeling and calculation. TDP forms a 1∶1 β-CD inclusion complex in aqueous solutions. The equilibrium constant K was calculated to be 553.49 L/mol at pH 5.9 and 1 318.20 L/mol at pH 10.0 respectively for the inclusion complex reaction by using the modified Benesi-Heldbrand equation. After inclusion TDP's structure is changed especially at the inclusion part with the bond order becoming larger,which results in inhibitive photodegradation during direct photooxidation and H2O2 assisted photooxidation.     

Theoretical study on magneto-structural correlation of trinuclear copper （II） complex with the hydroxo bridge and bidentate syn-syn carboxylate group

During the past decade, molecular magnetism has received much attention both experimentally and theo- retically. Especially, the study of magneto-structure correlation attracts a continuous interest due to its fun-damental role in the design of molecular-…     

~1H NMR Investigation of Supramolecular Complex between β-Cyclodextrin and Cholesterol

A supramolecular complex between β-cyclodextrin and cholesterol was synthesized and characterized via proton 1H NMR spectroscopy. In the supramolecular complex,the stoichiometric proportion of β-cyclodextrin to cholesterol is 1:2. The possible conformation of the supramolecular complex was depicted according to the chemical shift variance of proton 1H NMR of the host and guest molecules inside the inclusion complex. Removal efficiency of cholesterol complexed by β-cyclodextrin in our work is increased to a remarkable extent. This result can be applied in the field of drug development to reduce cholesterol in blood and other human organs.     

Research of Inclusion Complexation of 4,4＇-Thiodiphenol Effected by β-Cyclodextrin in Aqueous Solutions and the Effect on Photodegradation

The inclusion behavior of 4, 4＇ -Thiodiphenol （TDP）, a typical bisphenol and endocrine disruptor, reacts with β-cyclodextrin （β-CD） in aqueous solutions has been investigated by means of UV absorption spectrum and quantum-chemical calculation with Gaussian 98 software. The results show that the inclusion behavior of TDP is quite different in acidic solutions （pH 5.9） from that in alkaline solutions （pH 10.0）. This behavior difference is attributed to the different formula structures in aqueous solutions at acidic and alkaline pH values that are demonstrated by quantum- chemical modeling and calculation. TDP forms a 1 ： 1 fl-CD inclusion complex in aqueous solutions. The equiiibrium constant K was calculated to be 553.49 L/mol at pH 5.9 and 1 318.20 L/mol at pH 10.0 respectively for the inclusion complex reaction by using the modified Benesi-Heldbrand equation. After inclusion TDP＇s structure is changed especially at the inclusion part with the bond order becoming larger, which results in inhibitive photodegradation during direct photooxidation and H2O2 assisted photooxidation.     

Formation of Ferric Porphyrinoids with Unusual Electronic and Magnetic Properties

1 Results Energy levels of the metal 3d orbitals in iron(Ⅲ) porphyrinoids are controlled by various factors such as the nature and number of axial ligands, electronic and steric effects of peripheral substituents, deformation and core modification of porphyrin ring, hydrogen bonding to the axial ligand, etc. By manipulating these factors, we are now able to prepare various iron(Ⅲ) porphyrinoids withunusual electronic and magnetic properties[1]. Here, we report the formation of such complexes as ⅰ) low-spin bis(tBuNC) complexes of OETArP and DAzP showing the (dxy)2(dxz, dyz)3 ground state[2], all the bis(tBuNC) complexes reported previously exhibit the (dxz, dyz)4(dxy)1 ground state, ⅱ) low-spin bis(HIm) complex of TPrC showing the (dxz, dyz)4(dxy)1 ground state; bis(HIm) complexes almost always adopt the (dxy)2(dxz, dyz)3 ground state[3] Ⅲ) one electron oxidation product of iron(Ⅲ) porphyrinate that shows S=0 electronic ground state, one electron oxidized products exhibit either iron(Ⅳ)(S=1) or iron(Ⅲ)(S=5/2 or S=1/2) radical cation(S=1/2). The spectroscopic data of these complexes are quite useful for further developing the material with unique properties(See Fig.1).     

Corrosion properties of bio-oil and its emulsions with diesel

Bio-oil is a new liquid fuel but very acidic. In this study, bio-oil pyrolyzed from rice husk and two bio-oil/diesel emulsions with bio-oil concentrations of 10 wt% and 30 wt% were prepared. Tests were carried out to determine their corrosion properties to four metals of aluminum, brass, mild steel and stainless steel at different temperatures. Weight loss of the metals immersed in the oil samples was recorded. The chemical states of the elements on metal surface were analyzed by X-ray photoelectron spectroscopy （XPS）. The results indicated that mild steel was the least resistant to corrosion, followed by aluminum, while brass exhibited slight weight loss. The weight loss rates would be greatly enhanced at elevated temperatures. Stainless steel was not affected under any conditions. After corrosion, in- creased organic deposits were formed on aluminum and brass, but not on stainless steel. Mild steel was covered with many loosely attached corrosion materials which were easy to be removed by washing and wiping. Significant metal loss was detected on surface of aluminum and mild steel. Zinc was etched away from brass surface, while metallic copper was oxidized to Cu20. Increased Cr203 and NiO were presented on surface of stainless steel to form a compact passive protection film. The two emulsions were less corrosive than the bio-oU. This was due to the protection effect of diesel. Diesel was the continuous phase in the emulsions and thus could limit the contact area between bio-oil and metals.