Effects of Hydrogen Bonding on the Transition Properties of Ethanol–Water Clusters: A TD-DFT Study

In this work, time-dependent density functional theory method was used to study the electronic transitions of hydrogen-bonded ethanol–water complexes Dimer-I, Dimer-II and Trimer. The intermolecular hydrogen bonds H₁···O₁ and O···H₂ were demonstrated by the optimized geometric structures of the three hydrogen-bonded ethanol–water complexes. It is demonstrated that the S₁-state electronic transitions for ethanol monomer and the hydrogen-bonded complex Dimer-I (through HB-I) should be of LE nature on the ethanol molecule, while those of complexes Dimer-II and Trimer should be of CT character from the hydrogen-bonded water molecule (through HB-II) to the ethanol moiety. The different electronic transition types should be the reasons for the tiny redshift of the S₁-state electronic energy for Dimer-I and the large blueshifts for Dimer-II and the Trimer compared with that of the ethanol monomer.     

The Transition in the Melt of Fluorinated Ethylene-Propylene Copolymer

The subject of the transition in linear polymer melt has been of particular interest since thediscovery of liquid crystal polymers.The transitions in several polymer melts have been recog-nized in recent years.These polymers are mainly rigid chain in nature and the transitions wereassigned as mesomorphic.Recently we have found a transition in the melt of tetrafluoroethylene-hexafluoropropylene copolymer (FEP copolymer). The authors~([1]) have found that the morphology of FEP copolymer is critically dependent onthe temperature of melt near 310?20?.When the melt was held at the temperature above itsmelting temperature and below 310?,the randomly arranged lamellas morphology was obtained.When the melt was held at the temperature above 320?,the spherulitic morphology was formed.When the copolymer crystallized from the intermediate temperature range,the rodlike morphologywas usually obtained.The variation of morphology with temperature can be easily detected by Small Angle Light Scattering technique.Also the crystallization curves,measured with the Per-     

Spectroscopy Investigation on Conformational Transition of Tea Glycoconjugate from Green Tea

The conformational transition of a new glycoconjugate, tea glycoconjugate (TGC), was investigated by spectroscopy techniques including circular dichroism (CD) and ultraviolet (UV) spectroscopy. The solution behaviors of TGC in the mediums of different temperature, pH value, and ions were compared. Results showed that the native conformation of TGC was partially ordered. The CD value and UV absorbance of TGC altered with the change of pH value, temperature, the addition of ions, and also accompanied order-disorder transition. Especially the conditions with temperature higher than the glass transition temperature (Tg=62℃), higher pH value or lower pH value will have the most impact on the conformation of TGC, which will destroy the hydrogen bonds between the TGC molecules. The results indicated that the outside factors play important roles on the stability of the conformation of TGC.     

Density Functional Theory and MP2 Calculations of the Transition States and Reaction Paths on Coupling Reaction of Methane through Plasma

The two possible reaction paths of producing ethane on coupling reaction of methane through plasma were theoretically investigated by B3LYP and MP2 methods with 6-311G^* respectively and further compared with the previous results calculated from B3LYP/6-31G^*. The new investigated results consistently confirmed the previous conclusion. And the influences of the calculation methods and basis sets on the calculated results were also discussed.     

Novel Shape-Memory Polymer with Two Transition Temperature Based on Two Different Memory Mechanism

As an important kind of intelligent materials, shape-memory materials have been received increasing attention on account of their interesting properties and potential applications in recent years. Particularly, the rise of shape-memory polymers by far surpasses well-known metallic shape-memory alloys in their shape-memory properties. The advantages of polymers compared to other materials are their easier availability and their wide range of mechanical and physical properties. The polymers des…     

An in vitro Study on Transition from NO-Hemoglobin to Methemoglobin： Oxygen Effect

The nitrosyl-hemoglobin (HbNO) is the carrier of nitric oxide (NO) which is the important messenger molecule displaying multiple physiologic and pathophysiologic roles. However it is still not clear for the fate of HbNO molecules during the venous-arterial transit. In this letter, the HbNO transition in vitro was studied by using the electron paramagnetic resonance (EPR) spectra. It was found that HbNO molecules were stable when oxygen did not exist in the system but not stable in aerobic conditions. The absorption spectra further revealed that the methemoglobin (metHb) was the product of HbNO in aerobic environment, showing that the HbNO changed to metHb when there were enough oxygen molecules in the system.     

Theoretical Studies on the Coordin

Theoretical　Studies　on　the　Coordin...     

Studies on the Complexes of N,N′-Bis[o-(diphenylphosphino)benzylidene]ethylenediamine with Transition Metal Ions

The thermodynamic parameters for the interaction of Cu²⁺, Ni²⁺, Co²⁺, Cd²⁺, andAg⁺ with the new title ligand have been determined by titration calorimetry in 50% THF–methanol (V/V) at 25 °C.Ag⁺ exhibited remarkably higher complexation selectivity.Ag⁺ and several transition metal ions have been transportedusing this ligand as carrier in a bulk liquid membrane. CompetitiveAg⁺–M²⁺ transport studies have also beencarried out for the same system. In this membrane transport study, high transport of Ag⁺ was observed in both single and competitiveAg⁺–M²⁺ transport studies. The complexformation of N,N-bis[o-(diphenylphosphino)benzylidene]ethylenediamine (P₂N₂) with silver,[Ag(P₂N₂)] (NO₃), (1) is reported. Complex 1 has been characterized by X-ray crystallography. 1 ismonoclinic, space group P2_1/n (No. 14), with cell dimensionsa = 13.398(4) , b=12.577(5) , c = 21.521(4) , =100.14(2) , V = 3570(2) ³ and Z = 4.     

Studies on the Effects of Epimedium Extract on Erythrocytes

Epimedium, one of representatives of traditional Chinese herb, is mainly composed of flavones and polysaccharide. It is famous for its antioxidant, antineoplastic and antiaging activities and has been widely used in the field of invigorating kidney and st…     

Gas-Phase Polymerization with Transition Metal Catalysts Supported on Montmorillonite – A Particle Morphological Study

This investigation focuses on the mechanism of particle fragmentation and growth when clay-supported metallocene catalysts are used to polymerize ethylene in gas-phase reactors. We supported bis(cyclopentadienyl)-zirconium dichloride (Cp₂ZrCl₂) on montmorillonite (MMT) pretreated with triisobutylaluminum and 10-undecence-1-ol to produce in-situ polyethylene-clay nanocomposites. During gas phase polymerization, the MMT layers were exfoliated by the growing polymer chains, starting from the openings of the clay galleries. After microtoming, the cross-section of the fragmented MMT particles showed bundles of distorted silicate layer stacks, proving that exfoliation took place during polymerization, producing an in-situ polyethylene-clay nanocomposite. Calculations of d-spacing by transmission electron microscopy (TEM) matched those measured by X-ray diffraction (XRD) analysis.     

Münchnone-Alkene Cycloadditions: Deviations from the FMO Theory. Theoretical Studies in the Search of the Transition State

The dipolar cycloaddition reactions of 3-methyl-2-(4-nitrophenyl)-4-phenyl-1,3-oxazolium-5-olate (1) and chiral nitroalkenes derived from D-galacto- and D-manno-hept-1-enitols 2 and 3 were found to proceed in a regiospecific manner to afford acyclic pyrrole C-nucleosides (5 and 6) in satisfactory yields. This protocol constitutes a novel and efficient route to such substances. Remarkably, the regiochemistry of this mesoionic-based cycloadditive process is exactly opposite that anticipated from the FMO view of 1,3-dipolar cycloadditions. A preliminary semiempirical PM3 study also reveals the inconsistencies of semiempirical studies with experimental data by applying the FMO approach to münchnone cycloadditions. The structural characteristics of the reagents, products, and transition states have been determined, and this calculation also evaluates the influence of steric and electronic factors involved. Ab initio MO calculations using a model system consisting of 1,3-oxazolium-5-olate with 2-(hydroxymethyl)nitroethylene were also performed. The ab initio study justifies, for the first time, the experimental results of 1,3-dipolar cycloadditions with münchnones. The process occurs through a concerted, slightly asynchronous transition state.     

Study on the Formation Mechanism of Oxygen-containing Groups on the Surfaces of Hypercrosslinked Polystyrenes

Davankov and Tsyurupa described a new series of hypercrosslinked polymeric networks in 19691. Owing to their high internal surface area, unique porosity, and excellent swelling feature, hypercrosslinked polymers have exhibited a good adsorption affinity t…     

pH-Sensitive Wettability Induced by Topologicaland Chemical Transition on the Self AssembledSurface of Block Copolymer简

pH-sensitive wettability of polystyrene-b-poly（4-vinylpyridine） （PS-b-P4VP） self assembled films, exhibiting superoleophobicity under water and hydrophilicity at low pH value, and oleophobicity under water and hydrophobicity at neutral condition, has been realized. The wettability properties resulted from the surface topological and chemical transition, which were confirmed by in situ AFM measurements under water at different pH. At low pH, P4VP chains, which were confined in the hexagonal-packed nanodomains, got protonated into a swollen state, while at high pH, P4VP chains were deprotonated into a collapsed state. The reversible protonation/deprotonation procedure on the molecular scale leads to surface topological and chemical transition, thereby pH-sensitive wettability.     

Catalytic Hydrogenation of Diacetyl Monoxime to Tetramethylpyrazine with the Soluble Transition Metal Catalysts

Tetramethylpyrazine(TMP)isausefulcompoundinfoodindustry'.InrecentyearsithasbeenfoundasanactiveingredientinChuanxi0ng(ligusticumwallichiifranch),whichisatraditionalChineseherb.NowTMPhasbeenwidelyusedinthetreatmentofpatientswithcerebralischemicdiseasesinChina2.OneoftheimportantmethodsforthepreParationoftetramethylpNazineistheselfcondensati0noftwomoleculesof2-aminobutanoneto2,5-dihydrotetramethlipyrazineandsubsequentoxidati0ntoTMP3.2-Aminobutanoneispreparedusuallyinsituviathereductionofthec…     

Studies on the Kinetics of the FO CO Reaction

IntroductionAproposedcycleinvolvingtheFOradicalsisl:ThecontributionofthiscycletothecatalyticdestrUctionofozoneisdeterndnedbythefirststep.Thereaction(l)isalsothoughttobeapossiblesinkforatInosphericCO2.Baueretal.3gavearateconstantofl.24.lO-i3cm3/sforreaction(l),whichwasbelievedtobecorrectwithinafactorof2at9(X)-l4(X)K.Theactivationenergywasestimatedtobe46.OkJ/mol.Bedzhanyanetal.4reportedk<4xlO-"and<5xlO-l6cm3/sat3ooand55OK,respectively.Alowerbarrierofl3.8kJ/molcanbeextrapoIated.Francisco…     

Studies on the effect of surfactants on the extraction rate by laser thermal lens spectrometry

The effect of different kinds of surfactants on the extraction process of Nile Blue-I- was investigated by laser thermal lens spectrometry . It was shown that the surfactants could accelerate or decelerate the extraction rate by varying the extractive's solubility and the interfacial tension of the extraction solution. The higher the concentration of surfactants was, the more obvious the effect.     

Studies on the biosynthesis of arteannuin

In previous communications we have reported that arteannuic acid(1,Scheme1)is a common precursor of the biosynthesis of both arteannuin(2)and arteannuinB(3)by the leaf homogenate of the plant Qinghao(Artemesia annua L.).It seemsthat most likely the oxidation of allylic tertiary carbon atom,C-6,may occur early inthe biosynthetic path of 2 and 3 from 1.Natural 6-epi-deoxyarteannuin B(4)isolated     

Studies on the Synthesis of Preverecynarmin

Prev~n1,acembranopditerpenoid,wasfirstisolatedfromsoftcoral(VeretilIumcoporium)inl99(),anditSmCtUrwasehablishedas(+)-(lE,3E,7E,llE)-cembra-l,3,7,ll-tetraen6-olaeetate[l].SofarasweknOW,thetotalSynthsisof1hasnobeenrePOrtedyet.Herein.wewishtodescribethetotalpeisoftheprecursor(9),theSynthhcroutewasouthnedbelowfa)HBr.80%;b).CH3C02Na.CH3CO2H,75%,c).Se02-I-Bu00H,70%,d).CCl',PPh3,83%,e).NaSQPh.DMF.9O%,O.K=CO3.MeOH,95%,g).DHP,Ts0H.8O%,h),TBAB,5O%NaOH,aq.,5%;i).Li-Effez.M,70%;j…