Molecular Structures and Mechanical Properties of Microbe Rapid Coagulation Natural Rubber

In this work,molecular structures,dynamic mechanical properties and glass transition temperatures of microbe coagulated natural rubber（NR） samples were analyzed by using pyrolysis gas chromatography-mass spectrometry（py-GC/MS）,rubber process analyzer（RPA） and dynamic mechanical thermal analysis（DMA）.And the cross-linked network structures and mechanical properties of the corresponding NR vulcanizates were further determined by using nuclear magnetic resonance（NMR） crosslink density spectrometer（XLDS-15） and universal testing machines.The results show that NR raw rubber produced by rapidly coagulated with microorganism exhibits a simple molecular structure composition and good dynamic mechanical properties,and the corresponding NR vulcanizates possess the aggregation structure of high cross-linked density,a high glass transition temperature of-61.5 ℃ and high mechanical properties（tensile strength reaches 25.2 MPa）,as compared with that coagulated with acetic acid.

Theoretical Studies on the Molecular Structures and Thermodynamic Properties of Polychlorinated Fluorenes

Geometric structures of 135 polychlorinated fluorene （PCFR） molecules were optimized using density functional theory （DFT） at the B3LYP/6-311G＊＊ level and their thermodynamic properties in the ideal gas state were calculated. The relations of these thermodynamic properties with the number and position of chlorine atoms were also explored, from which the relative stability of PCFR congeners was theoretically proposed according to the magnitude of the relative standard Gibbs free energy of formation （Δr,fGθ）. The results show that the geometric configuration of PCFR isomers is determined by the position of chlorine atoms. There exist two types of intramolecular weak interactions, i.e., C–H···Cl and Cl···Cl interactions in PCFR molecules. The change of ΔfHθ and ΔfGθ of most stable PCFR isomers with increasing the number of chlorine atoms is different from that in most unstable PCFR congeners. The values of ΔfHθ and ΔfGθ for PCFR isomers with the same number of chlorine atoms strongly depend on the position of chlorine atoms and the relative stability of PCFR congeners is mainly determined by intramolecular delocalized π bond and Cl···Cl nuclear repulsive interaction.

Design of the Metal Precursors Molecular Structures in Impregnating Solutions for Preparation of Efficient Ni Mo/Al_2O_3 Hydrodesulfurization Catalysts

The molecular structures of metal precursors in the impregnating solution were designed so as to prepare efficient Ni Mo/Al_2O_3 hydrodesulfurization(HDS) catalysts. At first, five typical impregnating solutions were designed; the existing metal precursors, such as [Mo4(citrate)2O11]^(4-)-like, [P2Mo18O62]^(6-)-like and [P2Mo5O23]^(6-)-like species in the solutions were confirmed by laser Raman spectroscopy(LRS). The UV-Vis spectra results indicated that the solutions containing both phosphoric acid and citric acid could change the existing form of nickel species. Five corresponding Ni Mo/Al_2O_3 catalysts were prepared by the incipient wetness impregnation method. The LRS analysis results of dried catalysts showed that the above metal precursors could be partly retained on alumina support after impregnation and drying, although the interface reaction between different metal precursors and alumina support unavoidably took place. Then the catalysts were sulfided and characterized by N2 physisorption, TEM and XPS analyses. The results showed that different metal precursors in impregnating solution could mainly result in the difference in both the morphology of(Ni)Mo S2 slabs and the promoting effect of Ni species. The catalyst prepared mainly with [P2Mo5O23]^(6-)-like species used as precursors exhibited worse dispersion of(Ni)Mo S2 slabs and lower ratio of Ni–Mo–S active phases than the one with [Mo4(citrate)2O11]^(4-)-like species. Promisingly, the catalyst prepared with co-existing [Mo4(citrate)2O11]^(4-)-like, [P2Mo18O62]^(6-)-like and [P2Mo5O23]^(6-)-like species showed better hydrodesulfurization activity for 4,6-DMDBT thanks to its more well-dispersed Ni–Mo–S active phases.

Theoretical Studies on the Molecular Structures and Thermodynamic Properties of Polychlorinated Acenaphthylenes

Geometric structures of 135 polychlorinated acenaphthylene （PCAC） molecules were optimized using density functional theory （DFT） at the B3LYP/6-311G^＊＊ level and some thermodynamic properties of them in the ideal gas state were calculated. The relations of these thermodynamic properties with the number and position of chlorine atoms were also explored, from which the relative stability of PCAC congeners was theoretically proposed according to the magnitude of the relative standard Gibbs free energy of formation （△r,fGθ）. The results show that all PCAC isomers have planar geometric configuration. There exists intramolecular Cl···Cl weak interaction in some PCAC molecules. The change of △fHθ and fGθ of most stable PCAC isomers with increasing the number of chlorine atoms is different from that in the least stable PCAC congeners. The values of fHθ and fGθ for PCAC isomers with the same number of chlorine atoms show a strong dependence on the position of chlorine atoms and the relative stability of PCAC congeners has close relation with the intramolecular Cl···Cl nuclear repulsive interaction.

DFT Study on Molecular Structures and ROS Scavenging Mechanisms of Novel Antioxidants from Lespedeza Virgata

The molecular structure and radical scavenging activity of three novel antioxidants from Lespedeza Virgata, lespedezavirgatol, lespedezavirgatal, and lespedezacoumestan, have been studied using density functional theory with the B3LYP and BhandHLYP methods. The optimized geometries of neutral, radical cation, radical and anion forms were obtained at the B3LYP/6-31G（d） level, in which it was found that all the most stable conformations contain intramolecular hydrogen bonds. The same results were obtained from the MP2 method. The homolytic O-H bond dissociation enthalpy and the adiabatic ionization potential of neutral and anion forms for the three new antioxidants and adiabatic electron affinity and H-atom affinity for hydroxyl radical, superoxide anion radical, and hydrogen peroxide radical were determined both in gas phase and in aqueous solution using IEF-PCM and CPCM model with UAHF or Bondi cavity. The antioxidant activities and reactive oxygen species scavenging mechanisms were then discussed, and the results obtained from different methods are consistent. Furthermore, the antioxidant activities are consistent with the experimental findings of the compounds under investigation.

C-H…O Hydrogen Bonds and π…π Interaction and the Crystal and Molecular Structures of 3-Nitro-benzylideneaniline-methyl-2’

The title compound (C14H12N2O2, Mr = 240.26) crystallizes in the monoclinic system, space group P21/a with a = 7.394(1), b = 21.334(3), c = 7.423(1) ? b = 89.82(1)? V = 1170.8(3) ?, Z = 4, Dc = 1.363 g/cm3, m(MoKa) = 0.93 cm-1 and F(000) = 504.00. The final R and wR are 0.0440 and 0.1370 for 2153 observed reflections (I > 2s(I)), respectively. The dihedral angle between the two phenyl rings is 52.9 and that between the NO2 group and its attached ring is 3.0. In the crystal, molecules are stacked along [100] through p…p interactions. The CH…O hydrogen bond (3.403 ? 120.4? laterally connects the stacks along [010] to form networks (001) which are further anti- parallelly connected by CH…O (3.382 ? 142.9) and p…p interactions extending along [001]. Also presented here is a brief study on the CH…O hydrogen bonds in nitro-substituted benzyl-ideneanilines which can be classified into five types, namely, )5(12R, )4(21R, )8(22R, )6(12R and )7(22R, with the first three occurring more often.

INFLUENCE OF MOLECULAR STRUCTURES OF SECONDARY AMINE TERMINATED POLY(ESTER-AMINE)S ON THE CURING PERFORMANCE WITH EPOXY RESIN

Five secondary amine terminated poly（ester-amine）s （defined as PEA） with controlled molecular structures were synthesized through reacting excessive piperazine with phthalicdiglycol diacrylate （PDDA） and 1,1,1-trimethylolpropane triacrylate （TMPTA） at a constant secondary amine/acrylate group ratio of 1.5/1 and at different PDDA/TMPTA molar ratios. Both IR and ^1H-NMR spectra indicated that all acrylate groups were consumed in the reaction, based on which the structural parameters were calculated from the ^1H-NMR spectra. With decreasing PDDA/TMPTA ratio, the content of secondary amine, degree of branching, molecular weight, Tg and Td increased accordingly. These polymers were further used as both crosslinkers and flexibilizers for a linear epoxy resin E51 to form cured films under ambient condition. The gel content, relative hardness and Tg of the resulting films increased as PEA molecules changed from linear to highly branching structures. Due to the flexibility of PEA molecules, all the films possessed excellent mechanical performance.

Rotational Spectra and Molecular Structures of Ethylanilines

The molecular structures of three ethylanilines,ortho-,meta-and para-ethylaniline,have been obtained by means of Fourier-transform microwave spectroscopy.Rotational spectra of all three molecules display the nuclear quadrupole hyperfine structures arising from the 14N nucleus.Comparison of the determined structures allows a direct study of the influence of the position of the ethyl substituent on the structure of the amino group communicated through the phenyl ring.

Theoretical Studies on the Molecular Structures and Thermodynamic Properties of Polychlorinated Fluoranthenes

DFT-B3LYP/6-311G＊＊ method has been used to optimize molecular geometric structures of 527 polychlorinated fluoranthene（PCFRT） congeners and calculate their thermo-dynamic properties in the ideal gas state,such as heat capacity at constant volume（Cv）,entropy（S）,standard enthalpy of formation（ΔfH） and standard Gibbs free energy of formation（ΔfG）.The relations of Cv,S,ΔfH and ΔfG with the number and position of chlorine atoms have also been explored,from which the relative stability of PCFRT congeners was theoretically proposed according to the magnitude of the relative standard Gibbs free energy of formation（Δr,fG）.It was found that some of the PCFRT isomers are in a nonplanar configuration and there are intramolecular Cl…Cl weak interactions in some of the isomers.With increasing the number of chlorine atoms,the values of ΔfH and ΔfG of the most stable PCFRT isomers decrease initially and then increase.The values of ΔfH and ΔfG of PCFRT congeners with the same number of chlorine atoms show a strong dependence on the positions of chlorine atoms.The relative thermodynamic stability of PCFRT isomers is determined mainly by intramolecular adjacent Cl…Cl nuclear repulsive interaction between Cl atoms at two different six-membered rings.Most PCFRT congeners are easier to form thermodynamically than their parent compound.

Crystal and Molecular Structures of Two Derivatives of 1, 3a, 5-Trisubstituted-3a ,4,5,11-Tetrahydro-1,2,4-Oxadiazolino[5,4-d] [1, 5]Benzothiazepine

The structures of two derivatives of the title compound [C24H22N2OS, Mr = 386. 5 for (1); C25H22N2O3S, Mr = 430. 5 for (2)] were determined by using X-ray single-crystal strcuture analysis method. The final discrepancies are R = 0. 071 and 0. 077, respectively, for the reflections measured on a four-circle diffractometer. The space group for compound (1) is P bca with a=1. 6639(4), b=2.0286(3), c= 1.1742(1) nm, V = 3. 964(1) nm3, F(000) = 1632 e, Z=8; and (2) belongs to P21/n space group, and the cell dimensions are a=1. 1115(4), b=0. 8932(7), c=2. 186(3) nm, β=97. 52 (1)°? V=2.151(4) nm3, F(000) = 904 e, Z=4.The molecular backbones are very similar, each is a tricyclic system. The central seven-membered ring is in a twisted-boat conformation, and is cis-fused to 1,2,4-oxa-diazolino ring, while the latter moiety is in an envelope form. There are conjugated but non-coplanar effects in each structure. All bond lengths and angles in the molecules are normally acceptable. The crystal structure on the whole is completely stabilized by Van der Waals interactions.

Photo-Induced Intermolecular Electron Transfer-Effect of Acceptor Molecular Structures

Photo-induced electron transfer versus molecular structure of acceptors is investigated using ultrafast time-resolved transient grating spectroscopy. Typical laser dyes Rhodamine 101 (Rh101) and Rhodamine 6G (Rh6G) in electron donor solvent-aniline are adopted as the objects. The forward electron transfer time constant from aniline to the excited singlet state of two Rhodamine dyes and subsequent back electron transfer from two dyes to aniline are measured. The experimental results denote that Rh6G presents faster electron transfer rates with aniline in both forward electron transfer and back electron transfer processes. With chemical calculation and qualitative analysis, it is found that the flexible molecular geometry of Rh6G leads to stronger electron coupling with donor solvent and further gives rise to larger electron transfer rates.

Effect of cis/trans molecular structures on pyrolysis performance and heat sink of decalin isomers

Decalin is considered as an important compound of high-energy-density endothermic fuel,which is an ideal on-board coolant for thermal management of advanced aircraft.However,decalin contains two isomers with a tunable composition,and their effects on the pyrolysis performance,such as the heat sink and coking tendency have not been demonstrated.Herein,we investigated the pyrolysis of decalin isomers,i.e.,cis-decalin,trans-decalin and their mixtures(denoted as mix-decalin),in order to clarify the effects of the cis-/trans-structures on the pyrolysis performance of decalin fuels.The pyrolysis results confirmed that conversion of the tested fuels(600–725℃,4 MPa)decreased in the order cis-decalin>mix-decalin>trans-decalin.Detailed analyses of the pyrolysis products were used to compare the product distributions from cis-decalin,mix-decalin and trans-decalin,and the yields of some typical components(such as cyclohexene,1-methylcyclohexene,benzene and toluene)showed significant differences,which could be ascribed to deeper cracking of cis-decalin.Additionally,the heat sinks and coking tendencies of the decalins decreased in the order cis-decalin>mix-decalin>trans-decalin.This work demonstrates the relationship between the cis/trans structures and the pyrolysis performance of decalin,which provides a better understanding of the structure-activity relationships of endothermic hydrocarbon fuels.

Degradation of neonicotinoids with different molecular structures in heterogeneous peroxymonosulfate activation system through different oxidation pathways

The elimination of neonicotinoids(NEOs)from water has been a research priority due to their threats to human health and ecosystems.In this study,we established the heterogeneous peroxymonosulfate(PMS)activation system using manganese catalyst(Mn NC)and cobalt catalyst(Co NC)to trigger the nonradical oxidation and synergistic oxidation pathway,respectively to remove NEOs.The results showed that the nonradical oxidation system exhibited superior NEOs degradation capability.The composition of organic pollutants in wastewater significantly impacted subsequent degradation processes.The charge distribution and reaction sites of various NEOs were analyzed using density functional theory(DFT)calculations,and it demonstrated the electron distribution and activity of NEOs were significantly influenced by the type and number of substituents.Nitro group(–NO_(2))and cyanide group(–C≡N)were identified as strong electron-withdrawing groups and prone to be attacked by negatively charged radicals.The transformation of NEOs was analyzed,and result showed that the C and N sites adjacent to the nitro group and cyanide group were more susceptible to oxidation attacks.S and N atoms,which possess strong electronegativity and high electron cloud density,were identified as key active sites in the degradation pathway.The outcomes of this study provide valuable guidance for the oriented regulation of oxidation pathways towards efficient removal of NEOs in water.

Secondary ligand engineering of nanoclusters:Effects on molecular structures,supramolecular aggregates,and optical properties

Developing new templates to evaluate the ligand engineering effect in manipulating nanoclusters from both molecular and supramolecular aspects remains highly desired in cluster science because it allows for an in-depth understanding of structure-property correlations.We herein presented the secondary ligand(i.e.,the phosphine ligand)engineering based on an Ag_(29) nanocluster template and its dual effects on intracluster structures and intercluster aggregates.The“dissociationcombination equilibrium”of phosphine ligands on the nanocluster surface was controlled by tailoring the C-H…πinteractions within the ligand shell,which led to the fabrication of a family of[Ag_(29)(BDT)_(12)(PR_(3))_(x)]^(3-)nanoclusters.On the molecular level,the dissociation of phosphine ligands contracted the nanocluster framework,while the overall configuration of[Ag_(29)(BDT)_(12)]^(3-)was retained.On the supramolecular level,the complete dissociation of phosphine ligands yielded a bare nanocluster,which followed a chiral crystallization mode,and its crystals displayed high optical activity,derived from circular dichroism and circularly polarized luminescence characterizations.Overall,this work presents the peripheral ligand effects in directionally controlling intracluster configurations and intercluster aggregations,which hopefully benefit future design and preparation of new nanoclusters or cluster-based nanomaterials with customized structures and performances.

PDBlocal:A web-based tool for local inspectionof biological macromolecular 3D structures

Functional research on biological macromolecules must fcus on specific loca regions.PDBlocal is aweb-based tool developed to overcome the limitations of traditional molecular visualization tools forthre-dimensional(3D)inspection of local regions.PDBlocal provides an intuitive and easy-to-manipulate web page interface and some new useful functions.It can kep loca regions flashing,display sequence text that is dynamically consistent with the 3D structure in local appearance undermultiple local manipulations,use two scenes to help users inspect the same local region withdifferent statuses,list all historical manipulation statuses with a tree structure,llow users toannotate regions ofinterest,and save ll historical statuses and other data to a web server for futureresearch.PDBlocal has met expectations and shown satisfactory performance for both expert andnovice users.This tool is available at http:/labsystem.scuec.edu.cn/pdblocal/.

MOLECULAR AND CRYSTAL STRUCTURES OF TETRANUCLEAR MOLYBDENUM CLUSTER[Mo_4(μ_3-O)_2O_4Cl_2(o-CH_3C_6H_4COO)~6]■

The new cluster[Mo_4(μ_3-O)_2O_4Cl_2(o-CH_3C_6H_4COO)_6]has been prepared by the reaction of molybdenum pentachloride and o-methylbenzoic acid.The crystal and molecular structures were determined by the X-ray diffraction method.It crystallizes in the orthorhombic space group Pnna with cell parameters:Mr=1361.6,a=13.792(4), b=17.957(3),c=20.974(9) ,V=5194(2) ~3,Z=4,Dc=1.74/cm^3,F(OOO)=2704,μ(MoK ) =11.0/cm,R=0.074.

Investigation on Molecular and Crystal Structures of Metal Complexes with Aminopolycarboxylic Acids(Ⅰ)─Synthesis and Structure of Na_2[Fe~Ⅲ(ida)2]2·3H_2O

The crystal structure of the title complex salt has been determined by single-crystal X-ray structure analysis. The crystal data are as follows; Monoclinic, P21/c, a=15.6480(10)A,b=16.7870(10)A, c=10.347(2)A, β=90.790(10), V=2717.7(6)A3, Z=3, and R=0.0333 for 4789 unique reflections. The complex anion has a pseudo-octahedral structure distorted more than the CrⅢand CoⅢ analogs, in which cach iminodiacetato ligand (ida2-) is coordinated in a facial fashion with the two N atoms in a cis configuration, resulting in an unsyin-fac structure.

LOCALIZED MOLECULAR ORBITAL STUDY ON ELECTRONIC STRUCTURES OF BOWL-SHAPED AROMATIC HYDROCARBONS

The localized molecular orbitals for typical bowl-shaped circulenes are obtained by the use of INDO-LMO method. It is found that these bowl-shaped circulenes with strained π-electron systems are still aromatic and the rim π-bonds with larger localization form reactive regions for formation of buckminsterfullerene.

Optical and Structural Properties of In_(0.52)Al_(0.48)As/InP Structures Grown at Very High Arsenic Overpressures by Molecular Beam Epitaxy

Growth of ln0.52Al0.48As epitaxial layers on lnP(100) substrates by molecular beam epitaxy at a wide range of arsenic overpressures (V/III flux ratios from 30 to 300) has been carried out. Analysis performed using low-temperature photoluminescence (PL) and double-axis X-ray diffraction (XRD) shows a strong and prominent dependence of the PL and XRD linewidths on the V/III flux ratio. Under our growth conditions, both the PL and XRD linewidths exhibit a minimum point at a V/III flux ratio of 150 which corresponds to a maximum in the PL intensity and XRD intensity ratio. Flux ratios exceeding 150 result in an increase in both the PL and XRD linewidths corresponding to a reduction in their associated intensities. Room temperature Raman scattering measurements show a narrowing in the lnAs-like and AlAs-like longitudinal-optic (LO)phonon linewidths which broaden at high flux ratios, while the LO phonon frequencies exhibit a gradual reduction as the flux ratio is increased. PL spectra taken at increasing temperatures show a quenching of the main emission peak followed by the evolution of a broad lower energy emission which is possibly associated with deep lying centres. This effect is more prominent in samples grown at lower V/III flux ratios. Hall effect measurements show a gradual reduction in the mobility in correspondence to an increase in the electron concentration as the flux ratio is increased.

Computational investigation on the molecular structure and chemical reactivity of a traditional Chinese medicine extract MK-1 molecule

MK-1 molecule(C_(16)H_(16)O_(2)),the simplest structure of vitamin K(VK)compound family,is an extract from traditional Chinese medicine Cymbopogon distans(Nees ex Steud.)Wats(Chinese name YunXiangCao),which has attracted a great deal of attention in recent years due to its antiasthmatic,antitussives and expectorant effects.To investigate the molecular structure and chemical reactivity of MK-1 molecule,computational investigations on six conformational minima structures were carried out at the MP2/6-311++G(2d,2p)level of theory.Several local reactivity descriptors including condensed Fukui function,average local ionization energy,and molecular electrostatic potential on each individual atom were determined to predict the intrinsic reactivity of MK-1 molecule.