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.

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.

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.

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.

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.

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.

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.

Board-invited review: Sensitivity and responses of functional groups to feed processing methods on a molecular basis

In complex feed structures, there exist main chemical functional groups which are associated with nutrient utilization and availability and functionality. Each functional group has unique molecular structure therefore produce unique molecular vibration spectral profile. Feed processing has been used to improve nutrient utilization for many years. However, to date, there was little study on processing-induced changes of feed intrinsic structure and functional groups on a molecular basis within intact tissue. This is because limited research technique is available to study inherent structure on a molecular basis. Recently bioanalytical techniques： such as Synchrotron Infrared Microspectroscopy as well as Diffuse Reflectance Infrared Fourier Transform molecular spectroscopy have been developed. These techniques enable to detect molecular structure change within intact tissues. These techniques can prevent destruction or alteration of the intrinsic protein structures during processing for analysis. However, these techniques have not been used in animal feed and nutrition research. The objective of this review was show that with the advanced technique, sensitivity and responses of functional groups to feed processing on a molecular basis could be detected in my research team. These functional groups are highly associated with nutrient utilization in animals.

Qualitative analysis of aromatic compounds via 1D TOCSY techniques

The aromatic compounds,including o-xylene,m-xylene,p-xylene,and ethylbenzene,primarily originate from the catalytic reforming of crude oil,and have a wide variety of applications.However,because of similar physical and chemical properties,these compounds are difficult to be identified by gas chromatography(GC)without standard samples.With the development of modern nuclear magnetic resonance(NMR)techniques,NMR has emerged as a powerful and efficient tool for the rapid analysis of complex and crude mixtures without purification.In this study,the parameters of one-dimensional(1D)total correlation spectroscopy(TOCSY)NMR techniques,including 1D selective gradient TOCSY and 1D chemicalshift-selective filtration(CSSF)with TOCSY,were optimized to obtain comprehensive molecular structure information.The results indicate that the overlapped signals in NMR spectra of nonpolar aromatic compounds(including o-xylene,m-xylene,p-xylene and ethylbenzene),polar aromatic compounds(benzyl alcohol,benzaldehyde,benzoic acid),and aromatic compounds with additional conjugated bonds(styrene)can be resolved in 1D TOCSY.More importantly,full molecular structures can be clearly distinguished by setting appropriate mixing time in 1D TOCSY.This approach simplifies the NMR spectra,provides structural information of entire molecules,and can be applied for the analysis of other structural isomers.

Crystal Structures of (Z)-1-Phenyl-1-phenylseleno- 2-(p-tolylsulfonyl)ethene and (Z)-1,3-Diphenyl-3- phenyl-seleno-2-(p-tolylsulfonyl)-2-propen-1-ol

The molecular structures of compounds (Z)-1-phenyl-1-phenylseleno-2-(p-tolyl- sulfonyl) ethene 1 (C21H18O2SSe, Mr = 413.37) and 1,3-diphenyl-3-phenylseleno-2-(p-tolylsulfonyl) -2-propen-1-ol 2 (C28H24O3SSe, Mr = 519.49) were determined by single-crystal X-ray diffraction analyses. Crystal 1 crystallizes in monoclinic, space group P21/n with a = 12.574(4), b = 12.087(3), c = 13.132(4) , b = 107.973(4), V = 1898.5(9) ?, Z = 4, Dc = 1.446 g/cm3, m = 2.098 mm-1, l = 0.71073 ? F(000) = 840, R = 0.0484 and wR = 0.1085. Crystal 2 crystallizes in monoclinic, space group P21/n with a = 7.0710(4), b = 14.6604(9), c = 24.3432(5) ? b = 94.76(1), V = 2514.8(3) 3, Z = 4, Dc = 1.372 g/cm3, m = 1.603 mm-1, l = 0.71073 ? F (000) = 1064, R = 0.0366 and wR = 0.0573. The X-ray diffraction analysis shows that both of the title compounds are in Z- configuration.

Coverless Information Hiding Based on the Molecular Structure Images of Material

The traditional information hiding methods embed the secret information by modifying the carrier,which will inevitably leave traces of modification on the carrier.In this way,it is hard to resist the detection of steganalysis algorithm.To address this problem,the concept of coverless information hiding was proposed.Coverless information hiding can effectively resist steganalysis algorithm,since it uses unmodified natural stego-carriers to represent and convey confidential information.However,the state-of-the-arts method has a low hidden capacity,which makes it less appealing.Because the pixel values of different regions of the molecular structure images of material(MSIM)are usually different,this paper proposes a novel coverless information hiding method based on MSIM,which utilizes the average value of sub-image’s pixels to represent the secret information,according to the mapping between pixel value intervals and secret information.In addition,we employ a pseudo-random label sequence that is used to determine the position of sub-images to improve the security of the method.And the histogram of the Bag of words model(BOW)is used to determine the number of subimages in the image that convey secret information.Moreover,to improve the retrieval efficiency,we built a multi-level inverted index structure.Furthermore,the proposed method can also be used for other natural images.Compared with the state-of-the-arts,experimental results and analysis manifest that our method has better performance in anti-steganalysis,security and capacity.

Molecular Structure of Kerogen in the Longmaxi Shale: Insights from Solid State NMR, FT-IR, XRD and HRTEM

Kerogen plays an important role in shale gas adsorption,desorption and diffusion.Therefore,it is necessary to characterize the molecular structure of kerogen.In this study,four kerogen samples were isolated from the organic-rich shale of the Longmaxi Formation.Raman spectroscopy was used to determine the maturity of these kerogen samples.Highresolution transmission electron microscopy(HRTEM),13 C nuclear magnetic resonance(13 C NMR),X-ray diffraction(XRD)and Fourier transform infrared(FT-IR)spectroscopy were conducted to characterize the molecular structure of the shale samples.The results demonstrate that VReqv of these kerogen samples vary from 2.3%to 2.8%,suggesting that all the kerogen samples are in the dry gas window.The macromolecular carbon skeleton of the Longmaxi Formation kerogen is mainly aromatic(fa’=0.56).In addition,the aromatic structural units are mainly composed of naphthalene(23%),anthracene(23%)and phenanthrene(29%).However,the aliphatic structure of the kerogen macromolecules is relatively low(fal*+falH=0.08),which is presumed to be distributed in the form of methyl and short aliphatic chains at the edge of the aromatic units.The oxygen-containing functional groups in the macromolecules are mainly present in the form of carbonyl groups(fac=0.23)and hydroxyl groups or ether groups(falO=0.13).The crystallite structural parameters of kerogen,including the stacking height(Lc=22.84?),average lateral size(La=29.29?)and interlayer spacing(d002=3.43?),are close to the aromatic structural parameters of anthracite or overmature kerogen.High-resolution transmission electron microscopy reveals that the aromatic structure is well oriented,and more than 65%of the diffractive aromatic layers are concentrated in the main direction.Due to the continuous deep burial,the longer aliphatic chains and oxygen-containing functional groups in the kerogen are substantially depleted.However,the ductility and stacking degree of the aromatic structure increases during thermal evolution.This study provides quantitative information on the molecular structure of kerogen samples based on multiple research methods,which may contribute to an improved understanding of the organic pores in black shale.