NMR molecular characterization of lubricating base oils: Correlation with their performance

The NMR technique was used to characterize some base oils of different nature (mineral, saturated polyolefins, hydrocracked and from waxes hydroisomerization) at the molecular level. Base oils are used in the formulation of lubricants with the addition of suitable additives which improve the final products performance. The studied base oils are used particularly in the formulation of engine oils. In this paper we have compared two “NMR editing” techniques which allow one to quantify the CH_n (n = 0?3) fractions of an “average” base oil molecule: 1) the gated spin echo (GASPE) and 2) the distortionless enhancement by polarization transfer (DEPT). We found that the quantitative data obtained from GASPE have a better accuracy than those from DEPT and so we chose GASPE to study the molecular characteristics of the aliphatic moieties of the base oils. On the basis of the GASPE data and of the average molecular mass obtained via VPO (Vapor Pressure Osmometry), the average number of branches and aliphatic rings were calculated. Moreover, on the basis of GASPE the distribution of side chain lengths and the positions of the methyl groups along the straight chain (methyls are the only groups for which the positions are directly obtained from NMR spectra) were obtained. A confirmation of the reliability of the NMR approach was achieved by comparing the branching degree, found with the NMR approach, of some base oils with their heats of fusion measured with the Differential Scanning Calorimetry (DSC). The heats of fusion are expected to be directly related to the length of straight CH₂ sequence and therefore to be lower for more branched molecules. We found that for base oils with similar aliphatic moieties, the heats of fusion are lower for more branched base oil molecules with a nearly linear correlation. The exception to this rule is represented by the two olefinic oils. Besides, we found that the fraction of the methyls on aliphatic chains longer than three carbons, determined with GASPE, correlates very well with the pour points values, with the only exception of the mineral oil.     

Photorefractive polymers sensitized by two-photon absorption

We demonstrate the recording of holograms and their nondestructive readout in a photorefractive polymer, using two-photon absorption. Sensitivity is provided by the excitation of the electroactive chromophore with femtosecond pulses, followed by charge injection into the photoconducting poly(N -vinylcarbazole) matrix. The holograms can be fully erased with a pulsed laser source but are insensitive to cw laser beams with the same wavelength. Studies of the field and intensity dependence of the diffraction efficiency indicate that the holograms are formed through the photorefractive effect.     

Mössbauer study of novel iron(II)-dioxime complexes with branched alkyl chains

Novel iron(II) oxime complexes with dimethyl-glyoxime, methyl-ethyl-glyoxime, methyl-isopropyl-glyoxime, [Fe(DioxH)₂L₂] with and without axial ligands have been synthesized. ⁵⁷Fe Mössbauer spectroscopy showed different spin states in complexes with short alkyl chain and with branched alkyl chain, respectively. It was shown that the asymmetry observed in the doublet line intensity of iron-bis-glyoximes is due to the texture effect. The effect of back-coordination was also studied in the case of iron-bis-dioxime complexes with branched alkyl chains, having different axial ligands.     

Chromophores of the green fluorescent protein studied in the gas phase

Absorption of gas-phase biomolecules has been studied at the heavy-ion storage ring ELISA. Here we discuss the absorption characteristics of the chromophores of the Green Fluorescent Protein (GFP). The gas-phase absorption maximum of the deprotonated chromophore (anion form) is at 479 nm. This is almost identical to one of the two absorption maxima of the protein, being at 477 nm, which is ascribed to a deprotonated chromophore in the protein. The protonated chromophore (cation form) has a maximum at 406 nm in the gas phase. We compare the gas-phase results with absorption profiles of GFP and chromophores in liquids, and argue that the absorption characteristics of GFP are mainly ascribed to intrinsic chemical properties of the chromophore. Evidently, the special β-can structure of GFP provides shielding of the chromophore from the surroundings without significantly changing the electronic structure of the chromophore through interactions with amino acid side chains. Received 28 December 2001 Published online 13 September 2002     

Effects of Carbon Black on Chain Mobility and Dynamic Mechanical Properties of Solution Polymerized Styrene-Butadiene Rubber

The structure of the bound rubber, the ¹H NMR (nuclear magnetic resonance) relaxation time, and the crosslink density of the physical network and the glass transition, were studied for solution polymerized styrene-butadiene rubber (SSBR) filled by carbon black, to investigate the effects of carbon black on the chain mobility and dynamic mechanical properties. It was found by ¹H NMR analysis that the rubber chains were adsorbed on the surface of carbon black to form physical crosslinks and restrict the mobility of the chains, especially for some high-mobility units such as chain ends. It was calculated, according to the molecular weight between adjacent crosslinks, that the main motion units of the tightly adsorbed chains appeared to be similar in size to the chain segments. The glass transition temperature (T _g) obtained by differential scanning calorimetry (DSC) could not be used to judge the effect of carbon black on chain mobility, while the appearance and change of the loss-tangent (tan δ) peak at high temperature in dynamic mechanical thermal spectrometry (DMTS) test showed that there were three chain states: free chains, loosely adsorbed chains, and tightly adsorbed chains. The dynamic rheology test showed that the unfilled SSBR compound had the rheological characteristics of entangled chain networks; however the nonlinear viscoelasticities of the filled SSBR were related to the gradual disentanglement of adsorbed chains and free chains. The peaks in tan δ vs. temperature curves implied that the motion unit size decreased with the increase of bound rubber content, and the modulus vs. temperature curve showed an apparently lower mobility of adsorbed chains than that of free chains through the very low dependence of modulus on temperature for the highly filled compounds. The extremely high tensile modulus of the vulcanizate with 63.6% carbon black at room temperature also implied that the adsorbed chains were in the glass state due to their restriction by the carbon black.     

Photorefractive effect of a novel conjugate polymer containing transition metal complex

The photorefractive effect (PR) of a novels σ-π alternating polymer having 2,2'-bipyridyl in the polymer backbone and their ruthenium complexes has been investigated. The ruthenium complex was used as the charge generator, the σ-π alternating polymer backbone as the charge transporting channel and second-order nonlinear (NLO) optical chromophore. The photorefractive properties were demonstrated by two-beam coupling (2BC), degenerated four-wave mixing (DFWM) and field-induced orientation birefringence at wavelength of 532 nm. This polymer shows a enhanced photorefractive effect due to the efficient photoinduced metal-to-ligand charge transfer (MLCT) inside the ruthenium complex. A net optical gain of about 22 cm^-1 and the diffraction efficiency about 10% were obtained at the external electric field of 30 V/μm. Received 21 December 1999 and Received in final form 7 July 2001     

低玻璃化转变温度的光折变聚合物中光敏剂作用研究

通过对光敏剂C₆₀含量不同的低玻璃化转变温度的光折变聚合物聚乙烯咔唑掺杂2,5-二甲基-4-(4′-硝基苯偶氮基)苯甲醚、N-乙基咔唑和C₆₀的空间相移角和二波耦合系数的测量,研究了光敏剂在此类光折变聚合物中的作用- 关键词：     

Vibrational spectra of activated rei of wolframile-phosphate glasses

The vibrational spectra of wolframile-phosphate glasses with a high concentration of WO ₂ ²⁺ and Ln³⁺ ions were investigated and the structure of these glasses was analized. It is shown that the investigated glasses are formed predominantly by chain polyphosphates. Tungstate enters into the net of the glass in octahedral coordination, “stitching” the polyphosphate chains together but not isomorphously substituting phosphorus. In the glass structure nonlinear wolframile groups with the multiple tungsten-oxygen bonds are formed. The introduction of lanthanide oxides into the glass composition causes the average degree of its polymerization to decrease. F. Skorina Gomel' State University, 104 Sovetskaya St., Gomel', 246699, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 2, pp. 236–241, March–April, 1997.     

Kinetics of “quenching” effect in C60 crystals

The thermodynamic transition in the C₆₀ crystals subjected to uniaxial compression at different temperatures and heat treatment has been investigated by differential scanning calorimetry (DSC). The kinetic parameters of the irreversible endothermic “quenching” effect are determined. It is revealed that the process is accompanied by the cooperative molecular motion, which is characteristic of the high-elasticity state of organic glasses.     

Crystallization Behavior of Modified Polyester with Varied Macromolecular Architecture

Several modified polyesters with varied macromolecular architecture, such as branched poly(ethylene terephthalate) (PET) based on glycerol (GL) from 0.004 to 0.05 mol ratio as a branching agent, blocked and branched poly(butylene terephthalate)‐polyether containing poly(tetramethylene oxide) (PTMO) as soft segment and GL as a branching unit, as well as segmented poly(ethylene terephthalate)‐polyether,were prepared. Their crystallization behavior was studied by differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction (WAXD), and polarized optical microscopy (POM). It was found that a small extent of branching may enhance the crystallization of poly(ethylene terephthalate), while high degrees of branching (0.035–0.05) could block the development of crystallization. On the other hand, for even a small extent of incorporation of GL in the more flexible poly(butylene terephthalate)‐polyether chains, no enhanced crystallization was observed; blocking of crystallization from a branching defect may play the main role. The introduction of PTMO in poly(ethylene terephthalate) chains to a small degree facilitated the nucleation and speeded crystallization, but decreased the melting points of the polymers. A small number of nuclei and the greater induction time were found for branched PETs. The spherulities developed in branched PETs were larger and more perfect than those in PET due to less truncation of spherulites resulting from fewer nuclei, whereas the size of spherulities in poly(ethylene terephthalate)‐polyether became smaller with the increase of PTMO.     

Molecular Simulation of Salt Ion Effect on Anionic Polyelectrolyte Chain

The effect of salt ions on anionic polyelectrolyte chain structure has been studied by molecular mechanics and molecular dynamics, and the reason for sedimentation of the anionic polyelectrolyte in the salt solution is explored. Considering sodium polyacrylate as a model compound of anionic polyelectrolytes, the conformation of polyacrylate in salt-free and CaCl₂ solution is studied. The simulation results showed that anionic polyelectrolytes in aqueous solution had an extended chain structure due to the role of strong electrostatic repulsion. After introduction of Ca²⁺ to the solution, the collapse of the anionic polyelectrolyte chain happens. By analysis of the radius of gyration and the radial distribution function, the basic reason for the collapse of anionic polyelectrolyte chains in salt solution is clarified with atomistic resolution.     

Effects of alkyl side chains on properties of aliphatic amino acids probed using quantum chemical calculations

Effects of alkyl side chains (R‐) on the electronic structural properties of aliphatic amino acids are investigated using quantum mechanical approaches. The carbon (C 1s) binding energy spectra of the aliphatic amino acids are derived from the C 1s spectrum of glycine (the parent spectrum) by the addition of spectral peaks, depending on the alkyl side chains, appearing in the lower energy region IP < 290 eV (where IP is the ionization potential). The two glycyl parent spectral peaks of the amide 291.0 eV [C₍₂₎] and carboxylic 293.5 eV [C₍₁₎] C atoms are shifted in the aliphatic amino acids owing to perturbations depending on the size and structure of the alkyl chains. The pattern of the N 1s and O 1s spectra in glycine is retained in the spectra of the other amino acids with small shifts to lower energy, again depending on the alkyl side chain. The Hirshfeld charge analyses confirm the observations. The alkyl effects on the valence binding energy spectra of the amino acids are concentrated in the middle valence energy region of 12–16 eV, and hence this energy region of 12–16 eV is considered as the `fingerprint' of the alkyl side chains. Selected valence orbitals, either inside or outside of the alkyl fingerprint region, are presented using both density distributions and orbital momentum distributions, in order to understand the chemical bonding of the amino acids. It is also observed that the HOMO–LUMO energy gaps of the aliphatic amino acids are reduced with the growth of the alkyl side chain.     

Synthesis and third-order nonlinear optical property of poly（urethane-imide）

The poly（urethane-imide） （PUI） which uses isophorone diisocyanate, dispersed red 19 （DR-19）, and py- romellitic dianhydride is synthesized. The PUI is characterized by Fourier transform infrared （FT-IR） spectroscopy, differential scanning calorimetry （DSC）, and thermogravimetric analysis （TGA）. The results of DSC and TGA indicate that the PUI exhibits high thermal stability up to its glass-transition temperature of 209 ℃ and 5° heat weight loss temperature of 296℃. The fluorescence spectra of PUI and DR-19 are measured, showing that the fluorescence effect of PUI is very similar to that of DR-19 except for the light decrease of fluorescence intensity, which indicates that the fluorescence effect of PUI is generated by the azobenzene groups in its macromolecular chains. The maximum molar absorption coefficient, absorp- tion wavelength, and chromophores density are measured and used to calculate the third-order nonlinear optical coefficient X（3） to be 3.96×10^-13 esu. The nonlinear refractive index coefficient and molecular hyperpolarizabilitv of PUI are also obtained. PUI is oroved to have an excellent ootical Performance.     

Dynamics of chain molecules in disordered materials

The dynamic behavior of hard chains in disordered materials composed of fixed hard spheres is studied using discontinuous molecular dynamics simulations. The matrix induces entanglements in the chain fluid, i.e., for high matrix densities the diffusion coefficient D scales with the chain length N as D is approximately N(-2). At high matrix densities the rotational relaxation time becomes very large but the translational diffusion is not affected significantly; i.e., the chains display a dynamic heterogeneity reminiscent of probe diffusion in supercooled liquids and glasses. We show that this is because some chains are trapped, and move via a hopping mechanism. There are no signatures of this dynamic heterogeneity in the matrix static structure, however, which is identical to that of a hard-sphere liquid.     

Efficiently Tuning the Absorption and Fluorescence Spectroscopy of the Novel Branched p-Nitro-stilbene Derivatives with Chemical Strategy

Suitable chemical strategy is a useful approach on the tuning color and photoluminescence of organic dyes. This paper presented tuning novel branched p-nitro-stilbene derivatives efficiently with a new chemical strategy through variation of chemical bridged bond. Linking bonds played significant effects on the absorption and fluorescence spectroscopy of the branched p-nitro-stilbene derivatives. A change from “D-π-A” to “A-π-A” chemical structural characteristics occurred for the branched p-nitro-stilbene derivatives as ester bond was attached. This led to not only large hypsochromic shift of the maximal absorption wavelength of the branched p-nitro-stilbene derivatives, but considerable reduction of the fluorescence intensity. While in contrast, the branched p-nitro-stilbene derivatives with ether bond exhibited longer wavelength absorption and much stronger fluorescence emission in modest polar solvent. The cyclic voltammograms of these branched p-nitro-stilbene derivatives were determined. Different electrochemistry processes were observed for the branched p-nitro-stilbene derivatives with various linking bonds. The energies of frontier orbital of the branched p-nitro-stilbene derivatives were estimated from their corresponding redox potentials. Molecular geometry optimization of the branched p-nitro-stilbene derivatives was performed, and the electron density distribution of frontier orbital was analyzed. Thermal stabilities of these branched nitro-stilbene derivatives were investigated via the analysis of the differential scanning calorimetry (DSC) and thermograving (TGA) curves. This paper presented strong evidences that the absorption and fluorescence spectroscopy of the branched stilbene derivatives could be mediated efficiently by chemical strategy.     

Intrinsic photorefractive effect of LiNbO3

The photorefractive effect of undoped LiNbO₃ crystals of high purity is studied by means of two-photon excitation of picosecond light pulses. We show that two-photon photorefractive recording is accompanied by characteristic changes of the optical absorption and electron spin resonance spectra due to the formation of color centers. The role of these centers for the photorefractive process in discussed.     

Photoelectric, nonlinear optical, and photorefractive properties of polymer composites including carbon nanotubes and cyanine dyes

The effect of cyanine dye additives on the photoelectric, nonlinear optical, and photorefractive properties of polyvinyl carbazole composites based on closed single-walled carbon nanotubes has been investigated. It has been found that these characteristics are affected by the dye in which the lowest unoccupied molecular orbital (LUMO) lies below the level of the photoexcited nanotube. The addition of this dye to the composite leads to a 14-fold increase in the quantum efficiency of the generation of mobile charge carriers under irradiation by a laser (1064 nm) in the absorption region of the nanotubes. Moreover, the addition of the dye to the composite decreases the third-order susceptibility χ⁽³⁾, presumably, due to the opposite orientations of dipoles of the dye and the nanotube upon adsorption of the dye on the nanotube. The addition of the dye to the composite also provides a twofold increase in the two-beam photorefractive amplification factor of the laser beam with a wavelength of 1064 nm. The obtained values of the two-beam photorefractive amplification factor reach 120 cm^?1.     

Analysis of branched oligophenylene by absorption and fluorescence spectra

A branched oligophenylene has been synthesized based on 1,3,5-tri(4′-bromophenyl)benzene. Absorption and fluorescence spectra were studied and fluorescence quantum yields and lifetimes were measured for the compound in solution. It is demonstrated that the absorption spectrum is a superposition of p-quaterphenyl, p-terphenyl, and biphenyl chromophore absorption bands in a 1:2:1 ratio. The oligomer fluorescence spectrum is found to depend on the excitation wavelength. It is shown that the oligomer fluorescence is determined by two fluorochromic groups, namely fragments with branched p-terphenyl and p-quaterphenyl units. The main fluorescence maxima for these fluorochromic groups coincide with each other and lie in the vicinity of λ = 360 nm. A very weak fluorescence band found in the region 380–440 nm is excited by light with a wavelength lying beyond the oligomer self-absorption region. The reasons for a decrease in fluorescence quantum yields of branched models and the studied oligophenylene as compared with those of linear p-polyphenylene chromophores are discussed.     

Higher-order diffraction images in photorefractive materials

We report some photorefractive higher-order diffraction phenomena of a liquid crystal polymer composite. The photorefractive composite consists of the polymer poly[N-vinylcarbazole] (PVK) doped with the chromophore 4,4′-n-entylcyanobiphenyl (5CB) and the sensitizer C₆₀. In two-wave coupling experiments, the signal beam was interfered by a mutually coherent reference beam within composite materials at a small incident angle. Results are given when the composite was placed behind the focal plane, in front of the focal plane, and in the focal plane. Higher-order diffraction images were obtained by amplification and reduction. A theory of the properties of higher-order diffraction images in a photorefractive liquid crystal polymer composite is developed. The theory is in good agreement with the results of experimental work. The experiments demonstrate the feasibility of optical image processing.