Oligomeric Composition Research Articles

Synthesis and Characterization of Poly (Erythritol Sebacate)

AbstractErythritol is a sweetener polyol widely distributed in nature. Its industrial production is based on biotechnological fermentative processes using yeasts. It is used essentially in nutrition and pharmaceutical fields. However, due to its still high price, the use of erythritol is not widespread and is lower than that of other polyols. The use of erythritol for polymer synthesis remains largely unexplored by the scientific community. This work describes the synthesis and characterization of polyester, poly (erythritol sebacate) (PES), obtained by thermal polycondensation of erythritol and sebacic acid in a two steps approach. A prepolymerization step was realized at different temperatures (150 °C, 160 °C and 170 °C, respectively) followed by a cure step at 150 °C. It was found that using a higher temperature allows the same degree of polymerization (50%) to be achieved in a shorter period, but this leads to prepolymers with a more heterogeneous oligomeric composition. This is reflected in the final properties of the polymers after curing. Synthesis at 150 °C produced a polymer with superior mechanical performance (ultimate tensile strength: 0.5 MPa; Young’s modulus: 0.44 MPa: elongation at break: 123%) and higher chemical resistance to solvents than polymers synthesized at 160 °C and 170 °C. The glass transition temperature (Tg) is between − 20 and 0 °C for all polymers and density is 1.08 g/cm3. Based on these results, we believe that PES is a good elastomer with tunable properties and potential for selective absorption of molecules, such as ethanol, that could be useful for beverage industry and biotechnological applications. Graphical Abstract

Selection of Aptamers for Use as Molecular Probes in AFM Detection of Proteins.

Currently, there is great interest in the development of highly sensitive bioanalytical systems for diagnosing diseases at an early stage, when pathological biomarkers are present in biological fluids at low concentrations and there are no clinical manifestations. A promising direction is the use of molecular detectors-highly sensitive devices that detect signals from single biomacromolecules. A typical detector in this class is the atomic force microscope (AFM). The high sensitivity of an AFM-based bioanalysis system is determined by the size of the sensing element of an atomic force microscope-the cantilever-the radius of the curvature of which is comparable to that of a biomolecule. Biospecific molecular probe-target interactions are used to ensure detection system specificity. Antibodies, aptamers, synthetic antibodies, and peptides can be used as molecular probes. This study has demonstrated the possibility of using aptamers as molecular probes for AFM-based detection of the ovarian cancer biomarker CA125. Antigen detection in a nanomolar solution was carried out using AFM chips with immobilized aptamers, commercially available or synthesized based on sequences from open sources. Both aptamer types can be used for antigen detection, but the availability of sequence information enables additional modeling of the aptamer structure with allowance for modifications necessary for immobilization of the aptamer on an AFM chip surface. Information on the structure and oligomeric composition of aptamers in the solution was acquired by combining small-angle X-ray scattering and molecular modeling. Modeling enabled pre-selection, before the experimental stage, of aptamers for use as surface-immobilized molecular probes.

Controlling the oligomeric composition and char yield of pyrene pitches via continuous supercritical extraction

Continuous supercritical extraction (SCE) was investigated for its ability to control the oligomeric composition of a pyrene pitch generated by the catalytic polymerization of pyrene in the presence of AlCl3. Key objectives of this work were the nearly complete removal of the starting monomer, generation of a well-defined pitch with a high char yield, and isolation of a fraction consisting exclusively of intermediate-sized oligomers. Following the design and construction of an SCE unit for processing up to 500 g/h of feed pyrene pitch with supercritical toluene (Tc = 319 °C, Pc = 41.1 bar), a 2-column setup was used to isolate ∼350 g of a fraction consisting of greater than 90 % isotropic dimer plus mesogenic trimer combined. Although the char yield of this oligomeric mixture was only moderate (i.e., 47.1 %), it still significantly exceeded the weighted average char yield (i.e., 30 %) of the individual monomers present, suggesting a synergistic interplay between the different species during charring. With the above results indicating that pyrene oligomers larger than trimer (i.e., X-mers) are needed to attain higher char yields, the focus of our next continuous SCE run was simply on removing as much unreacted monomer as possible, to the exclusion of all other oligomers. Using a one-column SCE setup, a ∼350 g fraction containing almost 90 % dimer and higher oligomers was isolated, and a respectable char yield of 65.2 % was obtained with this “monomer-depleted” pitch. Furthermore, the softening point was a relatively low 185 °C, quite respectable in terms of processability. In summary, these initial results indicate the potential of continuous SCE as a tool for controlling the properties of oligomeric pyrene pitches for selected applications.

Erratum to:Influence of Chlorides of Mono- and Divalent Metals on the Oligomeric Composition of Lysozyme Crystallization Solutions and Further Crystal Growth

Erratum to:Influence of Chlorides of Mono- and Divalent Metals on the Oligomeric Composition of Lysozyme Crystallization Solutions and Further Crystal Growth

Preparation and applications of two fluoroalkyl end-capped vinyltrimethoxysilane oligomeric composites possessing superoleophilic/superhydrophobic characteristic: a review

Preparation and applications of two fluoroalkyl end-capped vinyltrimethoxysilane oligomeric composites possessing superoleophilic/superhydrophobic characteristic: a review

Influence of Chlorides of Mono- and Divalent Metals on the Oligomeric Composition of Lysozyme Crystallization Solutions and Further Crystal Growth

The influence of the precipitant type (LiCl, NaCl, KCl, NiCl2, and CuCl2) on the formation of oligomers (dimers and octamers) in lysozyme crystallization solutions at two protein concentrations has been investigated by small-angle X-ray scattering (SAXS). The same solutions have been used to grow crystals in order to reveal the influence of the oligomeric composition on the crystal growth. The data obtained in this and previous studies on the influence of precipitant concentration yield an inversely proportional dependence of the total content of octamers and dimers on the cation atomic number, which is in agreement with the increase in the ion activity in the lyotropic series for Li+, Na+, and K+ and the increase in the ionic radius for Li+, Na+, K+, Ni2+, and Cu2+. It is shown that a decrease in the protein concentration in a crystallization solution leads to a decrease in octamer volume fraction at an invariable volume fraction of dimers and reduces the probability of crystal formation.

Ozone assisted autohydrolysis of wheat bran enhances xylooligosaccharide production with low generation of inhibitor compounds: A comparative study

In the present study, ozone assisted autohydrolysis (OAAH) was evaluated for enhanced generation of xylooligosaccharide (XOS) from wheat bran. The total XOS yield with optimum ozone dose of 3% (OAAH-3) was found to be 8.9% (w/w biomass) at 110 °C in comparison to 7.96% at 170 °C by autohydrolysis (AH) alone. Although, there was no significant difference in oligomeric composition (DP 2–6), significant decrease in degradation products namely furfural (2.78-fold), HMF (3.15-fold), acrylamide (nil) and acetic acid (1.06-fold), was observed with OAAH-3 as a pretreatment option. There was 1-fold higher xylan to XOS conversion and OAAH-hydrolysate had higher DPPH radical scavenging activity than AH. PCA plots indicated clear enhancement in XOS production and lower generation of inhibitors with decrease in treatment temperature. Results of the study therefore suggest OAAH can be an effective pretreatment option that can further be integrated with downstream processing for concentration and purification of XOS.

Development of imid-containing appretes for carbon fibers and carbon fabrics

AnnotationThe results of research on synthesis and approbation of new imide-containing high-molecular and oligomeric compounds as appretiruyuschih compositions for carbon fibers under thermoplastic polyetherimide matrix (“Ultem-1000”) are presented. It is shown that both polymeric and oligomeric compositions can be used for carbon fiber appreting, but the greatest effect is manifested when using oligomeric apprets.

Complex Analysis of Fluorescence Intensity Fluctuations of Molecular Compounds

A method is proposed for the complex analysis of fluctuations in the fluorescence intensity of molecular compounds, which allows determining the structural composition of protein oligomers. The idea of the method is to analyze the photon counting histograms of experimental measurements using principal component analysis to assess the presence of oligomeric compounds, and to perform hierarchical cluster analysis, to determine the data classes corresponding to various molecular compounds, followed by selecting cluster medoids to determine the oligomeric composition of protein complexes. The efficiency of the analysis algorithms developed within the framework of the proposed method was confirmed on simulated and experimental photon counting histograms of the measured fluorescence intensity fluctuations of monomeric and dimeric forms of green-fluorescent protein (GFP).

Tunable Electromechanical Liquid Crystal Elastomer Actuators

Liquid crystal elastomers (LCE) are soft materials which anisotropically shape morph in response to external stimuli. Herein, a method to produce large‐area carbon nanotube–LCE nanocomposite films with exceptional electrostrictive properties is examined. A methodology to produce telechelic precursor oligomeric composites at scale (>100 g) is presented along with the continuous casting and photocuring process. The carbon nanotubes are well‐aligned and well‐dispersed in the films, which exhibit exceptional anisotropic thermomechanical, optical, and thermal shape change characteristics. When an electric field is applied through the film thickness, the material quickly and reversibly contracts along the alignment direction. As an example, a compliant carbon nanotube–LCE film contracts >4% against a 140 kPa load, roughly comparable to the blocking force of many natural muscular tissues. Furthermore, it is demonstrated that this tunable contraction is dependent upon the electric field strength, and that the contraction mimics the form function of the input electric field (e.g., a sine wave). These compliant actuators are excellent candidates for incorporation into soft and/or biological systems.

Oligodots: Structurally Defined Fluorescent Nanoprobes for Multiscale Dual-Color Imaging in Vitro and in Vivo.

Nanoscale fluorescent probes are of great importance due to their capabilities for imaging on multiscale. Herein, we report the first synthesis of structurally well-defined nanoparticulate "oligodots" developed for multicolor imaging in vitro and in vivo. These nanoparticles are prepared via condensation and curing reactions where the engineering of the solvent results in the nanoparticles with green (λem = 550 nm) and red (λem = 650 nm) emission range. Differences found in the photophysical properties have been attributed to variations in oligomeric compositions produced during the synthesis as was corroborated by extensive physicochemical characterizations. Specifically, mass spectroscopy provided a picture of the formed species during the synthesis. The feasibility of the oligodots for multicolor imaging is demonstrated both in vitro and in vivo. The red-emitting oligodot is employed for dynamic whole-body imaging in mice. It is envisioned that oligodots would enable multicolor imaging of various biomarkers in complex diseases such as cancer where numerous molecular and metabolic phenotypes work in concert in their emergence.

Dodecamers derived from the crystal structure were found in the pre-crystallization solution of the transaminase from the thermophilic bacterium Thermobaculum terrenum by small-angle X-ray scattering

The pre-crystallization solution of the transaminase from Thermobaculum terrenum (TaTT) has been studied by small-angle X-ray scattering (SAXS). Regular changes in the oligomeric composition of the protein were observed after the addition of the precipitant. Comparison of the observed oligomers with the crystal structure of TaTT (PDB ID 6GKR) shows that dodecamers may act as building blocks in the growth of transaminase single crystals. Correlating of these results to the similar X-ray studies of other proteins suggests that SAXS may be a valuable tool for searching optimum crystallization conditions.AbbreviationSAXSsmall-angle X-ray scatteringTatransaminaseTaTTtransaminase from Thermobaculum terrenumPLPpyridoxal-5’-phosphateR-PEAR-(þ)-1-phenylethylamineBCATbranched-chain amino acid aminotransferaseDAATD-aminoacid aminotransferaseR-TAR-amine:pyruvate transaminaseCommunicated by Ramaswamy H. Sarma

Analysis of crystalline and solution states of ligand-free spermidine N-acetyltransferase (SpeG) from Escherichia coli.

Spermidine N-acetyltransferase (SpeG) transfers an acetyl group from acetyl-coenzyme A to an N-terminal amino group of intracellular spermidine. This acetylation inactivates spermidine, reducing the polyamine toxicity that tends to occur under certain chemical and physical stresses. The structure of the SpeG protein from Vibrio cholerae has been characterized: while the monomer possesses a structural fold similar to those of other Gcn5-related N-acetyltransferase superfamily members, its dodecameric structure remains exceptional. In this paper, structural analyses of SpeG isolated from Escherichia coli are described. Like V. cholerae SpeG, E.coli SpeG forms dodecamers, as revealed by two crystal structures of the ligand-free E. coli SpeG dodecamer determined at 1.75 and 2.9 Å resolution. Although both V. cholerae SpeG and E.coli SpeG can adopt an asymmetric open dodecameric state, solution analysis showed that the oligomeric composition of ligand-free E. coli SpeG differs from that of ligand-free V.cholerae SpeG. Based on these data, it is proposed that the equilibrium balance of SpeG oligomers in the absence of ligands differs from one species to another and thus might be important for SpeG function.

The calmodulin-binding tetraleucine motif of KCNE4 is responsible for association with Kv1.3.

The voltage-dependent potassium (Kv) channel Kv1.3 regulates leukocyte proliferation, activation, and apoptosis, and altered expression of this channel is linked to autoimmune diseases. Thus, the fine-tuning of Kv1.3 function is crucial for the immune system response. The Kv1.3 accessory protein, potassium voltage-gated channel subfamily E (KCNE) subunit 4, acts as a dominant negative regulatory subunit to both enhance inactivation and induce intracellular retention of Kv1.3. Mutations in KCNE4 also cause immune system dysfunction. Although the formation of Kv1.3-KCNE4 complexes has profound consequences for leukocyte physiology, the molecular determinants involved in the Kv1.3-KCNE4 association are unknown. We now show that KCNE4 associates with Kv1.3 via a tetraleucine motif situated within the carboxy-terminal domain of this accessory protein. This motif would function as an interaction platform, in which Kv1.3 and Ca2+/calmodulin compete for the KCNE4 interaction. Finally, we propose a structural model of the Kv1.3-KCNE4 complex. Our experimental data and the in silico structure suggest that the KCNE4 interaction hides a forward-trafficking motif within Kv1.3 in addition to adding a strong endoplasmic reticulum retention signature to the Kv1.3-KCNE4 complex. Thus, the oligomeric composition of the Kv1.3 channelosome fine-tunes the precise balance between anterograde and intracellular retention elements that control the cell surface expression of Kv1.3 and immune system physiology.-Solé, L., Roig, S. R., Sastre, D., Vallejo-Gracia, A., Serrano-Albarrás, A., Ferrer-Montiel, A., Fernández-Ballester, G., Tamkun, M. M., Felipe, A. The calmodulin-binding tetraleucine motif of KCNE4 is responsible for association with Kv1.3.

Estolide Molecular Weight Distribution via Gel Permeation Chromatography

AbstractUsing the universal calibration and the Mark‐Houwink equation (MHE) (), three batches of oleic estolide acids and their corresponding 2‐ethylhexyl esters were characterized using gel permeation chromatography (GPC). The MHE parameters in tetrahydrofuran (THF) at 40 °C were determined (for acids: α = 0.442 ± 0.003 and log10K=2.505 ± 0.007, for esters: α =0.531 ± 0.006 and log10K =2.794 ± 0.018). The fits of the GPC chromatograms yielded also the oligomeric composition of the estolides, which can be used to calculate the estolide number (EN) of an estolide mixture, and other molecular‐weight distribution parameters, such as number‐average molecular weight (Mn), weight‐average molecular weight (Mw), and dispersity (Ð). Using the Deming line fit, we concluded that the GPC should be expected to be approximately three times more sensitive than the currently used methods for determination of EN values.

Investigation of the Structure of Crystal-Forming Solutions of Potassium Dihydrogen Phosphate K(H2PO4) (KDP type) on the Basis of Modeling Precursor Clusters and According to Small-Angle X-Ray Scattering Data

The potassium dihydrogen phosphate K(H2PO4) (KDP) cluster structures formed in aqueous solutions have been theoretically and experimentally investigated. Cluster modeling of the self-assembly of supramolecular KDP structures is performed, and oligomer clusters (dimers, tetramers, and octamers) are determined. Oligomer clusters are found for the first time in saturated KDP aqueous solutions in the temperature range of 5–80°С by small-angle X-ray scattering; their oligomeric composition is quantitatively estimated. It is shown that potassium dihydrogen phosphate exists in the form of dimers in a supersaturated solution in a wide temperature range, and only sharp cooling leads to the occurrence of other clusters: first tetramers and then octamers; the latter are presumably primary chains of the KDP crystal structure. The distance between tetramer centers corresponds to the translation period c = 6.906 A.

Shape Determination of Bovine Fibrinogen in Solution Using Small-Angle Scattering Data

A 3D model of the shape of bovine fibrinogen, one of the proteins responsible for blood coagulation, is constructed based on small-angle X-ray scattering (SAXS) data on bovine fibrinogen in solution, and the oligomeric composition of fibrinogen in solution is estimated. It is shown that fibrinogen molecules form elongated vermicular structures with a length on the order of 50 nm and an effective cross section of about 10 nm. The volume of these particles correlates well with the volume of two fibrinogen dimers. The results obtained may be helpful when applying fibrinogen and its modifications in tissue engineering.

Isothermal Evaporation of α-Pinene Ozonolysis SOA: Volatility, Phase State, and Oligomeric Composition

We present measurements of the isothermal evaporation of α-pinene ozonolysis secondary organic aerosol (SOA). Using a novel, filter-based method, we reproduce literature observations of the time-dependent evaporation of SOA particles. We apply two detailed physical models to interpret the evaporative behavior of both the bulk SOA and individual components. Both models find that a combination of effectively nonvolatile products, together with reversibly formed oligomers (or otherwise reactive monomers) having a decomposition lifetime of 9 to 28 h, best explains the evolution of composition and volatility as particles age in the absence of both organic vapors and oxidants, even under an assumption of relatively viscous (soft wax-like with a minimum diffusion coefficient of 1 × 10–15 cm2 s–1) particles. We find that the residence time in the SOA formation chamber and time spent undergoing isothermal evaporation, both indicative of the physical age of the aerosol, are the most important experimental parameter...

Consensus Bayesian assessment of protein molecular mass from solution X-ray scattering data

Molecular mass (MM) is one of the key structural parameters obtained by small-angle X-ray scattering (SAXS) of proteins in solution and is used to assess the sample quality, oligomeric composition and to guide subsequent structural modelling. Concentration-dependent assessment of MM relies on a number of extra quantities (partial specific volume, calibrated intensity, accurate solute concentration) and often yields limited accuracy. Concentration-independent methods forgo these requirements being based on the relationship between structural parameters, scattering invariants and particle volume obtained directly from the data. Using a comparative analysis on 165,982 unique scattering profiles calculated from high-resolution protein structures, the performance of multiple concentration-independent MM determination methods was assessed. A Bayesian inference approach was developed affording an accuracy above that of the individual methods, and reports MM estimates together with a credibility interval. This Bayesian approach can be used in combination with concentration-dependent MM methods to further validate the MM of proteins in solution, or as a reliable stand-alone tool in instances where an accurate concentration estimate is not available.

Oligomeric Composition of Polyols From Fatty Acid Methyl Ester: The Effect of Ring‐Opening Reactants of Epoxide Groups

AbstractCommercial availability of fatty acid methyl ester (FAME) from palm oil targeted for biodiesel offers a good feedstock for the production of structurally well‐defined polyols for polyurethane applications. The effect of molecular weight (MW), odd and even carbon numbers, and the linear and branched structure reactants used in the ring‐opening reaction of epoxidized fatty acid methyl ester (E‐FAME) on the properties of polyols was investigated. Conversions of E‐FAME to PolyFAME polyols were confirmed by Fourier transform infrared analysis, oxirane oxygen content, and hydroxyl number. Gel permeation chromatography (GPC) calibrated against polyether polyols as a standard and vapor pressure osmometry were used for MW determination. GPC chromatograms of PolyFAME polyols clearly demonstrated the formation of oligomers during ring‐opening reactions. MW, and odd and even carbon numbers in a structure of linear diols and branched diol used in the syntheses of PolyFAME polyols did not have an effect on crystallinity, glass transition, or melt temperatures measured using Differential scanning calorimetry (DSC). PolyFAME polyols ring‐opened with water, methanol, and 1,2‐propanediol contained secondary hydroxyl groups, whereas PolyFAME polyols ring‐opened with linear diols contained a mixture of primary and secondary hydroxyl groups. It was found that the concentration of primary hydroxyl groups increased significantly by increasing the number of carbons from C2 to C3 in the linear diols. The viscosity of PolyFAME polyols also increased with the MW of linear diols used in the E‐FAME ring‐opening reaction. These findings would be beneficial for formulators in choosing the most cost effective polyols for polyurethane formulations.