Study of the Impact Resistance of Physically and Dynamically Vulcanized Mixtures of PP/EPDM

Physically and dynamically vulcanized (TPV) mixtures of polypropylene (PP) and ethylene propylene diene terpolymer (EPDM) are prepared by extrusion in order to improve the impact resistance of PP. To enhance the chemical compatibility and provide better interaction between the PP and EPDM in the physical mixtures, both polymers are modified with maleic anhydride (MAH) in solution using xylene as solvent and dicumyl peroxide (DCP) as initiator. The qualitative and quantitative determination of the degree of grafting is study by Fourier Transform Infrared Spectroscopy (FTIR) and varying the amount of DCP and/or amount of MAH in order to determine the optimum amounts to obtain the highest degree of grafting. The effect of the relation of PP/EPDM, the amount of reinforcement filler and mix rate are studied for modified polymer mixtures (PP-g-MAH/EPDM-g-MAH). For the TPV of PP/EPDM the effects of amount and triallylisocyanurate (TAC) as coupling agent in presence of different amounts of DCP are studied. The physical mixtures of modified polymers prepared with a PP/EPDM ratio of 80/20 and the TPVs blends prepared with a PP/EPDM ratio of 70/30 and containing 15% filler at 60 rpm show the highest impact resistance. The impact resistance, melt flow index and hardness of the different mixtures are measured to determine their possible applications to prepare front panels and bumpers for automobiles by injection molding.     

Molecular Dynamics Simulation for the Impact of External Electric Fields on CaCl2 Aqueous Solution

Non-equilibrium molecular dynamics(MD) simulations were performed according to the electronic anti-fouling technology, and some structural parameters and dynamic parameters of CaCl₂ aqueous solution were taken as indicators to compare the different effect on the anti-fouling performance by applying different electric fields. The results show that electric fields can effectively decrease the viscosity of CaCl₂ aqueous solution and enhance the ionic activity by enlarging the self-diffusion coefficient. In addition, with the same electric field strength, the electrostatic field is more effective at decreasing the viscosity of CaCl₂ aqueous solution and increasing the self-diffusion coefficient of water molecules, while the alternating electric field is more effective at increasing the self-diffusion coefficient of Ca²⁺. Furthermore, an alternating electric field with different frequencies was applied; the results show that an 800 kHz frequency is most effective to decrease the viscosity, and a 700 kHz frequency is most effective to enhance the self-diffusion coefficient of water molecule. Otherwise, 400 kHz is most effective to enhance the self-diffusion coefficient of Ca²⁺. Additionally, by studying the change of structure parameters, it was concluded that an external electric field can enhance the hydration between Ca²⁺ and coordinated water molecules, and the alterna- ting electric field is more effective in this respect.     

Impact of gel layer formation on colloid retention in membrane filtration processes

Colloidal particles in the feed streams of membrane filtration processes control membrane fouling rate in many instances. In this study, the non-gelling colloidal Na-alginate and the gelling colloidal Ca-alginate are employed to investigate the significance of gel layer formation in membrane filtration processes in terms of contribution to membrane fouling and supplementary impurity removal. The results show that contribution of colloidal particles to membrane fouling depends on the gelling propensity of the colloids and the operational mode (constant pressure or constant flux) implemented. A small dose of either Na-alginate or Ca-alginate was found to greatly increase membrane fouling rate during constant pressure filtration. Both the resistance to removal by application of shear and the lower susceptibility of the concentration polarization layer to shear resulted in more severe fouling during constant flux filtration in the presence of Ca-alginate assemblages than in the presence of Na-alginate. Apparent channel sizes of the Ca-alginate gel layer were calculated from the material properties of the fouling layer. Incomplete catalase retention highlighted the likely heterogeneity in size of liquid transport pathways. Adsorption also contributed to the trapping of colloidal particles according to the retention behaviour of BSA by the Ca-alginate gel layer. Gel layer formation propensity should be seriously considered for the operation of membrane filtration processes. Two simple methods based on (i) a permeability recovery experiment and (ii) comparison of dead-end filtration behaviour with and without shear application are proposed for evaluation of the gelling propensity of colloidal dispersions.     

Multidimensional Analytical Techniques for Studying the Thermo-Oxidative Degradation of Impact Poly(propylene)

Summary: Impact poly(propylene) copolymers (ICPP) are complex polymer systems containing various types of ethylene-propylene copolymers as well as the majority poly(propylene) phase. In this study, multidimensional analytical techniques are applied to study the thermo-oxidative degradation of these complex materials. The combination of size exclusion chromatography (SEC) and FTIR via an LC-transform interface allows for the identification and tracking of the low molecular weight oxidized products. The degradation has a significant effect on the crystallisability of the material. DSC analysis shows that as the degradation proceeds, there is a significant decrease in the onset of the melt endotherm as well as the development of a double melt peak and peak broadening. Preparative Temperature Rising Elution Fractionation (TREF) is used to isolate the various fractions according to crystallisability during the polymer degradation. TREF-SEC and TREF-(SEC-FTIR) allows for the isolation and identification of the polymer fractions undergoing oxidative degradation. It is shown that these multidimensional analytical techniques using crystallisability in the first dimensional fractionation provide more information on the mechanism and process of oxidative degradation than traditional bulk analysis methods.     

Induction of Liver Size Reduction in Zebrafish Larvae by the Emerging Synthetic Cannabinoid 4F-MDMB-BINACA and Its Impact on Drug Metabolism

Zebrafish (ZF; Danio rerio) larvae have become a popular in vivo model in drug metabolism studies. Here, we investigated the metabolism of methyl 2-[1-(4-fluorobutyl)-1H-indazole-3-carboxamido]-3,3-dimethylbutanoate (4F-MDMB-BINACA) in ZF larvae after direct administration of the cannabinoid via microinjection, and we visualized the spatial distributions of the parent compound and its metabolites by mass spectrometry imaging (MSI). Furthermore, using genetically modified ZF larvae, the role of cannabinoid receptor type 1 (CB1) and type 2 (CB2) on drug metabolism was studied. Receptor-deficient ZF mutant larvae were created using morpholino oligonucleotides (MOs), and CB2-deficiency had a critical impact on liver development of ZF larva, leading to a significant reduction of liver size. A similar phenotype was observed when treating wild-type ZF larvae with 4F-MDMB-BINACA. Thus, we reasoned that the cannabinoid-induced impaired liver development might also influence its metabolic function. Studying the metabolism of two synthetic cannabinoids, 4F-MDMB-BINACA and methyl 2-(1-(5-fluoropentyl)-1H-pyrrolo[2,3-b]pyridine-3-carboxamido)-3,3-dimethylbutanoate (7′N-5F-ADB), revealed important insights into the in vivo metabolism of these compounds and the role of cannabinoid receptor binding.     

Effect of Ethylene-Propylene Copolymer Composition on Morphology and Surface Properties of Impact Poly(propylene) Copolymer

Summary: Impact poly(propylene) copolymers (IPC) having various ethylene-propylene rubber (EPR) compositions were prepared using a high activity Ziegler-Natta catalyst. EPR composition was characterized by temperature rising elution fractionation (TREF) analysis and FT-IR spectroscopy. Effect of EPR composition on the morphology and surface properties of IPC was investigated by scanning electron microscopy (SEM), 3D profiler, and gloss meter. Composition and amount of amorphous and crystalline EPR were quantified by TREF and found to be dependent on the ethylene content in EPR. From the SEM result, it was found EPR composition has a strong influence on its shape and size. IPCs containing propylene-rich EPR exhibited a finer dispersion of EPR phase. The surface roughness decreased with decreasing ethylene content in EPR. The comparison of EPR composition and morphology and surface properties exhibited strong correlations.     

Synthesis of a Dicyclohepta[a,g]heptalene-Containing Polycyclic Conjugated Hydrocarbon and the Impact of Non-Alternant Topologies

Incorporating non-hexagonal rings into polycyclic conjugated hydrocarbons (PCHs) can significantly affect their electronic and optoelectronic properties and chemical reactivities. Here, we report the first bottom-up synthesis of a dicyclohepta[a,g]heptalene-embedded PCH ( 1 ) with four continuous heptagons, which are arranged in a “Z” shape. Compared with its structural isomer bischrysene 1 R with only hexagonal rings, compound 1 presents a distinct antiaromatic character, especially the inner heptalene core, which possesses clear antiaromatic nature. In addition, PCH 1 exhibits a narrower highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) energy gap than its benzenoid contrast 1 R , as verified by experimental measurements and theoretical calculations. Our work reported herein not only provides a new way to synthesize novel PCHs with non-alternant topologies but also offers the possibility to tune their electronic and optical properties.     

Impact of carbon dioxide on the surface tension of 1-hexanol aqueous solutions

Effects of carbon dioxide presence on the surface tension and adsorption kinetics of 1-hexanol solutions were investigated. Experiments were performed at a range of carbon dioxide vapor pressures and varying concentrations of 1-hexanol aqueous solution. Both dynamic and steady-state surface tensions of 1-hexanol aqueous solution were found to decrease with carbon dioxide pressure, and a linear relationship was observed between the steady-state surface tension and carbon dioxide pressure. To explain the experiments, adsorption and desorption of the two species (1-hexanol and carbon dioxide) from two sides of the vapor-liquid interface were considered. A modified Langmuir isotherm, the modified Langmuir equation of state and the modified kinetic transfer equation were developed. The resulting steady-state and dynamic surface tension data were modeled using the modified Langmuir equation of state and the modified kinetic transfer equation, respectively. Equilibrium constants and adsorption rate constants of 1-hexanol and carbon dioxide were evaluated through a minimization procedure for CO₂ pressures ranging from 0 to 690 kPa. From the steady-state modeling, the equilibrium parameters for 1-hexanol and carbon dioxide adsorption from vapor phase and liquid phase were found unchanged at different pressures of carbon dioxide. From the dynamic modeling, the adsorption rate constants for 1-hexanol and carbon dioxide from vapor phase and liquid phase were found to decrease with carbon dioxide pressure. Some fluctuations in the fitting parameters of the dynamic modeling (adsorption rate constants) were observed. These fluctuations may be due to experimental errors, or more likely the limitations of the model used. A major limitation of the model is related to large differences in adsorption/desorption between initial and final stages of the process, and a single set of property parameters cannot describe both initial and final states of the system. Variations may occur depending on which set of data, of initial or final states, is used in the model predictions over the entire time range.     

Polylactide (PLA) and Highly Filled PLA - Calcium Sulfate Composites with Improved Impact Properties

Summary: Starting from gypsum as by-product of lactic acid fabrication process, novel high performance composites have been produced by melt-blending PLA and this filler after a previous specific dehydration performed at 500 °C for min. 1h. Due to PLA sensitivity towards hydrolysis, the utilization of β-anhydrite II (AII) as filler is a prerequisite. Characterized by attractive mechanical and thermal properties due to good filler dispersion throughout the polyester matrix, these composites are interesting in biodegradable rigid packaging or technical applications. Interestingly, tensile strength of PLA – AII composites proved remarkably high, e.g. higher than 35 MPa at 50 wt-% filler content. However a decrease of impact properties has been recorded. To increase the toughness of these composites while preserving high stiffness an impact modifier based on ethylene copolymer has been mixed with both the polymer matrix and AII by melt-compounding. The effectiveness of the impact modifier was confirmed in both neat PLA and AII-based composites. Addition of 5-10 wt-% impact modifier into highly filled composites (30 to 40 wt-% filler) leads to an attractively threefold increase of impact strength with respect to the compositions without modifier, remarkable thermo-mechanical performances and good filler dispersion.     

新型温度敏感性自组装胶束P(NiPAAm-co-DMAA)-co-P(L-Ala)的合成和性能

通过原子转移自由基聚合(ATRP)合成了一种带有活性—NH2基团的温度敏感性亲水型共聚物P(NiPAAm-co-DMAA), 并将其作为引发剂, 合成了P(NiPAAm-co-DMAA)-co-P(L-Ala), 其分子量分布(PDI)在1.3左右. 聚合物通过自组装形成纳米胶束. 透射电镜(TEM)结果表明, 胶束大小200~300 nm, 具有明显的核壳结构. 共聚物的最低临界溶解温度(LCST)为45.5 ℃. 温度低于LCST时, 聚合物溶解形成胶束; 高于LCST时, 胶束解离, 聚合物不溶. 聚合物对温度的响应是快速而可逆的.     

CO2 Hydroboration: Impact of the Boryl Moieties on the Reactivity of Four Bis(boryl)acetal Compounds toward 2,6-Diisopropylaniline

The hydroboration of CO₂ into bis(boryl)acetal (BBA) compounds is an important transformation, since it enabled to selectively reduce CO₂ by 4e^- and to subsequently use the BBA compounds as C₁ and C_n sources. However, the influence of the nature of the boryl moieties on the reactivity of BBA compounds has not been evaluated so far. In the present study, four BBA compounds – including two new ones – were reacted with 2,6-diisopropylaniline to afford the expected imine. Significant differences in the rate of the reaction from minutes to weeks have been observed depending on the BBA used, showing the importance of the nature of the boryl moieties. Theoretical investigations enabled to propose a mechanism involving the addition of the aniline to the BBA as the rate-determining step and to determine that the steric hindrance of the BBA compounds is the main factor driving the rate of this condensation reaction.     

手性二噁唑啉吡啶铁和镍配合物的制备与表征

Tridentate bis(oxazolinylpyridine)(1) reacted with nickel chloride or ferrous chloride in anhydrous ethanol to form bis(oxazolinylpyridine) Nickel(Ⅱ) and Iron(Ⅱ) complexes. The stable solid complexes were characterized with IR， UV， MS， XPS and elemental analysis. No stable complexes were formed with bidentate bis(oxazoline)(2) ins- tead of bis(oxazolinylpyridine).     

Asymmetric Synthesis of (R)-and (S)-Moprolol

A simple and effective procedure for the enantioselective synthesis of (R)-and (S)-moprolol was described.The key step was the asymmetric synthesis of enantiopure (R)-and (S)-guaifenesin,which were synthesized from enantioenriched (R)-3-chloro-1,2-propanediol and (S)-epichlorohydrin via kinetics of hydrolysis resolution of racemic epichlorohydrin by chiral Salen-CoIIII complex.The e.e.values of both the optical compounds were above 98%,and the chemical structures of the target compounds were confirmed by 1H NMR,13C NMR,IR,and MS.     

界面缩聚法合成双(烯基环戊二烯基)钛(锆)聚醚的研究

本文通过界面缩聚法利用双(烯基环戊二烯基)钛(锆)二氯化物与二酚反应,制成了16个新的高分子化合物,对它们进行了IR、TGA和分子量的测定。文中还对反应条件与分子量的关系进行了讨论。     

U(IV)/LN(III) unexpected mixed site in polymetallic oxalato complexes. Part II. Substitution of U(IV) for Ln(III) in the new oxalates (N2H5)Ln(C2O4)2·nH2O (Ln=Nd, Gd)

Two new hydrazinium lanthanide(III) oxalates, (N₂H₅)[Nd(C₂O₄)₂(H₂O)]·4H₂O (1) and (N₂H₅)[Gd(C₂O₄)₂(H₂O)]·4.5H₂O (2) have been prepared and their crystal structures determined by single-crystal X-ray diffraction. The crystal structures were solved by the direct methods and Fourier difference techniques, and refined by a least-squares method on the basis of F² for all unique reflections. Crystallographic data: 1, triclinic, space group , , b=9.762(4), , α=62.378(5), β=76.681(5), γ=73.858(5), Z=2, R₁=0.0335 for 172 parameters with 3430 reflections with I?2σ(I); 2, triclinic, space group , , b=9.51(3), , α=62.11(4), β=76.15(5), γ=73.73(5), Z=2, R₁=0.0325 for 172 parameters with 1742 reflections with I?2σ(I). The two isotypic structures are built from a three-dimensional (3D) arrangement of lanthanide and oxalate ions. The lanthanide atom is coordinated by eight oxygen atoms from four tetradentate oxalate ions and one aqua oxygen. Alternating lanthanide and oxalate ions form six-membered rings that delimit tunnels running down three directions and occupied by hydrazinium and water molecules. Starting from these lanthanide(III) compounds two isotypic mixed Ln(III)/U(IV) oxalates, (N₂H₅)_0.75[Nd_0.75U_0.25(C₂O₄)₂(H₂O)]·4.5H₂O (3) and (N₂H₅)_0.75[Gd_0.75U_0.25(C₂O₄)₂(H₂O)]·4H₂O (4), are obtained by partial substitution of Ln(III) by U(IV) in the nine-coordinated site, the charge excess being compensated by removal of monovalent ions from the tunnels. Finally, using Na⁺ gel, two mixed Ln(III)/U(IV) sodium oxalates, Na_0.5[Nd_0.5U_0.5(C₂O₄)₂(H₂O)]·3H₂O (5) and Na_0.65[Gd_0.65U_0.35(C₂O₄)₂(H₂O)]·4.5H₂O (6) have been obtained without any change in the 3D framework.     

U(IV)/Ln(III) unexpected mixed site in polymetallic oxalato complexes. Part I. Substitution of Ln(III) for U(IV) from the new oxalate (NH4)2U2(C2O4)5·0.7H2O

A new ammonium uranium (IV) oxalate (NH₄)₂U₂(C₂O₄)₅·0.7H₂O (1) and three mixed uranium (IV)-lanthanide (III) oxalates, (N₂H₅)_2.6U_1.4M_0.6(C₂O₄)₅·xH₂O (M=Nd (2) and M=Sm (3)), Na_2.56U_1.44Nd_0.56(C₂O₄)₅·7.6H₂O (4) and Na₃UCe(C₂O₄)₅·10.4H₂O (5), have been prepared. The crystal structures of compounds 1, 4 and 5 have been determined by single-crystal X-ray diffraction. The crystal structures were solved by the direct methods and Fourier difference techniques, and refined by a least square method on the basis of F² for all unique reflections. Compounds 2 and 3 are isotypic with 1. Crystallographic data: 1, hexagonal, space group P6₃/mmc, a=19.177(3), c=12.728(4) Å, Z=6, R₁=0.0575 for 52 parameters with 1360 reflections with I?2σ(I); 2, hexagonal, space group P6₃/mmc, a=19.243(4), c=12.760(5) Å, Z=6; 3, hexagonal, space group P6₃/mmc, a=19.211(3), c=12.274(4) Å, Z=6; 4, orthorhombic, space group Pbcn, a=18.79(3), b=11.46(1), c=12.77(2) Å, Z=4, R₁=0.0511 for 183 parameters with 3026 reflections with I?2σ(I); 5, monoclinic, space group C2/c, a=18.878(6), b=11.684(4), c=12.932(4) Å, β=95.97(1)°, Z=4, R₁=0.0416 for 213 parameters with 4060 reflections with I?2σ(I). The honeycomb-like structure of the five compounds is built from the same three-dimensional arrangement of metallic and oxalate ions. Similar hexagonal rings of alternating metallic and oxalate ions form layers parallel to the (001) plane that are pillared by another oxalate ion. Indeed, some torsions or rotations of the bridging oxalate ligands led to modifications of the network symmetry. The monovalent cations and the water molecules occupy the hexagonal tunnels running down the [001] direction. Starting from the uranium (IV) compound A₂U₂(C₂O₄)₅·0.7H₂O with A=NH₄⁺ (1), the mixed U(IV)/Ln(III) oxalates are obtained by partial substitution of U(IV) by Ln(III) in a ten-coordinated site, the charge deficit being compensated by intercalation of supplementary monovalent ions within the tunnels. The distortion of the arrangement in the [001] direction for the Na-containing compounds allows the accommodation of a greater number of water molecules that insure an octahedral coordination of the Na atoms.     

Impact of Single Basepair Mismatches on Electron‐Transfer Processes at Fc‐PNA⋅DNA Modified Gold Surfaces

Gold‐surface grafted peptide nucleic acid (PNA) strands, which carry a redox‐active ferrocene tag, present unique tools to electrochemically investigate their mechanical bending elasticity based on the kinetics of electron‐transfer (ET) processes. A comparative study of the mechanical bending properties and the thermodynamic stability of a series of 12‐mer Fc‐PNA?DNA duplexes was carried out. A single basepair mismatch was integrated at all possible strand positions to provide nanoscopic insights into the physicochemical changes provoked by the presence of a single basepair mismatch with regard to its position within the strand. The ET processes at single mismatch Fc‐PNA?DNA modified surfaces were found to proceed with increasing diffusion limitation and decreasing standard ET rate constants k⁰ when the single basepair mismatch was dislocated along the strand towards its free‐dangling Fc‐modified end. The observed ET characteristics are considered to be due to a punctual increase in the strand elasticity at the mismatch position. The kinetic mismatch discrimination with respect to the fully‐complementary duplex presents a basis for an electrochemical DNA sensing strategy based on the Fc‐PNA?DNA bending dynamics for loosely packed monolayers. In a general sense, the strand elasticity presents a further physicochemical property which is affected by a single basepair mismatch which may possibly be used as a basis for future DNA sensing concepts for the specific detection of single basepair mismatches.