Exploring Microstructures and Interphase Properties of Surface- Grafted Diblock Copolymers in a Homopolymer Melt by Self-Consistent Field Theory Simulations

Polymeric self-consistent field theory is used to investigate microstructures and interphase properties of diblock copolymers grafted onto solid surfaces in a homopolymer melt. The calculations show that the grafted diblock copolymers can self-assemble into hemispherical microstructures at low grafting densities of the diblock copolymers. The morphology transforms into hemicylinder-like and sandwich-like lamellar microstructures with an increase in the chain-grafting density. The effective thickness of the grafted block layer and the interphase width between the homopolymer melt and the grafted copolymers strongly depend on the physicochemical parameters of the system, such as the composition of the grafted copolymer, the chemical incompatibility between the different components, the length ratio of grafted copolymer to homopolymer, and the grafting density of the diblock copolymers. In addition, the above computational results of microphase-separated structures and interphase properties are qualitatively compared with our previous experimental observations. The comparison indicates that our theoretical results not only reproduce the general feature of the experimental observations, but also elucidate the internal structural information and complement the findings in the region of high grafting densities of diblock copolymers.     

Predicting Polymorphism of Electrospun Polyvinylidene Fluoride Membranes by Their Morphologies

Although electrospinning of polyvinylidene fluoride (PVDF) has been studied for more than 10 years, the crystalline phase differentiation of the electrospun mats is still normally through the combination of different characterization techniques, and the relationship between polymorphism and morphology of the fibers in electrospun PVDF membranes has never been reported. Here, we show their close relationships by conducting room-temperature electrospinning experiments on various polymer/solvent systems. The electrospun membranes full of bead-free fibers have a very high fraction of β-phase, F(β), over 90%, and high orientation, whereas the membranes comprising beads and/or a large number of beaded fibers most often result in a low fraction of β-phase (F(β) normally below 50%) and low orientation. On the other hand, electrospun membranes consisting of both bead-free fibers and a very limited number of beaded fibers showed a medium high fraction of β-phase, F(β) more than 70% but less than 90%. These findings suggest the feasibility of intuitively predicting the crystalline phase of electrospun PVDF membranes directly by their morphologies, which is obviously simple, inexpensive and convenient for future investigations.     

Composition heterogeneity of tetrafluoroethylene-hexafluoropropylene random copolymers characterized by successive self-nucleation and annealing

In the present work, successive self-nucleation and annealing (SSA) was applied to a series of tetrafluoroethylene-hexafluoropropylene random copolymers (FEPs). Multiple melting peaks were observed for all FEP samples after SSA thermal treatment. The lamellar crystal thicknesses were calculated from the melting temperatures, and the mass percentages of the crystals of specific thickness were obtained from the areas of the melting peaks. As a result, distributions of the lamellar thickness, which can be correlated to the composition distribution, were determined. It was found that the composition distribution of the FEP samples tended to become more heterogeneous as the content of hexafluoropropylene (HFP) comonomer increases. Samples with the same HFP content might also have different composition distributions.     

Thermal stability of phosphorus-containing styrene–acrylic copolymer and its fire retardant performance in waterborne intumescent coatings

Phosphorus-containing styrene–acrylic copolymers are synthesized by free radical seeded emulsion polymerization with the monomers of MMA/St/BA/MAA and phosphorus-containing vinyl monomer (SIPOMER PAM100). The properties of copolymer films are characterized by water adsorption test, thermogravimetry, Fourier transform infrared spectroscopy (FTIR), and energy dispersive spectroscopy (EDS), etc. The copolymer emulsions are used as the binder in an intumescent coatings formulation, and the fire-retardant performances of the coatings are determined by an instrument which the furnace temperature is analoging the cellulose fire temperature. The water adsorption of copolymer film increases remarkably owing to the increasing of phosphoric acid group in the polymer chain. The thermal decomposition stability and thermal-oxidative decomposition stability of the copolymer are improved when PAM100 is introduced into its chain, which is strongly supported by the FTIR and EDS results of copolymer residual treated at different temperature. The EDS results also illustrate that the fire retardancy enhanced by PAM100 during combustion owing to the condensed-phase mechanism. The fire-retardant test results show that the intumescent coatings using StA-P_1.5 copolymer emulsion as the binder obtains the best fire retardant performance. We suggested that StA-P_1.5 presents the lower reactivity with the acid source (APP) in 275–400 °C, and the higher reactivity with APP when the temperature is greater than 500 °C would be benefit for the swelling–charring process and the final fire retardant performance. The exorbitant crosslinking in StA-P₇ brings a negative effect on the fire-retardant performance of intumescent coatings, even if it introduces a densy swollen char layer.     

Development and validation of a rapid and sensitive assay for the determination of anisodamine in 50 μL of beagle dog plasma by LC–MS/MS

A simple, rapid, high‐throughput, and highly sensitive LC–MS/MS was developed to determine anisodamine in a small volume (50 μL) of beagle dog plasma using atropine sulfate as the internal standard. The analyte and internal standard were isolated from 50 μL plasma samples after a one‐step protein precipitation using Sirocco 96‐well protein precipitation filtration plates. The separation was accomplished on a Hanbon Hedera CN column (100 × 4.6 mm, 5 μm) and the run time was 4 min. A Micromass Quatro Ultima mass spectrometer equipped with an ESI source was operated in the multiple reaction monitoring mode with the precursor‐to‐product ion transitions m/z 306.0→140.0 (anisodamine) and 290.0→123.9 (atropine) used for quantitation. The method was sensitive with a low LOQ of 0.05 ng/mL, and good linearity in the range 0.05–50 ng/mL for anisodamine (r² ≥ 0.995). All the validation data, such as accuracy, intra‐ and interrun precision, were within the required limits. The method was successfully applied to the pharmacokinetic study of anisodamine hydrochloride injection in beagle dogs.     

Nickel-catalyzed synthesis of 9-monoalkylated fluorenes from 9-fluorenone hydrazone and alcohols

A practical protocol was disclosed for the nickel-catalyzed C-alkylation of 9-fluorenone hydrazone with alcohols using t-BuOK as the base, and 9-monoalkylated fluorene derivatives were obtained in good yields under the benign conditions.     

Synthesis of 3-Trifluoromethyl-Substituted Benzo[f]chromene Derivatives in a One-Pot Reaction

In the presence of 1,8-diazabicycolo[5.4.0]undec-7-ene (DBU) and concentrated H₂SO₄, 2-naphthol reacted smoothly with α,β-unsaturated trifluoromethyl ketones in CH₂Cl₂ at room temperature, affording the 3-trifluoromethyl-substituted benzo[f]chromene derivatives in good to excellent yields in a one-pot reaction.

[Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the following free supplemental resource: Full experimental and spectral details].     

Practical synthesis of C1–8 fragment of autolytimycin via a chelation-controlled diastereoselective addition of diisopropenylzinc to α-methoxy aldehyde

The C1–8 fragment of autolytimycin was synthesized via a reliable 10-step route capable of delivering 41% overall yield at multi-gram scale. As a key step, a chelation-controlled isopropenylation of α-oxygenated aldehydes was established with a reagent combination of diisopropenylzinc, magnesium halide, and a dichloromethane/toluene mixed solvent. Cram-chelate isopropenylation products dominated for aldehydes with a small α-substituents, such as –OMe and –OBn groups, while the Felkin product could be obtained with a bulky –OTBS group.     

Synthesis of oxazole and furan derivatives via Rh2(OAc)4-catalyzed C≡X bond insertion of cyclic 2-diazo-1,3-diketones with nitriles and arylacetylenes

Abstract

A convenient and efficient procedure for the synthesis of 2-substituted-6,7-dihydrobenzo[d]oxazol-4(5H)-ones and 2-aryl-6,7-dihydrobenzofuran-4(5H)-ones through a Rh₂(OAc)₄-catalyzed C≡X (X?=?N, C) insertion of cyclic 2-diazo-1,3-diketones with nitriles and aromatic alkynes has been developed. This reaction uses readily available starting materials and stable cyclic 2-diazo-1,3-diketone compounds, with desired products formed in good to high yields. A tentative mechanism involving a C≡X bond insertion and 1,5-dipolar electrocyclization/ring opening and cyclization sequence for this reaction is proposed.     

Synthesis and Morphology Control of AM‐6 Nanofibers with Tailored ‐V‐O‐V‐ Intermediates

Microporous vanadosilicates with octahedral VO₆ and tetrahedral SiO₄ units, better known as AM‐6, have been hydrothermally synthesized with different morphologies by controlling the Na/K molar ratio of the initial gel mixtures. The morphology of the AM‐6 materials changed from bulky cube to nanofiber aggregates as the Na/K molar ratio decreased from 1.9 to 0.2. Raman spectroscopy revealed that the VO₃^? intermediate species plays an important role in the formation of the nanofiber morphology. The orientation of ‐V‐O‐V‐ chains in nanofiber aggregates was examined by confocal polarized micro‐Raman spectroscopy. It was found that these aggregates are assemblies of short ‐V‐O‐V‐ chains perpendicular to the axis of nanofibers. The obtained AM‐6 nanofibers greatly increase the exposed proportion of V? O terminals, and thus improve the catalytic performance.