Asphaltene Inhibition and Flow Improvement of Crude Oil with a High Content of Asphaltene and Wax by Polymers Bearing Ultra-Long Side Chain

A high content of asphaltene and wax in crude oil leads to difficulties in the recovery and transportation of crude oil due to the precipitation of asphaltenes and the deposition of waxes. Comb-like polymers were found to be capable of inhibiting the aggregation of asphaltenes and crystallization of waxes. In this work, comb-like bipolymers of α-olefins/ultra-long chain (C18, C22 and C28) alkyl acrylate were synthesized and characterized by FT-IR and 1H NMR spectra. The results show that, for a model oil containing asphaltene, the initial precipitation point (IPP) of asphaltene was prolonged by UV, and the asphaltene particle size was reduced after adding the biopolymers, as revealed by dynamitic light scattering (DLS). The bipolymer containing the longer alkyl chain had a better asphaltene inhibition effect. However, DSC and rheological results show that the wax appearance temperature (WAT) of the typical high asphaltene and high wax content of crude oil was obviously reduced by adding bipolymers with shorter alkyl chains. The bipolymer (TDA2024-22) with a mediate alkyl chain (C22) reduced the viscosity and thixotropy of the crude oil by a much larger margin than others. Compared with the previously synthesized bipolymer with phenyl pendant (PDV-A-18), TDA2024-22 exhibited a better performance. Therefore, bipolymers with appropriate alkyl side chains can act as not only the asphaltene inhibitors but also wax inhibitors for high asphaltene and wax content of crude oil, which has great potential applications in the oil fields.

Hydrophobic Optimization of Functional poly(TPAE-co-suberoyl chloride) for Extrahepatic mRNA Delivery following Intravenous Administration

Messenger RNA (mRNA) has generated great attention due to its broad potential therapeutic applications, including vaccines, protein replacement therapy, and immunotherapy. Compared to other nucleic acids (e.g., siRNA and pDNA), there are more opportunities to improve the delivery efficacy of mRNA through systematic optimization. In this report, we studied a high-throughput library of 1200 functional polyesters for systemic mRNA delivery. We focused on the chemical investigation of hydrophobic optimization as a method to adjust mRNA polyplex stability, diameter, pKa, and efficacy. Focusing on a region of the library heatmap (PE4K-A17), we further explored the delivery of luciferase mRNA to IGROV1 ovarian cancer cells in vitro and to C57BL/6 mice in vivo following intravenous administration. PE4K-A17-0.2C8 was identified as an efficacious carrier for delivering mRNA to mouse lungs. The delivery selectivity between organs (lungs versus spleen) was found to be tunable through chemical modification of polyesters (both alkyl chain length and molar ratio in the formulation). Cre recombinase mRNA was delivered to the Lox-stop-lox tdTomato mouse model to study potential application in gene editing. Overall, we identified a series of polymer-mRNA polyplexes stabilized with Pluronic F-127 for safe and effective delivery to mouse lungs and spleens. Structure–activity relationships between alkyl side chains and in vivo delivery were elucidated, which may be informative for the continued development of polymer-based mRNA delivery.

Solution Self-Assembly of Coil-Crystalline Diblock Copolypeptoids Bearing Alkyl Side Chains

Polypeptoids, a class of synthetic peptidomimetic polymers, have attracted increasing attention due to their potential for biotechnological applications, such as drug/gene delivery, sensing and molecular recognition. Recent investigations on the solution self-assembly of amphiphilic block copolypeptoids highlighted their capability to form a variety of nanostructures with tailorable morphologies and functionalities. Here, we review our recent findings on the solutions self-assembly of coil-crystalline diblock copolypeptoids bearing alkyl side chains. We highlight the solution self-assembly pathways of these polypeptoid block copolymers and show how molecular packing and crystallization of these building blocks affect the self-assembly behavior, resulting in one-dimensional (1D), two-dimensional (2D) and multidimensional hierarchical polymeric nanostructures in solution.

Synthesis of New Derivatives of BEDT-TTF: Installation of Alkyl, Ethynyl, and Metal-Binding Side Chains and Formation of Tris(BEDT-TTF) Systems

The syntheses of new BEDT-TTF derivatives are described. These comprise BEDT-TTF with one ethynyl group (HC≡C-), with two (n-heptyl) or four (n-butyl) alkyl side chains, with two trans acetal (-CH(OMe)2) groups, with two trans aminomethyl (-CH2NH2) groups, and with an iminodiacetate (-CH2N(CH2CO2−)2 side chain. Three transition metal salts have been prepared from the latter donor, and their magnetic properties are reported. Three tris-donor systems are reported bearing three BEDT-TTF derivatives with ester links to a core derived from benzene-1,3,5-tricarboxylic acid. The stereochemistry and molecular structure of the donors are discussed. X-ray crystal structures of two BEDT-TTF donors are reported: one with two CH(OMe)2 groups and with one a -CH2N(CH2CO2Me)2 side chain.

Self-Assembled Membrane-like Nanomaterials from Sequence-Defined Peptoid Block Copolymers

Sequentially defined membrane-like nanomaterials have potential applications in biomedical and chemical fields due to their unique physical and chemical properties. However, these natural and synthetic nanomaterials have not been widely developed due to their complicated molecular sequence and structure, difficulties in synthesis etc. Here, we report a stable membrane-like nanomaterial composed of a monolayer or bilayer that was self-assembled from sequence-defined amphiphilic peptoid triblock (poly(N-aminoethyl glycine)-b-poly(N-octyl glycine)-b-poly(N-carboxyethyl glycine)) and diblock (poly(N-carboxyethyl glycine)-b-poly(N-octyl glycine) and poly(N-aminoethyl glycine)-b-poly(N-octyl glycine)) copolymers separately. A series of peptoid block copolymers were synthesized, and it was observed that long alkyl side chains and abundant hydrophobic blocks were necessary to form the membranes. The prepared membrane-like nanomaterials were fairly stable. They did not change obviously in shape and size with time, and they can survive after sonication. This study is expected to enrich the nanomaterial family, as well as polypeptoid science, and expand their applications in biomedicine and other fields.

Human metabolism and kinetics of the UV absorber 2-(2H-benzotriazol-2-yl)-4,6-di-tert-pentylphenol (UV 328) after oral administration

Abstract2-(2H-Benzotriazol-2-yl)-4,6-di-tert-pentylphenol (UV 328; CAS: 25973-55-1) is an ultraviolet light (UV) absorber which belongs to the class of hydroxy phenol benzotriazoles. Therefore, UV 328 is added to plastics and other polymers due to its photostability to prevent discoloration and prolong product stability which may result in an exposure of consumers. However, information about the toxic effects on humans and the human metabolism are still lacking. In the present study, human metabolism pathways of UV 328 and its elimination kinetics were explored. For that purpose, three healthy volunteers were orally exposed to a single dose of 0.3 mg UV 328/kg bodyweight. UV 328 and its metabolites were investigated in blood and urine samples collected until 48 and 72 h after exposure, respectively. Thereby, previously published analytical procedures were applied for the sample analysis using dispersive liquid–liquid microextraction and subsequent measurement via gas chromatography coupled to tandem mass spectrometry with advanced electron ionization. UV 328 was found to be oxidized at its alkyl side chains leading to the formation of hydroxy and/or oxo function with maximum blood concentrations at 8–10 h after exposure for UV 328-6/3-OH, UV 328-4/3-OH and UV 328-4/3-CO. In contrast, a plateau for UV 328-4/3-CO-6/3-OH levels was reached around 10 h post-dosage. The highest blood levels were found for native UV 328 at 8 h after ingestion. Furthermore, biphasic elimination kinetics in blood were revealed for almost all detected metabolites. UV 328 and its metabolites did not occur in blood as conjugates. The renal elimination kinetics were very similar with the kinetics in blood. However, the prominence of the metabolites in urine was somewhat different compared to blood. In contrast, mostly conjugated metabolites occurred for renal elimination. In urine, UV 328-4/3-CO-6/3-OH was found to be the most dominant urinary biomarker followed by UV 328-6/3-OH and UV 328-4/3-OH. In total, approximately 0.1% of the orally administered dose was recovered in urine within 72 h. Although high levels of UV 328 in blood proved good resorption and high systemic availability of the substance in the human body, the urine results revealed a rather low quantitative metabolism and urinary excretion rate. Consequently, biliary excretion as part of the enterohepatic cycle and elimination via feces are assumed to be the preferred pathways instead of renal elimination.

AIE-Active Poly(phenyleneethynylene)s for Fluorescence and Raman Dual-Modal Imaging and Drug-Resistant Bacteria Killing

Poly(phenyleneethynylene) (PPE) is a widely used functional conjugated polymer with applications ranging from organic optoelectronics and fluorescence sensors to optical imaging and theranostics. However, the fluorescence efficiency of PPE in aggregate states is generally not as good as their solution states, which greatly compromises their performance in fluorescence-related applications. Herein, we design and synthesize a series of PPE derivatives with typical aggregation-induced emission (AIE) properties. In these PPEs, the diethylamino-substituted tetraphenylethene units function as the long-wavelength AIE source and the alkyl side chains serve as the functionalization site. The obtained AIE-active PPEs with large π-conjugation show strong aggregate-state fluorescence, interesting self-assembly behaviors, inherently enhanced alkyne vibrations in the Raman-silent region of cells, and efficient antibacterial activities. The PPE nanoparticles with good cellular uptake capability can clearly and sensitively visualize the tumor region and residual tumors via their fluorescence and Raman signals, respectively, to benefit the precise tumor surgery. After post-functionalization, the obtained PPE-based polyelectrolyte can preferentially image bacteria over mammalian cells and possesses efficient photodynamic killing capability against Gram-positive and drug-resistant bacteria. This work provides a feasible design strategy for developing multifunctional conjugated polymers with multimodal imaging capability as well as photodynamic antimicrobial ability.