Linear Oligomers Research Articles

The intramolecular aggregation of phosphaphenanthrene groups and benzene-terminated effect within linear phosphonate oligomers effectively enhanced the flame retardancy and toughness of epoxy resin

To explore the potential of a flame retardant molecular structure that simultaneously enhances the flame retardancy and physical properties of epoxy resin (EP), benzene-terminated linear phosphonate oligomers Bz-DQPC-n were synthesized. Compared with the previously prepared linear bisphenol phosphonate oligomers DQPC-n, the benzene-terminated effect of Bz-DQPC-n molecules endows EP composites with better flame retardancy and toughness. In the vertical combustion (UL 94) test, Bz-DQPC-n/EP reached a V-0 rating. For the Bz-DQPC-2 molecule, the results revealed that under the same phosphorus contents, the limiting oxygen index (LOI) value of the Bz-DQPC-2/EP reached 38.2 %, which was higher than that of DQPC-2/EP. Furthermore, the peak heat release rate (pk-HRR) and total heat release rate (THR) of Bz-DQPC-2/EP were 677 kW/m2 and 83 MJ/m2. These values decreased by 54.7 % and 27.2 % in comparison to pure EP, respectively. In addition, the incorporation of Bz-DQPC-n can enhance the glass transition temperature (Tg) of EP composites. The flame retardant mechanism research demonstrated that Bz-DQPC-n molecules produced phosphorus-containing free radicals and aromatic compound fragments during gas-phase pyrolysis. These phosphorus-containing free radicals can interrupt or inhibit the combustion chain reaction process. A proportion of the aggregated phosphaphenanthrene groups decomposed to produce aromatic compounds that remained in the condensed phase, thereby enhancing the quality of the char layer. The investigation of the impact of the end-capping effect within Bz-DQPC-n molecules on the flame retardant behavior of EP composites offers a valuable reference for designing phosphaphenanthrene compounds with high flame retardant efficiency.

An alternative approach for compliance testing of food and skin contact silicone elastomers by specific determination of volatile cyclic siloxane oligomers via GC-FID

To date, silicone elastomers intended for food and skin contact are considered compliant as long as their weight loss during a thermal treatment (200 °C, 4 h) is below 0.5 wt.%. The common assumption is that this weight loss is caused almost entirely by potentially harmful volatile siloxane oligomers. The present study questions this assumption, first time balancing the initial content and the thermal removal of volatile siloxanes in 48 silicone materials. A GC-FID method for a specific determination of linear (L4 up to L24) and cyclic siloxane oligomers (D4 up to D25) was developed and validated against 1H-NMR and thermal desorption GC-MS analysis. All samples contained significant amounts of cyclic siloxanes, while linear trimethylsiloxy terminated oligomers were not detected. Only a weak correlation between the weight loss after thermal treatment and the initial content of cyclic siloxanes was determined for most samples. However, rapid adsorption of humidity from ambient air and its incomplete removal during sample conditioning were determined as crucial aspects in conventional gravimetric compliance testing for silicone articles. Consequently, the specific determination of volatile cyclic siloxane profiles via GC-FID is suggested as the more reliable approach for a compliance decision.

Navigating a 1E+60 Chemical Space of Peptide/Peptoid Oligomers.

Herein we report a virtual library of 1E+60 members, a common estimate for the size of the drug-like chemical space. The library consists of linear or cyclic oligomers forming molecules within the size range of peptide drugs. We demonstrate ligand-based virtual screening using a genetic algorithm.

Polymers Containing Diethylsiloxane Segment and Active Functional Group by Ring-Opening Polymerization of Hexaethylcyclotrisiloxane under the Catalysis of Linear Chlorinated Phosphazene Acid.

Linear chlorinated phosphazene acid is prepared using PCl5 and NH4Cl as raw materials. Using hexaethylcyclotrisiloxane as the monomer, 1,1,3,3-tetramethyldisiloxane or 1,3-divinyl-1,1,3,3-tetramethyldisiloxane as the end-capping agent, and linear chlorinated phosphazene acid as the catalyst, polydiethylsiloxane oligomers terminated with active Si-H or Si-CH=CH2 groups have been prepared. Using hexaethylcyclotrisiloxane and 1,3,5,7-octamethylcyclotetrasiloxane as comonomers, 1,1,3,3-tetramethyldisiloxane or hexamethyldisiloxane as the end-capping agent, or using hexaethylcyclotrisiloxane and octamethylcyclotetrasiloxane as comonomers, 1,1,3,3-tetramethyldisiloxane as the end-capping agent, copolymers containing active Si-H bonds and dimethylsiloxane segments have been prepared under the catalysis of linear chlorinated phosphazene acid. The effects of catalyst dosage, reaction temperature, reaction time, end-capping agent, and polymerization monomer dosage on polymer yield and structure were investigated. Using 300 ppm of linear chlorinated phosphazene acid, oligomers and copolymers containing an active Si-H bond and diethylsiloxane segment were prepared under mild conditions. The molecular weight of the obtained polymers was close to their designed values, but their PDI values were small. The highest yield of α, ω-bisdimethylsiloxyl-terminated PDES oligomers reached 93%. Using oligomers and copolymers containing Si-H bonds and diethylsiloxane segments as crosslinkers, a silicone gel containing diethylsiloxane segments was prepared by hydrosilylation reaction. With the introduction of a diethylsiloxane segment, the glass transition temperature of the silicone gel decreased relative to that of the PDMS oligomer, but the temperature at 5% weight loss in nitrogen atmosphere decreased from 347 °C to 312 °C. The mechanism of the ring-opening polymerization of hexaethylcyclotrisiloxane catalyzed by linear chlorinated phosphazene acid is also discussed.

Insight into HTPB pyrolysis mechanism under high-temperature: A reactive molecular dynamics study

Hydroxyl-terminated polybutadiene (HTPB) is widely utilized in solid and hybrid rocket propellants due to its mechanical properties and combustion performance. Insight into its pyrolysis process is key to enhancing combustion efficiency in rocket engines. This study employs ReaxFF molecular dynamics (MD) simulations to explore the pyrolysis mechanism of HTPB under extreme conditions, with temperatures ranging from 1000 K to 2000 K. The results identify the primary degradation products and elucidate their formation mechanisms. The simulation reveals that C-C bond cleavage at polymerization sites is the initial step, followed by the formation of linear oligomers and butadiene. Subsequent reactions, including hydrogenation and dehydrogenation, lead to the generation of smaller molecular species. The kinetic analysis confirms that HTPB pyrolysis follows first-order reaction kinetics, with an activation energy of 8.12 kcal/mol. The findings are compared with existing experimental data, highlighting the influence of thermal environments on pyrolysis mechanisms and product distributions.

Conformational preferences of cocoa oligomeric proanthocyanidins and their influence on polarity

Proanthocyanidins (OPACs) are the second largest class of plant metabolites after lignans. Although knowledge of their 3D conformations would add greatly to our understanding of their biological properties, very little has been published on the conformations of OPACs with a degree of polymerization (DP) above 4. We investigated the conformations of the linear epicatechin oligomers, prominent representatives of OPACs prevalent in apples and cocoa, where the epicatechin units are interconnected through the 4β-8 bonds. For DP-2 to DP-10 oligomers, conformational preferences reflected in the arrangement of consecutive flavan-3-ol units, are characterized by the φ torsion. For dimers, there are two energy wells corresponding to two preferred φ torsions, designated as compact and extended form. This behaviour is preserved in OPACs with higher DPs, but the most energetically favoured conformations are a combination of both, with compact-only or extended-only conformations being very unlikely. Thus, oligomers with DP ≥ 7 tend to assume an overall conformation approximating a spherical shape. This shape has a significant influence on the polarity of the OPAC oligomers expressed as 3D polar surface area, calculated using Spartan software for geometry-optimized 3D models, and possibly on other physicochemical properties. The results of polarity calculations provide a molecular-level rationale for the polarity-based chromatographic separation of the cocoa B-type procyanidins with DP range 4 to 10. In our experiments, using centrifugal partition chromatography (CPC) (a solvent system consisting of EtOAc-EtOH-water (6:1:5) v/v/v with aqueous phase stationary and upper phase mobile) we found that an enriched mixture of proanthocyanidins eluted first DP-1 (epicatechin) followed by consecutive elution of the DP-2 to DP-10 in the linear 4β-8 form. We demonstrated that such separation would not be possible if compact-only or extended-only conformations were present in solution. However, for the energy-favoured, spherically shaped conformations, the observed CPC elution order is fully justified.

PROTIC POLYMERIC IONIC LIQUID OF A BLOCK OLIGOMERIC STRUCTURE WITH IONIC BONDS IN THE MAIN CHAIN

A method for the synthesis of protic polymeric ionic liquid (PIL) of a block oligomeric structure with ionic bonds in the main chain, which turns into a liquid state at temperatures below 50 °C, was developed. Ionic bonding was used to form a polymer chain. It was formed as a result of neutralization reaction between oligomers of telechelic structure with terminal acidic and basic groups. A new linear oligomer containing basic tertiary nitrogen atoms at the ends of the oligoether chain (PEO-2NEt2) was obtained by reaction of α,ω-diglycidyl ether of polyethylene glycol MW 1000 with N,N-diethylamine. A linear oligomer with terminal sulfonic acid groups (PEO-2SO3H), which is a product of the interaction of polyethylene glycol (MW 1000) with the cyclic anhydride of 2-sulfobenzoic acid, was used as an acidic linear oligomer. The synthesis of PIL [PEO-2H-2NEt2]2+ [PEO-2SO3]2- was carried out by neutralization of basic oligomer PEO-2NEt2 with the acidic oligomer PEO-2SO3H in their molar ratio of 1:1. The structure of the obtained compound was characterized by the methods of FTIR and 1H NMR spectroscopy. According to the DSC data, the synthesized PIL contains an amorphous phase with a glass transition temperature of -49.7 °С and a crystalline phase with a melting temperature of 34.5 °С. The decomposition onset temperature corresponding to 5% weight loss is 271 °C according to the TGA. The ionic conductivity of PIL studied by dielectric relaxation spectroscopy under anhydrous conditions in the range from 40 °C to 100 °C increases with increase in temperature and reaches 2.7·10-4 S/cm. The resulting compound is promising as a proton-conducting medium for various electrochemical devices.

Strong yet Tough Catalyst-Free Transesterification Vitrimer with Excellent Fire-Retardancy, Durability, and Closed-Loop Recyclability.

Despite great advances in vitrimer, it remains highly challenging to achieve a property portfolio of excellent mechanical properties, desired durability, and high fire safety. Thus, a catalyst-free, closed-loop recyclable transesterification vitrimer (TPN1.50) with superior mechanical properties, durability, and fire retardancy is developed by introducing a rationally designed tertiary amine/phosphorus-containing reactive oligomer (TPN) into epoxy resin (EP). Because of strong covalent interactions between TPN and EP and its linear oligomer structure, as-prepared TPN1.50 achieves a tensile strength of 86.2MPa and a toughness of 6.8MJm-3, superior to previous vitrimer counterparts. TPN1.50 containing 1.50 wt% phosphorus shows desirable fire retardancy, including a limiting oxygen index of 35.2% and a vertical burning (UL-94) V-0 classification. TPN1.50 features great durability and can maintain its structure integrity in 1M HCl or NaOH solution for 100 days. This is because the tertiary amines are anchored within the cross-linked network and blocked by rigid P-containing groups, thus effectively suppressing the transesterification. Owing to its good chemical recovery, TPN1.50 can be used as a promising resin for creating recyclable carbon fiber-reinforced polymer composites. This work offers a promising integrated method for creating robust durable fire-safe vitrimers which facilitate the sustainable development of high-performance polymer composites.

The third-order nonlinear optical responses of zinc porphyrin oligomers: Cycles vs linear chains

Porphyrins are widely used as potential nonlinear optical (NLO) materials because of their highly delocalized π electrons and feasible synthesis and functionalization with broad biological applications. A variety of linear and cyclic porphyrin derivatives have been synthesized, and the correlation between their structures and NLO properties awaits being disclosed. In this work, the electronic structures and third-order NLO properties of linear and cyclic butadiyne-linked zinc porphyrin oligomers have been studied by quantum chemical methods and sum-over-states model. The static second hyperpolarizability (<γ0>) increases exponentially with the number of zinc porphyrin units ([<γ0>n] = 0.67[<γ0>1]n2.63, n = 2 ∼ 6) in linear π-conjugated oligomers, and the <γ0> of the linear hexamer is about 74 times that of the monomer. Such enhancement of <γ0> in linear oligomers originates from closely-lying frontier molecular orbitals available for low energy electron excitations and strong charge transfer-based excitations across porphyrins. The <γ0>s of cyclic porphyrins are lower than that of the linear hexamer, though the interaction between the ring and the ligand enhances the <γ0> of some cyclic zinc porphyrin complexes. The large two-photon absorption cross sections confer on these zinc porphyrin derivatives excellent candidates for two-photon absorption applications.

Clustered protocadherin cis-interactions are required for combinatorial cell–cell recognition underlying neuronal self-avoidance

In the developing human brain, only 53 stochastically expressed clustered protocadherin (cPcdh) isoforms enable neurites from individual neurons to recognize and self-avoid while simultaneously maintaining contact with neurites from other neurons. Cell assays have demonstrated that self-recognition occurs only when all cPcdh isoforms perfectly match across the cell boundary, with a single mismatch in the cPcdh expression profile interfering with recognition. It remains unclear, however, how a single mismatched isoform between neighboring cells is sufficient to block erroneous recognitions. Using systematic cell aggregation experiments, we show that abolishing cPcdh interactions on the same membrane (cis) results in a complete loss of specific combinatorial binding between cells (trans). Our computer simulations demonstrate that the organization of cPcdh in linear array oligomers, composed of cis and trans interactions, enhances self-recognition by increasing the concentration and stability of cPcdh trans complexes between the homotypic membranes. Importantly, we show that the presence of mismatched isoforms between cells drastically diminishes the concentration and stability of the trans complexes. Overall, we provide an explanation for the role of the cPcdh assembly arrangements in neuronal self/non-self-discrimination underlying neuronal self-avoidance.

Structural Insights into Ciona intestinalis Septins: Complexes Suggest a Mechanism for Nucleotide-dependent Interfacial Cross-talk

Septins are filamentous nucleotide-binding proteins which can associate with membranes in a curvature-dependent manner leading to structural remodelling and barrier formation. Ciona intestinalis, a model for exploring the development and evolution of the chordate lineage, has only four septin-coding genes within its genome. These represent orthologues of the four classical mammalian subgroups, making it a minimalist non-redundant model for studying the modular assembly of septins into linear oligomers and thereby filamentous polymers. Here, we show that C. intestinalis septins present a similar biochemistry to their human orthologues and also provide the cryo-EM structures of an octamer, a hexamer and a tetrameric sub-complex. The octamer, which has the canonical arrangement (2-6-7-9-9-7-6-2) clearly shows an exposed NC-interface at its termini enabling copolymerization with hexamers into mixed filaments. Indeed, only combinations of septins which had CiSEPT2 occupying the terminal position were able to assemble into filaments via NC-interface association. The CiSEPT7-CiSEPT9 tetramer is the smallest septin particle to be solved by Cryo-EM to date and its good resolution (2.7 Å) provides a well-defined view of the central NC-interface. On the other hand, the CiSEPT7-CiSEPT9 G-interface shows signs of fragility permitting toggling between hexamers and octamers, similar to that seen in human septins but not in yeast. The new structures provide insights concerning the molecular mechanism for cross-talk between adjacent interfaces. This indicates that C. intestinalis may represent a valuable tool for future studies, fulfilling the requirements of a complete but simpler system to understand the mechanisms behind the assembly and dynamics of septin filaments.

Inelastic Neutron Scattering Studies of Propene and 1-Octene Oligomerisation in H-ZSM-5

Neutron scattering methods such as quasielastic neutron scattering (QENS) and inelastic neutron scattering (INS) have been used to study the reactivity of propene and 1-octene over the acid zeolite catalyst H-ZSM-5. The high activity of the catalyst causes the alkenes to form linear oligomers below room temperature. INS has shown that the reaction proceeds through a hydrogen-bonded intermediate. Studies using propane as an inert analogue for propene have found that the adsorbed C3 molecules spend much of their time undergoing short jumps within the pore channels of the zeolite. Hydrothermal dealumination plays an important role in determining the activity of zeolite catalysts. Dealumination was found to delay the onset of catalytic activity for oligomerisation to higher temperatures and increase the mobility of hydrocarbons within the zeolite, both due to reduced acid-hydrocarbon interactions.

Mechanically robust poly(urethane-imide) aerogels with excellent thermal insulation and sound absorption by ambient drying

Polyimide (PI) aerogels are the great candidates for sound absorption, thermal insulation and mechanical cushioning materials due to their low density, excellent mechanical properties and good thermal stability. However, the high shrinkage and hydrophilicity of PI aerogels, as well as the time-consuming and complexity of the process directly limit their wide application in many fields. Herein, a facile one-step method for the synthesis of porous monolithic poly(urethane-imide) (PUI) aerogels was successfully developed. Hydrothermal synthesis and ambient drying methods were adopted in the construction of monolithic chemically cross-linked PUI aerogels, which avoids the complex imidization process. PUI aerogels were homogeneously produced by a chemical cross-linking copolymerization reaction between polyurethane (PU) oligomers, Benzene-1,2,4,5-tetracarboxylic dianhydride (PMDA) and 1, 3, 5-tris (6-isocyanatohexyl)-1, 3, 5-triazine-2, 4, 6(1H, 3H, 5H)-trione without any catalysts. Interestingly, the introduction of linear flexible PU oligomers chain segments effectively prevented the shrinkage of the network backbone and enhanced the hydrophobicity of PUI aerogels. The obtained PUI aerogels have low density (0.196 g/cm3), low shrinkage (9.30%), high porosity (79.54%) and hydrophobicity (water contact angle of 129.2°). Under high pressure, PUI aerogel was compressed but not break and the compression Young's modulus as high as 3.638 MPa. Moreover, the thermal conductivity of PUI aerogels was only 59.92 mW/m/K at 150 °C. When the back cavity depth was 5 mm, the highest sound absorption coefficient of PUI aerogel was up to 0.7219. This work provides a new method for the development of lightweight, high-mechanical-strength polymer aerogels, and the prepared aerogels have a potential application in the field of multifunctional integrated sound absorption materials.

Bioinspired Water Preorganization in Confined Space for Efficient Water Oxidation Catalysis in Metallosupramolecular Ruthenium Architectures.

ConspectusNature has established a sustainable way to maintain aerobic life on earth by inventing one of the most sophisticated biological processes, namely, natural photosynthesis, which delivers us with organic matter and molecular oxygen derived from the two abundant resources sunlight and water. The thermodynamically demanding photosynthetic water splitting is catalyzed by the oxygen-evolving complex in photosystem II (OEC-PSII), which comprises a distorted tetramanganese-calcium cluster (CaMn4O5) as catalytic core. As an ubiquitous concept for fine-tuning and regulating the reactivity of the active site of metalloenzymes, the surrounding protein domain creates a sophisticated environment that promotes substrate preorganization through secondary, noncovalent interactions such as hydrogen bonding or electrostatic interactions. Based on the high-resolution X-ray structure of PSII, several water channels were identified near the active site, which are filled with extensive hydrogen-bonding networks of preorganized water molecules, connecting the OEC with the protein surface. As an integral part of the outer coordination sphere of natural metalloenzymes, these channels control the substrate and product delivery, carefully regulate the proton flow by promoting pivotal proton-coupled electron transfer processes, and simultaneously stabilize short-lived oxidized intermediates, thus highlighting the importance of an ordered water network for the remarkable efficiency of the natural OEC.Transferring this concept from nature to the engineering of artificial metal catalysts for fuel production has fostered the fascinating field of metallosupramolecular chemistry by generating defined cavities that conceptually mimic enzymatic pockets. However, the application of supramolecular approaches to generate artificial water oxidation catalysts remained scarce prior to our initial reports, since such molecular design strategies for efficient activation of substrate water molecules in confined nanoenvironments were lacking. In this Account, we describe our research efforts on combining the state-of-the art Ru(bda) catalytic framework with structurally programmed ditopic ligands to guide the water oxidation process in defined metallosupramolecular assemblies in spatial proximity. We will elucidate the governing factors that control the quality of hydrogen-bonding water networks in multinuclear cavities of varying sizes and geometries to obtain high-performance, state-of-the-art water oxidation catalysts. Pushing the boundaries of artificial catalyst design, embedding a single catalytic Ru center into a well-defined molecular pocket enabled sophisticated water preorganization in front of the active site through an encoded basic recognition site, resulting in high catalytic rates comparable to those of the natural counterpart OEC-PSII.To fully explore their potential for solar fuel devices, the suitability of our metallosupramolecular assemblies was demonstrated under (electro)chemical and photocatalytic water oxidation conditions. In addition, testing the limits of structural diversity allowed the fabrication of self-assembled linear coordination oligomers as novel photocatalytic materials and long-range ordered covalent organic framework (COF) materials as recyclable and long-term stable solid-state materials for future applications.

Design of Triazolium-Grafted Peptidomimetic Macrocycles with Facial Amphipathicity to Target Pathogenic Bacteria.

Access to 1,2,3-triazolium-grafted peptoid macrocycles was developed by macrocyclization and multivalent postmodification of linear peptoid oligomers carrying an alternance of benzylic and propargyl groups as side chains. X-ray analysis and NMR studies revealed a conformational preference for constrained hairpin-shaped structures leading to the facial amphipathic character of these macrocycles. A preliminary evaluation showed the antimicrobial activities of these new cationic amphipathic architectures.

Tunable Fluorescence, Morphology, and Antibacterial Behaviors of Conjugated Oligomers via Host-Guest Supramolecular Self-Assembly.

Host-guest supramolecular self-assembly has become one facile but efficient way to regulate the optical properties of conjugated oligomers and construct promising photofunctional materials. Herein, we design two linear conjugated oligomers terminated with two or four pyridinium moieties, which show different 1:1 'head-to-tail' binding patterns with cucurbit[8]uril (CB[8]) to form host-guest supramolecules. After being encapsulated in the hydrophobic cavity of the CB[8] host, the fluorescence emission of the conjugated oligomers undergoes significant changes, resulting in tunable fluorescence color with enhanced quantum yields. Triggered by the aggregation of supramolecules, the regular or rigid binding modes lead to the formation of cuboids and spheroids in nanoscale, respectively. Due to the macrocyclic-confinement effect, the light-driven reactive oxygen species (ROS) production of the host-guest complex is increased significantly, thereby improving the photodynamic antibacterial performance toward Staphylococcus aureus (S. aureus).

Molecular rheology of nanoconfined oligomer melts

We use nonequilibrium atomistic molecular dynamics simulations of unentangled melts of linear and star oligomer chains (C25H52) to study the steady-state viscoelastic response under confinement within nanoscale hematite (α−Fe2O3) channels. We report (i) the negative (positive) first (second) normal stress difference and (ii) the presence of viscoelastic tension at low Wi. With the aim of uncovering the molecular mechanism of viscoelasticity, we link these effects to bond alignment such that absorbed chains near the surface can carry the elastic force exerted on the walls, which decays as the chains become more aligned in the flow direction. This alignment is observed to be independent of the film thickness but enhanced as the shear rate increases or the surface attraction weakens.

Template-Directed Synthesis of Strained meso-meso-Linked Porphyrin Nanorings.

Strained macrocycles display interesting properties, such as conformational rigidity, often resulting in enhanced π-conjugation or enhanced affinity for non-covalent guest binding, yet they can be difficult to synthesize. Here we use computational modeling to design a template to direct the formation of an 18-porphyrin nanoring with direct meso-meso bonds between the porphyrin units. Coupling of a linear 18-porphyrin oligomer in the presence of this template gives the target nanoring, together with an unexpected 36-porphyrin ring by-product. Scanning tunneling microscopy (STM) revealed the elliptical conformations and flexibility of these nanorings on a Au(111) surface.

Efficient gene delivery by multifunctional star poly (β-amino ester)s into difficult-to-transfect macrophages for M1 polarization

Gene delivery to macrophages holds great promise for cancer immunotherapy. However, traditional gene delivery methods exhibit low transfection efficiency in macrophages. The star-shaped topological structure of polymers is known to encapsulate genes inside their cores, thereby facilitating sustained release of the genetic material. Herein, combining the structural advantages of star polymers and the transfection advantages of poly (β-amino ester)s (PAEs), we developed a novel linear oligomer grafting-onto strategy to synthesize a library of multi-terminal star structured PAEs (SPAEs), and evaluated their gene delivery efficiency in various tissue cells. The transfection with human hepatocellular carcinoma cells (HepG2, HCC-LM3 cells and MHCC-97H cells), rat normal liver cells (BRL-3 A cells), human ovarian cancer cells (A2780 cells), African green monkey kidney cells (Vero cells), human cervical cancer cells (HeLa cells), human chondrosarcoma cells (SW1353 cells), and difficult-to-transfect human epidermal keratinocytes (HaCaT cells) and normal human fibroblast cells (NHF cells) showed that SPAEs exhibited superior transfection profile. The GFP transfection efficiency of top-performing SPAEs in HeLa cells (96.1%) was 2.1-fold, and 3.2-fold higher compared to jetPEI and Lipo3000, respectively, indicating that the star-shaped topological structure can significantly enhance the transfection efficiency of PAEs. More importantly, the top-performing SPAEs could efficiently deliver Nod2 DNA to difficult-to-transfect RAW264.7 macrophages, with a high transfection efficiency of 33.9%, which could promote macrophage M1 polarization and enhanced CD8+ T cell response in co-incubation experiments. This work advances gene therapy by targeting difficult-to-transfect macrophages and remodeling the tumor immune microenvironment.

Safety profile of ZnO active packaging PBAT based biomaterial for food packaging. First tier evaluation

Materials produced with polybutylene adipate terephthalate (PBAT) and starch are raising great interest for packaging and food contact applications, including as support for active antimicrobial agents such as zinc oxide nanoparticles (ZnO). Studies focusing on the safety of these materials as evaluated with the current reference rules for food contact materials, are lacking. A commercially available PBAT/starch-based material was incorporated with ZnO and the overall and specific migration of the films were studied at different conditions of simulants and temperature. The overall migration (OM) limit is exceeded due to the release of starch as confirmed by infrared spectroscopy. The impact of temperature on the OM was higher for the ethanol 10%. The incorporation of ZnO particles reduced the OM, for both temperatures tested for ethanol 10%. The impact of incorporating ZnO in the migration into acetic acid was relevant at 20 °C only. Beside starch, most relevant migrants were PBAT oligomers made of butanediol and two different kinds of diacids, terephthalic acid or adipic acid. The cyclic diester of 1,4-butanediol and adipic acid, butenyl butanediol adipate in either cyclic and linear form and oligomers terephthalic acid, but-3-enyl hexadecyl ester were detected in an untargeted screening with GC-MS. A second TPA oligomer was not fully identified. The specific migration was in several cases, depending on the simulant and on the temperature, higher than 50 μgkg−1 (semi-quantification), the threshold value for requiring additional toxicity test (genotoxicity tests applied to oligomers below 1000 Da). This indicates the need for more detailed studies with more precise quantification to verify the need for toxicity tests.