Multifunctional Integrated Organic-Inorganic-Metal Hybrid Aerogel for Excellent Thermal Insulation and Electromagnetic Shielding Performance.

Vehicles operating in space need to withstand extreme thermal and electromagnetic environments in light of the burgeoning of space science and technology. It is imperatively desired to high insulation materials with lightweight and extensive mechanical properties. Herein, a boron-silica-tantalum ternary hybrid phenolic aerogel (BSiTa-PA) with exceptional thermal stability, extensive mechanical strength, low thermal conductivity (49.6 mW m-1 K-1), and heightened ablative resistance is prepared by an expeditious method. After extremely thermal erosion, the obtained carbon aerogel demonstrates noteworthy electromagnetic interference (EMI) shielding performance with an efficiency of 31.6 dB, accompanied by notable loading property with specific modulus of 272.8 kN·m kg-1. This novel design concept has laid the foundation for the development of insulation materials in more complex extreme environments.

Prognostic impact of tertiary lymphoid structures in breast cancer prognosis: a systematic review and meta-analysis.

BACKGROUND: Tertiary lymphoid structures (TLSs), organizationally resemble lymph nodes, are frequently present in breast cancer (BCa). It is usually, but not always, associated with a positive prognosis or immunotherapy response in cancer patients. This meta-analysis was performed to assess the prognostic and clinical impact of TLSs in BCa. METHODS: We conducted a systematic search in PubMed, Embase, Cochrane Library, Web of Science, China National Knowledge Infrastructure, and WanFang Database to obtain eligible research data up to May 30, 2021. This meta-analysis is focusing on the studies evaluated the prognostic value of TLSs and the associated clinicopathologic indicators, related gene expression and survival. STATA software 16.0 software was used to assess the prognostic significance and clinical impact of TLSs. RESULTS: Nine studies involved with 2281 cases were incorporated in this meta-analysis, in which four of them evaluated the prognostic value of TLSs. There are 6 studies assessed the relationship of TLSs and 4 studies investigated the clinicopathologic parameters as well as the key gene expression, respectively. The results showed the presence of TLSs were predicting a better OS (HR = 0.61, 95% CI: 0.51-0.73, p < 0.001) and DFS (HR = 0.40, 95% CI: 0.17-0.93, p < 0.001) of BCa patients. It also revealed that the presence of TLSs was significantly correlated with tumor differentiation (p < 0.001), pTNM stage (p < 0.001), lymph node metastasis (p < 0.001), and TILs density (p < 0.001) of BCa, and the expression of Her2 (p < 0.001), ER (p < 0.001), PR (p < 0.001) and Ki67 (p = 0.009) of the tumor cell. CONCLUSION: Our results indicated that high levels of TLSs could predict a favorable prognosis for BCa. Moreover, the TLSs were significantly correlated with the clinicopathological indicators and the critical gene expression of BCa, indicating its potential clinical impact on BCa patients.

Precise positioning of enzymes within hierarchical polymer nanostructures for switchable bioelectrocatalysis.

The ability to reversibly switch bioelectrocatalytic sensors is attractive for the design of biomonitoring platforms displaying a complex environmental response, or for the protection of biosensors. However, the retention of reversible biocatalytic properties upon multiple environmental cycles, with broad detection range, low signal-to-noise and limit of detection remains challenging. In this report, we demonstrate the precise positioning of the enzyme glucose oxidase within block-copolymer brush nanostructures, via the re-initiation of N-isopropylacrylamide (NIPAM) polymerisation from enzyme-decorated poly(dimethylaminoethyl methacrylate) (PDMAEMA) blocks. We find that the precise design of polymer brush grafting density, thickness and crosslinking of the PNIPAM block enables the stable positioning of biocatalytic sites close to electrode surfaces. The control of the polymer brush nanostructure, its conformation and the distribution of biocatalytic sites is characterised via a combination of in situ ellipsometry, X-ray photoelectron spectroscopy, grazing angle FTIR and surface plasmon resonance. In turn, cyclic voltammetry and electrochemical impedance spectroscopy demonstrate that such control of the polymeric nanostructures confers a unique combination of low limit of detection (23.9 µM), a broad dynamic range of glucose sensing (0.05-12.8 mM) and true "OFF" state upon pH or thermal stimulation, whilst retaining excellent performance over repeated switching cycles of the sensor. Therefore, hierarchical biocatalytic polymer brushes display unique properties for the design of responsive biosensors and complex multi-functional gating platforms.

Core-independent approach for polymer brush-functionalised nanomaterials with a fluorescent tag for RNA delivery.

Here we describe a core-independent approach enabling the grafting of polymer brushes from the surface of nanomaterials and microparticles for oligonucleotide delivery. This method is based on the adsorption of a polyelectrolyte macroinitiator (MI) combined with a fluorescent conjugated polymer for efficient and stable labelling. This allows dense brushes to be generated, with growth kinetics comparable to those observed from mono-functional initiators, for the imaging of nanomaterial cellular localisation and uptake. We also study the impact of brush chemistry on interactions with cell membranes and on transfection efficiency. The method we report offers a unique freedom of design of the core size and shape as well as surface chemistry, whilst enabling tagging, for the study of transfection processes or theragnostic applications.

A Kinetic Model of Oligonucleotide-Brush Interactions for the Rational Design of Gene Delivery Vectors.

Polymer brushes are attractive candidates for the design of gene delivery vectors as they allow the systematic study of the impact of structural (type, size, and shape of nanomaterials core) and physicochemical parameters (cationic monomer chemistry, brush thickness, and grafting density) on transfection efficiency. However, relatively little is known of their interactions of oligonucleotides. To study such interactions, we use surface plasmon resonance and developed a kinetic model of brush binding and infiltration. We identify the striking impact that brush grafting density and thickness have on oligonucleotide kinetics of infiltration, binding affinity, and maximum loading. Surprisingly, double-stranded RNA molecules are found to load at significantly higher levels compared to DNA molecules of identical sequence (apart from uracils/thymines). Furthermore, analysis of the kinetics of adsorption of these oligonucleotides indicates that the stoichiometry of binding (ratio of amine versus phosphate residues) is close to parity for the uptake of 20 bp double-stranded RNA. Finally, nanoparticles were designed to be used as gene transfection vectors and to quantify if the brush grafting density and thickness significantly impact transfection efficiencies in a small interfering RNA knockdown assay. Therefore, this study demonstrates the rational design of polymer brush-based nanoparticle vectors for efficient delivery of oligonucleotides. The model developed will allow to uncover how the refinement of the physicochemical and structural properties of polymer brushes enable the tuning of RNA binding and allow the systematic study of cationic vectors efficiency for RNA delivery.