In the effort toward sustainable advanced functional materials, nanocelluloses have attracted extensive recent attention. Nanocelluloses range from rod-like highly crystalline cellulose nanocrystals to longer and more entangled cellulose nanofibers, earlier denoted also as microfibrillated celluloses and bacterial cellulose. In recent years, they have spurred research toward a wide range of applications, ranging from nanocomposites, viscosity modifiers, films, barrier layers, fibers, structural color, gels, aerogels and foams, and energy applications, until filtering membranes, to name a few. Still, nanocelluloses continue to show surprisingly high challenges to master their interactions and tailorability to allow well-controlled assemblies for functional materials. Rather than trying to review the already extensive nanocellulose literature at large, here selected aspects of the recent progress are the focus. Water interactions, which are central for processing for the functional properties, are discussed first. Then advanced hybrid gels toward (multi)stimuli responses, shape-memory materials, self-healing, adhesion and gluing, biological scaffolding, and forensic applications are discussed. Finally, composite fibers are discussed, as well as nanocellulose as a strategy for improvement of photosynthesis-based chemicals production. In summary, selected perspectives toward new directions for sustainable high-tech functional materials science based on nanocelluloses are described.

https://www.onlinelibrary.wiley.com/doi/pdf/10.1002/adma.202004349

Nanocellulose: Recent Fundamental Advances and Emerging Biological and Biomimicking Applications.

Covalent layer-by-layer (LbL) assembly is a powerful method used to construct functional ultrathin films that enables nanoscopic structural precision, componential diversity, and flexible design. Compared with conventional LbL films built using multiple noncovalent interactions, LbL films prepared using covalent crosslinking offer the following distinctive characteristics: (i) enhanced film endurance or rigidity; (ii) improved componential diversity when uncharged species or small molecules are stably built into the films by forming covalent bonds; and (iii) increased structural diversity when covalent crosslinking is employed in componential, spacial, or temporal (labile bonds) selective manners. In this review, we document the chemical methods used to build covalent LbL films as well as the film properties and applications achievable using various film design strategies. We expect to translate the achievement in the discipline of chemistry (film-building methods) into readily available techniques for materials engineers and thus provide diverse functional material design protocols to address the energy, biomedical, and environmental challenges faced by the entire scientific community.

Covalent layer-by-layer films: chemistry, design, and multidisciplinary applications

Sediment extracts from three polluted sites of the river Elbe basin were fractionated using a novel online fractionation procedure. Resulting fractions were screened for mutagenic, aryl hydrocarbon receptor (AhR)-mediated, transthyretin (TTR)-binding, and estrogenic activities and their potency to inhibit gap junctional intercellular communication (GJIC) to compare toxicity patterns and identify priority fractions. Additionally, more than 200 compounds and compound classes were identified using GC-MS/MS, LC-MS/MS, and HPLC-DAD methods. For all investigated end points, major activities were found in polar fractions, which are defined here as fractions containing dominantly compounds with at least one polar functional group. Nonpolar PAH fractions contributed to mutagenic and AhR-mediated activities while inhibition of GJIC and estrogenic and TTR-binding activities were exclusively observed in the polar fractions. Known mutagens in polar fractions included nitro- and dinitro-PAHs, azaarenes, and keto-PAHs, while parent and monomethylated PAHs such as benzo[a]pyrene and benzofluoranthenes were identified in nonpolar fractions. Additionally, for one sample, high AhR-mediated activities were determined in one fraction characterized by PCDD/Fs, PCBs, and PCNs. Estrone, 17β-estradiol, 9H-benz[de]anthracen-7-one, and 4-nonylphenol were identified as possible estrogenic and TTR-binding compounds. Thus, not only nonpolar compounds such as PAHs, PCBs, and PCDD/Fs but also the less characterized and investigated more polar substances should be considered as potent mutagenic, estrogenic, AhR-inducing, TTR-binding, and GJIC-inhibiting components for future studies.

/pdf/polar-compounds-dominate-in-vitro-effects-of-sediment-l30o1ic712.pdf

Polar Compounds Dominate in Vitro Effects of Sediment Extracts

Automated fractionation procedure for polycyclic aromatic compounds in sediment extracts on three coupled normal-phase high-performance liquid chromatography columns

Efficient and selective aqueous-phase hydrogenation of phenol by a novel Pd catalyst supported on dually and selectively functionalized mesoporous MMT-1 silica nanoparticles has been developed. The catalyst features small (∼1.1 nm) Pd nanoparticles surrounded by unevenly distributed nitrogen- or heteroatom-free organic groups in the helical mesopores and the presence of non-hydrogen-bonded isolated silanol groups on the mesopore surface. The catalyst exhibited superior conversion of phenol and high selectivity of cyclohexanone at room temperature under atmospheric pressure of hydrogen and remained highly active after ten catalytic runs. The catalyst was active for the aqueous-phase hydrogenation of a variety of mono- and dihydroxylated aromatic compounds. The green protocol with the designed catalyst would be practical for the hydrogenation of phenol and other derivatives.

Efficient Room-Temperature Aqueous-Phase Hydrogenation of Phenol to Cyclohexanone Catalyzed by Pd Nanoparticles Supported on Mesoporous MMT-1 Silica with Unevenly Distributed Functionalities

https://pubs.acs.org/doi/pdf/10.1021/acs.biomac.9b00979

Revealing the Architecture of the Cell Wall in Living Plant Cells by Bioimaging and Enzymatic Degradation.

The adsorption of phenol, an aromatic compound with a hydrogen-bonding group, onto a silica surface in cyclohexane was investigated by colloidal probe atomic force microscopy (AFM), attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), and adsorption isotherm measurements. ATR-FTIR measurements on the silica surface indicated the formation of surface macroclusters of phenol through hydrogen bonding. The ATR-FTIR spectra were also measured on the H-terminated silicon surface to observe the effect of the silanol groups on the phenol adsorption. The comparison of the ATR-FTIR spectra for both the silicon oxide and H-terminated silicon surfaces proved that the silanol groups are necessary for the formation of phenol clusters on the surface. The surface force measurement using colloidal probe AFM showed a long-range attraction between the two silica surfaces in phenol-cyclohexane mixtures. This long-range attraction resulted from the contact of the adsorbed phenol layers for the phenol concentrations below 0.6 mol %, at which no significant phenol clusters formed in the bulk solution. The attraction started to decrease at 0.6 mol % phenol due to the exchange of the phenol molecules between the clusters in the bulk phase and on the surface. The surface density of phenol in the adsorbed layer was calculated on the basis of the long-range attraction and found to be much smaller than the liquid phenol density. The plausible structure of the adsorbed phenol layer was drawn by referring to the crystal structure of the bulk phenol and orientation of the phenol molecules on the surface, estimated by the dichroic analysis of ATR-FTIR spectroscopy. The investigation of the phenol adsorption on the silica surface in a nonpolar solvent using this novel approach demonstrated the effect of the aromatic ring on the surface packing density.

Molecular macrocluster formation on silica surfaces in phenol-cyclohexane mixtures.

Molecular nonwoven fabrics in the form of ultrathin layer-by-layer (LbL) helical polymer films with covalent cross-linking were assembled on substrates by an alternate ester–amide exchange reaction between poly(γ-methyl l-glutamate) (PMLG) and cross-linking agent ethylene diamine or 4,4′-diamino azobenzene. The regular growth of helical monolayers without excessive adsorption and the formation of amide bonds were confirmed by ultraviolet–visible (UV–vis) spectrophotometry, quartz crystal microbalance (QCM), ellipsometry, and infrared reflection–absorption spectroscopy (IR-RAS) measurements. Nanostructures with high uniformity and ultrathin films with few defects formed by helical rod segments of PMLG were characterized by atomic force microscopy (AFM) and Kelvin probe force microscopy (KFM).

Construction and characterization of molecular nonwoven fabrics consisting of cross-linked poly(γ-methyl-L-glutamate).

Among gene delivery systems, peptide-based gene carriers have received significant attention because of their selectivity, biocompatibility, and biodegradability. Since cellular membranes function as a barrier toward exogenous molecules, cell-penetrating peptides (CPPs), which are usually cationic and/or amphiphilic, can serve as efficient carriers to deliver cargo into the cytosol. Here, we examined the interactions of carrier peptides and their DNA complexes with lipid membranes using a quartz crystal microbalance (QCM) and high-speed atomic force microscopy (HS-AFM). The carrier peptides are a 12-residue partial presequence of yeast cytochrome c oxidase subunit IV (Cytcox) and BP100, which are a mitochondria-targeting signal peptide and a CPP, respectively. QCM data showed that BP100 has a higher binding affinity than Cytcox to both plasma membrane- and mitochondrial membrane-mimicking lipid bilayers. The DNA complexes with either Cytcox or BP100 exhibited the same tendency. Furthermore, HS-AFM data demonstrated that the DNA complexes of either peptide can disrupt the lipid membranes, forming larger pores in the case of Cytcox. Our results suggest that the binding affinity of the peptide/DNA complex to the plasma membrane is more critical than its membrane disruption ability in enhancing the cellular uptake of DNA.

Neval Yilmaz

Papers

Revealing the Architecture of the Cell Wall in Living Plant Cells by Bioimaging and Enzymatic Degradation.

Molecular macrocluster formation on silica surfaces in phenol-cyclohexane mixtures.

Construction and characterization of molecular nonwoven fabrics consisting of cross-linked poly(γ-methyl-L-glutamate).

Lipid Membrane Interaction of Peptide/DNA Complexes Designed for Gene Delivery

Zwitterionic Polypeptides: Chemoenzymatic Synthesis and Loosening Function for Cellulose Crystals.