Trimethylsilyl Cellulose Research Articles

Effects of ZnO/trimethylsilyl cellulose nano-composite coating on anti-UV and anti-fungal properties of papers

Trimethylsilyl cellulose (TMSC) was employed as the coating matrix for the application of zinc oxide nanoparticles (ZnO) onto paper surfaces and the protections of ZnO/TMSC coating against UV-induced damages and fungal spoilage were evaluated. Filter papers were immersed in 2% w/v TMSC solution loaded with ZnO and air-dried. Three ZnO/TMSC suspensions were prepared with 0.1, 0.5, and 1% w/v ZnO NPs. The presences of ZnO/TMSC protective layers were confirmed with ATR-IR spectroscopy. The coated papers exhibited high surface hydrophobicities. After the coated papers were subject to 365-nm UV irradiation at 400 W for 3 h, the contact angles dramatically dropped. The trimethylsilyl (TMS) groups exposed on the surface formed a moisture barrier and were partially removed on UV exposure. ATR-IR revealed that more TMS groups were removed in the protective layer with no ZnO. UV-irradiated papers turned yellow and papers protected with 1% ZnO/TMSC exhibited significantly lower color changes than that of the uncoated one. Compared to the TMSC-coated paper, the addition of ZnO resulted in a significant reduction in tensile strength at maximum. However, after UV irradiation, significant increases in both the strain at break and strength at maximum were only observed in 1% ZnO/TMSC-protected papers. Regarding their anti-fungal properties, the 1% ZnO/TMSC films were effective in growth inhibitions of Aspergillus sp. and Penicillium sp. on the nonirradiated papers. Despite being hydrophilic after UV-irradiation, growths of the molds were severely suppressed on the UV-irradiated paper.

Integrated lateral flow immunoassays using trimethylsilyl cellulose barriers for the enhanced sensitivity of COVID-19 diagnosis

Lateral flow immunoassays (LFIAs) serve as rapid and convenient tools for disease screening. However, there is room for enhancing diagnostic sensitivity. Therefore, this paper introduces a novel material combined with lateral flow immunoassays to improve the sensitivity of COVID-19 detection and diagnosis. Trimethylsilyl cellulose (TMSC) was printed on the device between the test and control line to delay the flow of the solution, which resulted in a more excellent binding of the immunoassay. These delay-LFIAs (d-LFIAs) were developed for the diagnosis of COVID-19, targeting the detection of immunoglobulins G and M, as well as the COVID-19 antigen. Under optimized conditions, the d-LFIA increased the sensitivity by up to 5 times compared to that of conventional LFIAs. Moreover, it exhibited the ability to detect IgG, IgM, and SARS-CoV-2 antigens as low as 1 ng/mL (limit of detection) by the naked eye. In addition, the application of this device to real samples yielded highly consistent results with those obtained from other LFIAs and standard SARS-CoV-2 diagnostic methods (such as enzyme-linked immunosorbent assay and reverse transcription polymerase chain reaction) diagnosis. Therefore, we expect this device to be a new platform for highly sensitive, easy, and affordable immunoassay strip testing to certify future emerging diseases.

Interplay of electrolyte concentration and molecular weight of polyDADMAC on cellulose surface adsorption

Cationic polyelectrolytes (PEs) are commonly used additives in manufacturing of cellulose based products such as regenerated fibers and paper to tailor their product properties. Here we are studying the adsorption of poly(diallyldimethylammonium chloride), PD, on cellulose, using in situ surface plasmon resonance spectroscopy (SPR) measurements. We employ model surfaces from regenerated cellulose xanthate (CX) and trimethylsilyl cellulose (TMSC), mimicking industrially relevant regenerated cellulose substrates. The effects of the PDs molecular weight were strongly depending on the ionic strength and type of electrolyte (NaCl vs CaCl2). Without electrolytes, the adsorption was monolayer-type, i.e. independent of molecular weight. At moderate ionic strength, adsorption increased due to more pronounced PE coiling, while at high ionic strength electrostatic shielding strongly reduced adsorption of PDs. Results exhibited pronounced differences for the chosen substrates (cellulose regenerated from xanthate (CXreg) vs. regenerated from trimethylsilyl cellulose, TMSCreg). Consistently higher adsorbed amounts of the PD were determined on CXreg surfaces compared TMSC. This can be attributed to a more negative zeta potential, a higher AFM roughness and a higher degree of swelling (investigated by QCM-D) of the CXreg substrates.

A novel delayed lateral flow immunoassay for enhanced detection of SARS-CoV-2 spike antigen.

A new detection strategy was developed to improve the sensitivity of a lateral flow immunoassay platform utilizing a delayed hydrophobic barrier fabricated with trimethylsilyl cellulose (TMSC). The SARS-CoV-2 spike receptor-binding domain (SARS-CoV-2 SP RBD) antigen was chosen as a model analyte to demonstrate the superior detectability of this scheme. The novel device consists of 2 separate layers, so-called delayed lateral flow immunoassay (d-LFIA). The upper layer is intended for the analyte or sample flow path, where the test solution flows freely straight to the detection zone to bind with the primary antibody. The lower layer, located just underneath, is designed for the SARS-CoV-2 spike receptor-binding domain-conjugated gold nanoparticles (SARS-CoV-2 SP RBD-AuNPs) used for producing a colorimetric signal. This layer is fabricated with a TMSC barrier to time-delay the movement of SARS-CoV-2 SP RBD-AuNPs, thus allowing the antigen to bind with the primary antibody more efficiently. This platform exhibited a 2.6-fold enhancement in the sensitivity and 9.1-fold improvement in the limit of detection (LOD) as compared with the conventional LFIA. In addition, this d-LFIA device was satisfactorily applied to accurate screening of COVID-19 patients.Graphical abstract Supplementary InformationThe online version contains supplementary material available at 10.1007/s00604-022-05467-3.

Highly stable nano magnesium oxide organic coatings for nondestructive protection of acidic paper documents

Paper documents possess significant cultural, history and art values. However, acidification as the main factor causes rapid degradation of paper documents. For the nondestructive protection of acidic paper documents, the highly stable nano magnesium oxide (MgO) organic coatings based on the synergistic dispersion of trimethylsilylcellulose (TMSC) and isopropanol (IPA) were prepared. It was clarified in detail by experimental and computational studies. IPA played a significant role in aggregation inhibition of nano MgO through the reduction of interparticle attraction potential to reduce the particle size. Meanwhile, the dispersion stability was further improved with the greater steric hindrance of TMSC (more than 1 month). The highly stable nano MgO organic coatings were applied for deacidification of the acidic paper documents via impregnation. Evaluation showed that nano MgO particles were evenly deposited on the paper, which has little influence on the clarity of writing by increasing the optical density of ink. Moreover, acidic paper after treatment, with a good alkaline reserve and anti-mold performance, is expected to have excellent stability during aging.

Growing of Artificial Lignin on Cellulose Ferulate Thin Films.

Thin films of cellulose ferulate were designed to study the formation of dehydrogenation polymers (DHPs) on anchor groups of the surface. Trimethylsilyl (TMS) cellulose ferulate with degree of substitution values of 0.35 (ferulate) and 2.53 (TMS) was synthesized by sophisticated polysaccharide chemistry applying the Mitsunobu reaction. The biopolymer derivative was spin-coated into thin films to yield ferulate moieties on a smooth cellulose surface. Dehydrogenative polymerization of coniferyl alcohol was performed in a Quartz crystal microbalance with a dissipation monitoring device in the presence of H2O2 and adsorbed horseradish peroxidase. The amount of DHP formed on the surface was found to be independent of the base layer thickness from 14 to 75 nm. Pyrolysis-GC-MS measurements of the DHP revealed β-O-4 and β-5 linkages. Mimicking lignification of plant cell walls on highly defined model films enables reproducible investigations of structure-property relationships.

Humidity Response of Cellulose Thin Films.

Cellulose–water interactions are crucial to understand biological processes as well as to develop tailor made cellulose-based products. However, the main challenge to study these interactions is the diversity of natural cellulose fibers and alterations in their supramolecular structure. Here, we study the humidity response of different, well-defined, ultrathin cellulose films as a function of industrially relevant treatments using different techniques. As treatments, drying at elevated temperature, swelling, and swelling followed by drying at elevated temperatures were chosen. The cellulose films were prepared by spin coating a soluble cellulose derivative, trimethylsilyl cellulose, onto solid substrates followed by conversion to cellulose by HCl vapor. For the highest investigated humidity levels (97%), the layer thickness increased by ca. 40% corresponding to the incorporation of 3.6 molecules of water per anhydroglucose unit (AGU), independent of the cellulose source used. The aforementioned treatments affected this ratio significantly with drying being the most notable procedure (2.0 and 2.6 molecules per AGU). The alterations were investigated in real time with X-ray reflectivity and quartz crystal microbalance with dissipation, equipped with a humidity module to obtain information about changes in the thickness, roughness, and electron density of the films and qualitatively confirmed using grazing incidence small angle X-ray scattering measurements using synchrotron irradiation.

Microencapsulation of camphor using trimethylsilylcellulose

Microencapsulation of camphor by trimethylsilylcellulose was performed using oil-in-water emulsion method. Trimethylsilylcellulose (TMSC) with the DS value of 2.41 (CHN analysis) was synthesized by dissolving commercial cellulose in N, N-dimethylacetamide/LiCl followed by reacting with hexamethyldisilazane. Sodium dodecyl sulfate (SDS) in acidic aqueous solution and tetramethylammonium chloride (TMACl) in water were attempted as emulsifiers. The oil phase composed of TMSC and camphor in ethyl acetate was dispersed in emulsifier solution. The mass ratio of TMSC to camphor and emulsifier concentration were optimized to produce high quality microcapsules. Using the mass ratio of 3:7 and 1% (w/v) SDS solution gave well separated microcapsules of TMSC_C_SDS (1). The diameter size in the micron range (10–110 mm) and high camphor content (∼21.07%) were obtained from this sample. The larger size of the capsules obtained from TMACl system indicated the coalescence of the oil droplets. The hydrolysis of the external surface of the microcapsules was observed in the SDS system. However, this caused a minor effect on the cellulose stability in TMSC_C_SDS (1). The freshly prepared microcapsules of TMSC_C_SDS (1) showed the fast release of camphor during first 2 h and reached the equilibrium after 7 h.

Patterning a cellulose based dual-tone photoresist via deep X-ray lithography

The desire to combine properties such as ready availability, low price and biodegradability makes cellulose derivatives such as Trimethylsilyl cellulose (TMSC) an ideal precursor suited to study different applications on the abundant material, cellulose. Here we introduce a lithographic approach to pattern the cellulose derivative, TMSC, via photoinduced X-ray conversion. Thin films of this biopolymer were irradiated by means of proximity deep X-ray lithography. With increasing energy dose, we found distinct structural and chemical changes resulting in two polarity transitions and related thereto material solubility alterations. Based on this, we demonstrate that positive and negative tone structures can be obtained in one single exposure at the same energy dose. Notably, the positive tone pattern is produced when applying Isopropyl alcohol (IPA) or purified water to dissolve the exposed surface. In contrast, the negative tone structure is produced with toluene. These findings suggest TMSC as a potential dual-tone photoresist applicable in microelectronics or surface chemistry where it can be applied as a dielectric layer, a pattern template, used in microfluidics or functionalized for bioassays.

Highly Norbornylated Cellulose and Its "Click" Modification by an Inverse-Electron Demand Diels-Alder (iEDDA) Reaction.

A facile, catalyst-free synthesis of a norbornylated cellulosic material (NC) with a high degree of substitution (2.9) is presented by direct reaction of trimethylsilyl cellulose with norbornene acid chloride. The resulting NC is highly soluble in organic solvents and its reactive double bonds were exploited for the copper-free inverse-electron demand Diels–Alder (iEDDA) “click” reaction with 3,6-di(pyridin-2-yl)-1,2,4,5-tetrazine. Reaction kinetics are comparable to the well-known Huisgen type 1,3-dipolar cycloaddition of azide with alkynes, while avoiding toxic catalysts.

Comparison of Trimethylsilyl Cellulose-Stabilized Carbonate and Hydroxide Nanoparticles for Deacidification and Strengthening of Cellulose-Based Cultural Heritage.

Herein, colloidal dispersions of alkaline nanoparticles (NPs: CaCO3 and Mg(OH)2) are stabilized by trimethylsilyl cellulose (TMSC) in hexamethyldisiloxane and employed to treat historical wood pulp paper by an effortless dip-coating technique. Both alkaline NPs exhibit high stability and no size and shape changes upon stabilization with the polymer, as shown by UV–vis spectroscopy and transmission electron microscopy. The long-term effect of NP/TMSC coatings is investigated in detail using accelerated aging. The results from the pH-test and back-titration of coated papers show a complete acid neutralization (pH ∼ 7.4) and introduction of adequate alkaline reserve even after prolonged accelerated aging. Scanning electron microscopy–energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and infrared and water contact angle measurements showed the introduction of a thin and smooth hydrophobic NP/TMSC coating on the paper fibers. Acid-catalyzed desilylation of TMSC was observed by declining C-Si infrared absorbance peaks upon aging. The CaCO3 coatings are superior to Mg(OH)2 with respect to a reduced yellowing and lower cellulose degradation upon aging as shown by colorimetric measurements and degree of polymerization analysis. The tensile strength and folding endurance of coated and aged papers are improved to 200–300 and 50–70% as illustrated by tensile strength and double folding endurance measurements.

Bubble Attachment to Cellulose and Silica Surfaces of Varied Surface Energies: Wetting Transition and Implications in Foam Forming.

To better understand the complex system of wet foams in the presence of cellulosic fibers, we investigate bubble–surface interactions by following the effects of surface hydrophobicity and surface tension on the contact angle of captive bubbles. Bubbles are brought into contact with model silica and cellulose surfaces immersed in solutions of a foaming surfactant (sodium dodecyl sulfate) of different concentrations. It is observed that bubble attachment is controlled by surface wetting, but a significant scatter in the behavior occurs near the transition from partial to complete wetting. For chemically homogeneous silica surfaces, this transition during bubble attachment is described by the balance between the energy changes of the immersed surface and the frictional surface tension of the moving three-phase contact line. The situation is more complex with chemically heterogeneous, hydrophobic trimethylsilyl cellulose (TMSC). TMSC regeneration, which yields hydrophilic cellulose, causes a dramatic drop in the bubble contact angle. Moreover, a high interfacial tension is required to overcome the friction caused by microscopic (hydrophilic) pinning sites of the three-phase contact line during bubble attachment. A simple theoretical framework is introduced to explain our experimental observations.

Study of xylan and cellulose interactions monitored with solid-state NMR and QCM-D

Abstract Development of physical properties of bleached eucalyptus kraft pulp is typically based on the refining process. However, many studies have reported that xylan deposition is a viable alternative. As the mechanisms of xylan and cellulose interactions are not clear, the main goal of this study was to achieve a better understanding of these interactions. Considering that a sample of pulp enriched with xylan is a very complex matrix, a model system was developed. Cellulosic thin films were prepared by spincoating and the Langmuir-Schaefer (LS) method from trimethylsilylcellulose (TMSC). Their interactions with xylan were analyzed using the quartz crystal microbalance with dissipation (QCM-D) monitoring technique. The topological changes on cellulose were studied using atomic force microscopy (AFM). For the 13C solid-state nuclear magnetic resonance (NMR) studies, samples were prepared using commercial microcrystalline cellulose (MCC) and xylan. The xylan was extracted from bleached birch kraft pulp using a cold caustic extraction (CCE) method. The QCM-D monitoring showed deposition only with higher concentrations of xylan solution (1 mg · l−1) for the LS method. The AFM images showed that xylan deposits as agglomerates on the cellulose surface, and the NMR experiments showed that there are interactions for the more ordered region of the cellulose fiber and for the less-ordered region.

Structural Order in Cellulose Thin Films Prepared from a Trimethylsilyl Precursor.

Biopolymer cellulose is investigated in terms of the crystallographic order within thin films. The films were prepared by spin-coating of a trimethylsilyl cellulose precursor followed by an exposure to HCl vapors; two different source materials were used. Careful precharacterization of the films was performed by infrared spectroscopy and atomic force microscopy. Subsequently, the films were investigated by grazing incidence X-ray diffraction using synchrotron radiation. The results showed broad diffraction peaks, indicating a rather short correlation length of the molecular packing in the range of a few nanometers. The analysis of the diffraction patterns was based on the known structures of crystalline cellulose, as the observed peak pattern was comparable to cellulose phase II and phase III. The dominant fraction of the film is formed by two different types of layers, which are oriented parallel to the substrate surface. The stacking of the layers results in a one-dimensional crystallographic order with a defined interlayer distance of either 7.3 or 4.2 Å. As a consequence, two different preferred orientations of the polymer chains are observed. In both cases, polymer chain axes are aligned parallel to the substrate surface, and the orientation of the cellulose molecules are concluded to be either edge-on or flat-on. A minor fraction of the cellulose molecules form nanocrystals that are randomly distributed within the films. In this case, the molecular packing density was found to be smaller in comparison to the known crystalline phases of cellulose.

Design of Friction, Morphology, Wetting, and Protein Affinity by Cellulose Blend Thin Film Composition.

Cellulose derivate phase separation in thin films was applied to generate patterned films with distinct surface morphology. Patterned polymer thin films are utilized in electronics, optics, and biotechnology but films based on bio-polymers are scarce. Film formation, roughness, wetting, and patterning are often investigated when it comes to characterization of the films. Frictional properties, on the other hand, have not been studied extensively. We extend the fundamental understanding of spin coated complex cellulose blend films via revealing their surface friction using Friction Force Microscopy (FFM). Two cellulose derivatives were transformed into two-phase blend films with one phase comprising trimethyl silyl cellulose (TMSC) regenerated to cellulose with hydroxyl groups exposed to the film surface. Adjusting the volume fraction of the spin coating solution resulted in variation of the surface fraction with the other, hydroxypropylcellulose stearate (HPCE) phase. The film morphology confirmed lateral and vertical separation and was translated into effective surface fraction. Phase separation as well as regeneration contributed to the surface morphology resulting in roughness variation of the blend films from 1.1 to 19.8 nm depending on the film composition. Friction analysis was successfully established, and then revealed that the friction coefficient of the films could be tuned and the blend films exhibited lowered friction force coefficient compared to the single-component films. Protein affinity of the films was investigated with bovine serum albumin (BSA) and depended mainly on the surface free energy (SFE) while no direct correlation with roughness or friction was found. BSA adsorption on film formed with 1:1 spinning solution volume ratio was an outlier and exhibited unexpected minimum in adsorption.

Deposition of Cellulose-Based Thin Films on Flexible Substrates.

This study investigates flexible (polyamide 6.6 PA-6.6, polyethylene terephthalate PET, Cu, Al, and Ni foils) and, for comparison, stiff substrates (silicon wafers and glass) differing in, for example, in surface free energy and surface roughness and their ability to host cellulose-based thin films. Trimethylsilyl cellulose (TMSC), a hydrophobic acid-labile cellulose derivative, was deposited on these substrates and subjected to spin coating. For all the synthetic polymer and metal substrates, rather homogenous films were obtained, where the thickness and the roughness of the films correlated with the substrate roughness and its surface free energy. A particular case was the TMSC layer on the copper foil, which exhibited superhydrophobicity caused by the microstructuring of the copper substrate. After the investigation of TMSC film formation, the conversion to cellulose using acidic vapors of HCl was attempted. While for the polymer foils, as well as for glass and silicon, rather homogenous and smooth cellulose films were obtained, for the metal foils, there is a competing reaction between the formation of metal chlorides and the generation of cellulose. We observed particles corresponding to the metal chlorides, while we could not detect any cellulose thin films after HCl treatment of the metal foils as proven by cross-section imaging using scanning electron microscopy (SEM).

Strengthening of paper by treatment with a suspension of alkaline nanoparticles stabilized by trimethylsilyl cellulose

Control over the mechanical properties of cellulose-based artifacts (e.g. paper) is highly important in cultural heritage science. Especially, a non-aqueous method that does not cause swelling but can be applied to either single paper sheets or bound cellulose items (e.g., books) without any preselection is currently needed. Herein, we present a new multilayer deposition method that can simultaneously deposit alkaline reserve and improve the mechanical properties of historic wood pulp (HWP) paper, which often suffers from high fragility and brittleness. Alkaline nanoparticles (magnesium hydroxide Mg(OH)2NPs) stabilized by hydrophobic cellulose derivative i.e., trimethylsilyl cellulose (TMSC) in hexamethyldisiloxane (HMDSO) are prepared and deposited in the form of multiple layers on HWP paper by a technically effortless dip coating procedure. An enhanced and irreversible deposition of Mg(OH)2 NPs–TMSC and an alkaline reserve (AR) up to 4% (139 meq[OH−]/100g) are achieved as revealed by infrared spectroscopy and back-titration measurement. The tensile strength of uncoated HWP paper (1.6 MPa) is increased to 5.5 MPa after coating with Mg(OH)2NPs/TMSC (before aging) and then to ca 9 MP (after accelerated aging). In the latter case, the TMSC is transformed to cellulose by cleaving of O–Si bonds. The surfaces are evenly covered with thin and transparent coatings of hydrophobized nanoparticles as demonstrated by electron scanning microscopy and contact angle measurements.

Cellulose-polyethyleneimine blend membranes with anomalous nanofiltration performance

A unique method for the preparation of cellulose-polyethyleneimine (PEI) blend membranes for nanofiltration is presented. Trimethylsilyl cellulose was used as a precursor for the blend membrane fabrication followed by a simple hydrolysis to regenerate the cellulose structure. The resulting homogeneous blend membranes exhibited high neutral solute rejection in water, which was surprisingly better than the performance of the individual membranes due to the strong interactions between the blended polymers. More interestingly, the same membrane demonstrated over five times higher flux of methanol after solvent activation with water as compared to the fluxes of the pure membranes, attributed to formation of nanocracks. High rejection of negatively charged dyes in this solvent with around 450 Da molecular weight cut-off was obtained at an exceptionally high flux of 160 Lm−2 h−1 at a pressure of 4.5 bar. The membranes will be beneficial in nanofiltration of polar solvents containing neutral and charged molecules.

High dehumidification performance of amorphous cellulose composite membranes prepared from trimethylsilyl cellulose

Composite membranes with a thin cellulose layer with outstanding flux and selectivity for water vapour are achieved via coating with trimethylsilyl cellulose.

Smart functional polymer coatings for paper with anti-fouling properties.

Cellulose, as the main component of paper, is becoming more and more important for several high tech applications because of its beneficial properties, such as abundance, low cost, renewability, mechanical robustness and biocompatibility. To make cellulose accessable for new applications it is necessary to introduce new properties, which can be done by surface modification e.g. grafting of polymers onto surfaces. In this work, two comb copolymers, poly[(2-methyl-2-oxazoline methacrylate)-co-glycidyl methacrylate] and poly[(2-methacryloyloxyethyl phosphorylcholine)-co-glycidyl methacrylate], were synthesized by free radical polymerization of glycidyl methacrylate and oligo(2-methyl-2-oxazoline) as well as 2-methacryloyloxyethyl phosphorylcholine. After extensive characterization the polymers were covalently attached to thin cellulose model layers and filter paper using a one-step grafting-to approach. For the comprehensive analysis of these layers, thin cellulose films were fabricated on silicon wafers by spin coating of trimethylsilyl cellulose followed by acid hydrolysis which resulted in homogeneous layers as substrates for the grafting process of the functional polymers. The layers were characterized by X-ray photoelectron spectroscopy (XPS), attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), atomic force microscopy (AFM) and energy-dispersive X-ray spectroscopy (EDX). To demonstrate the high potential of such polymer-modified cellulose materials, protein repellance of the cellulose films, containing peptidomimetic 2-methyl-2-oxazoline and zwitterionic phosphorylcholine groups after successful functionalization, is shown. Cell adhesion experiments using Bacillus subtilis, Escherichia coli and Saccharomyces cerevisiae indicate the considerable anti-fouling capacity against both Gram-positive and Gram-negatve bacteria as well as the yeast fungus.