Assessment of Cellulose Nanofiber-Based Elastase Biosensors to Inflammatory Disease as a Function of Spacer Length and Fluorescence Response.

Inflammatory disease biomarker detection has become a high priority in point-of-care diagnostic research in relation to chronic wounds, with a variety of sensor-based designs becoming available. Herein, two primary aspects of biosensor design are examined: (1) assessment of a cellulose nanofiber (CNF) matrix derived from cotton ginning byproducts as a sensor transducer surface; and (2) assessment of the relation of spacer length and morphology between the CNF cellulose backbone and peptide fluorophore as a function of sensor activity for porcine pancreatic and human neutrophil elastases. X-ray crystallography, specific surface area, and pore size analyses confirmed the suitability of CNF as a matrix for wound care diagnostics. Based upon the normalized degree of substitution, a pegylated-linker connecting CNF transducer substrate to peptide fluorophore showed the greatest fluorescence response, compared to short- and long-chain alkylated linkers.

Washable Antimicrobial Wipes Fabricated from a Blend of Nanocomposite Raw Cotton Fiber.

In this study, a simple and effective way to produce washable antimicrobial wipes was developed based on the unique ability of raw cotton fiber to produce silver nanoparticles. A nanocomposite substructure of silver nanoparticles (25 ± 3 nm) was generated in raw cotton fiber without reducing and stabilizing agents. This nanocomposite raw cotton fiber (2100 ± 58 mg/kg in the concentration of silver) was blended in the fabrication of nonwoven wipes. Blending small amounts in the wipes-0.5% for antimicrobial properties and 1% for wipe efficacy-reduced the viability of S. aureus and P. aeruginosa by 99.9%. The wipes, fabricated from a blend of 2% nanocomposite raw cotton fiber, maintained their antibacterial activities after 30 simulated laundering cycles. The washed wipes exhibited bacterial reductions greater than 98% for both Gram-positive and Gram-negative bacteria.

Self-induced transformation of raw cotton to a nanostructured primary cell wall for a renewable antimicrobial surface.

Herein, raw cotton is shown to undergo self-induced transformation into a nanostructured primary cell wall. This process generates a metal nanoparticle-mediated antimicrobial surface that is regenerable through multiple washings. Raw cotton, without being scoured and bleached, contains noncellulosic constituents including pectin, sugars, and hemicellulose in its primary cell wall. These noncellulosic components provide definitive active binding sites for the in situ synthesis of silver nanoparticles (Ag NPs). Facile heating in an aqueous solution of AgNO3 activated raw cotton to produce Ag NPs (ca. 28 nm in diameter and 2261 mg kg-1 in concentration). Compared with scoured and bleached cotton, raw cotton requires lower concentrations of AgNO3-ten times lower for Klebsiella pneumonia and two times lower for Staphylococcus aureus-to achieve 99.9% reductions of both Gram-positive and Gram-negative bacteria. The Ag NPs embedded in the primary cell wall, which was confirmed via transmission electron microscopy images of the fiber cross-sections, are immobilized, exhibiting resistance to leaching as judged by continuous laundering. A remarkable percentage (74%) of the total Ag NPs remained in the raw cotton after 50 laundering cycles.

Intrafibrillar Dispersion of Cuprous Oxide (Cu2O) Nanoflowers within Cotton Cellulose Fabrics for Permanent Antibacterial, Antifungal and Antiviral Activity.

With increasingly frequent highly infectious global pandemics, the textile industry has responded by developing commercial fabric products by incorporating antibacterial metal oxide nanoparticles, particularly copper oxide in cleaning products and personal care items including antimicrobial wipes, hospital gowns and masks. Current methods use a surface adsorption method to functionalize nanomaterials to fibers. However, this results in poor durability and decreased antimicrobial activity after consecutive launderings. In this study, cuprous oxide nanoparticles with nanoflower morphology (Cu2O nanoflowers) are synthesized in situ within the cotton fiber under mild conditions and without added chemical reducing agents from a copper (II) precursor with an average maximal Feret diameter of 72.0 ± 51.8 nm and concentration of 17,489 ± 15 mg/kg. Analysis of the Cu2O NF-infused cotton fiber cross-section by transmission electron microscopy (TEM) confirmed the internal formation, and X-ray photoelectron spectroscopy (XPS) confirmed the copper (I) reduced oxidation state. An exponential correlation (R2 = 0.9979) between the UV-vis surface plasmon resonance (SPR) intensity at 320 nm of the Cu2O NFs and the concentration of copper in cotton was determined. The laundering durability of the Cu2O NF-cotton fabric was investigated, and the superior nanoparticle-leach resistance was observed, with the fabrics releasing only 19% of copper after 50 home laundering cycles. The internally immobilized Cu2O NFs within the cotton fiber exhibited continuing antibacterial activity (≥99.995%) against K. pneumoniae, E. coli and S. aureus), complete antifungal activity (100%) against A. niger and antiviral activity (≥90%) against Human coronavirus, strain 229E, even after 50 laundering cycles.

Thermosensitive textiles made from silver nanoparticle-filled brown cotton fibers.

Filling fibers with nanomaterials can create new functions or modify the existing properties. However, as nanocomposite formation for natural cellulosic fibers has been challenging, little information is available on how the embedded nanomaterials alter the properties of cellulosic fibers. Here we filled brown cotton fibers with silver nanoparticles (Ag NPs) to examine their thermosensitive properties. Using naturally present tannins in brown cotton fibers as a reducing agent, Ag NP-filled brown cotton fibers (nanoparticle diameter of about 28 nm, weight fraction of 12 500 mg kg-1) were produced through a one-step process without using any external agents. The in situ formation of Ag NPs was uniform across the nonwoven cotton fabric and was concentrated in the lumen of the fibers. The insertion of Ag NPs into the fibers shifted the thermal decomposition of cellulose to lower temperatures with increased activation energy and promoted heat release during combustion. Ag NPs lowered the thermal effusivity of the fabric, causing the fabric to feel warmer than the control brown cotton. Ag NP-filled brown cotton was more effectively heated to higher temperatures than control brown cotton under the same heating treatments.

Silver Nanoparticle-Infused Cotton Fiber: Durability and Aqueous Release of Silver in Laundry Water.

Although the application of silver nanoparticles to commercial antibacterial items is well-established, there have been increasing concerns that such particles might leach out, particularly into laundry water from textile products. A recently developed process wherein silver nanoparticles are synthesized in situ within the cotton fiber itself promises, however, to achieve the desired washing durability. In this study, the silver release behavior of the silver nanoparticle-infused cotton fabric during consecutive launderings in water and a detergent solution was analyzed. Silver nanoparticles (12 ± 3 nm in diameter) were uniformly produced throughout the entire volume of cotton fiber with a concentration of 3017 ± 56 mg/kg. A combination of colorimetric, spectroscopic, and elemental analyses showed (1) nonlinear silver release behavior, with a rapid release from externally formed nanoparticles during the initial washing and a plateau-like release from internally formed nanoparticles during extended washing, and (2) superior nanoparticle-leach resistance compared to those in commercial and laboratory-prepared textiles analyzed in the literature. The internal nanoparticles immobilized within cotton fiber exhibited persistent antibacterial activity after 50 home laundering cycles.

Thermal properties and surface chemistry of cotton varieties mineralized with calcium carbonate polymorphs by cyclic dipping.

In this study, hydroentangled cotton nonwovens were identified as effective hosts for mineralization of calcium carbonate (CaCO3) polymorphs to modify and improve their properties. All cotton varieties studied, including raw white cotton, scoured white cotton, and raw brown cotton, readily crystallized CaCO3 via a simple cyclic dipping process. A combination of analyses agreed that the surface chemistry of cotton fibers influenced the formation of different CaCO3 polymorphs. Scoured white cotton that consisted of almost pure cellulose predominantly produced the most stable calcite, whereas raw white and raw brown cottons that contain proteins facilitated the production of partial metastable vaterite. The morphology of calcite was better defined on the scoured cotton. The mineralization altered the hydrophobic surface of raw cottons to be hydrophilic, i.e., two-fold increase in moisture regain and decrease in water contact angle from 130 to 0 degrees. The mineralized cottons also exhibited improved thermal resistance, i.e., slower thermal decomposition with decreased activation energies and reduction in heat release capacity by up to 40%.

Method for identifying the triple transition (glass transition-dehydration-crystallization) of amorphous cellulose in cotton.

Although having a full picture of the heat-induced alterations in the fine structure of cellulosic materials is essential for designing their thermal processing, there have been no reliable methods to identify thermal transition temperatures. This study shows that colorimetric, thermogravimetric, and thermal kinetic parameters were sensitive to the thermochemical and thermo-structural changes in cotton fiber at low temperatures. Among these parameters, the activation energy for the thermal decomposition, evolving two local maxima against the preheating temperature, identified sequential thermal transformations in amorphous cellulose: 1) glass transition at 160-180 °C (Tg), 2) cellulose dehydration at 200-220 °C, and 3) crystallization at 240-260 °C. These results indicated that results of the mechanical tests or other methods discussed in the literature, which have produced inconsistent and higher Tg values (200-240 °C) for cellulosic materials, might have been misled by the dehydration of amorphous cellulose.

A reinforced thermal barrier coat of a Na-tannic acid complex from the view of thermal kinetics.

The poor burning resistance of cotton necessitates the control of its pyrolytic reactions, but many approaches have relied on the use of synthetically engineered chemicals. Herein, we show how a natural polyphenol from plants-tannic acid-acts with sodium ions to create a robust thermal barrier coat on cotton, with a focus on thermal kinetics. The kinetic information, combined with thermal and spectral analyses, revealed that the outer layer of galloyl units in tannic acid decomposes via a two-step reaction, producing a multicellular char of crosslinked aromatic rings, followed by the blowing of carbonaceous cells into a further expanded structure. This intumescent function of tannic acid was found to be enhanced upon its complexation with sodium ions, which greatly increased the activation energy for the first step of the reaction of tannic acid, to promote the formation of a stable char. The resulting blown char coated the cotton fiber below the thermal decomposition temperature of cellulose and was sustained throughout the decomposition. The enhanced thermal barrier performance of the Na-tannic acid complex was demonstrated by the reduced heat release capacity of cotton, the value of which was only about one-third that of tannic acid itself, and the inhibition of flame generation on cotton.

Precision Switching in a Discrete Supramolecular Assembly: Alkali Metal Ion-Carboxylate Selectivities and the Cationic Hofmeister Effect.

A cavitand host has been shown to switch from a dimeric assembly to a tetrameric assembly in the presence of cations. Induced by pseudo-specific cation binding attenuating the net negative charge of each host, switching was shown to be highly cation selective. Thus, the concentration of cation required to induce assembly switching ranged from 2 mM in the case of N(n-Bu)4+ to ∼80 mM in the case of Na+ . Overall cation affinity was found to be essentially the reverse of Collins' law of matching water affinities, which predicts Na+ to have the strongest affinity for carboxylate groups. Combined with previous data, these results highlight the point that cation affinity for carboxylates are in large part dictated by context.

Synthesis of Water-Soluble Deep-Cavity Cavitands.

An efficient, four-step synthesis of a range of water-soluble, deep-cavity cavitands is presented. Key to this approach are octahalide derivatives (4, X = Cl or Br) that allow a range of water-solubilizing groups to be added to the outer surface of the core host structure. In many cases, the conversion of the starting dodecol (1) resorcinarene to the different cavitands avoids any chromatographic procedures.

Molecular Shape and the Hydrophobic Effect.

This review focuses on papers published since 2000 on the topic of the properties of solutes in water. More specifically, it evaluates the state of the art of our understanding of the complex relationship between the shape of a hydrophobe and the hydrophobic effect. To highlight this, we present a selection of references covering both empirical and molecular dynamics studies of small (molecular-scale) solutes. These include empirical studies of small molecules, synthetic hosts, crystalline monolayers, and proteins, as well as in silico investigations of entities such as idealized hard and soft spheres, small solutes, hydrophobic plates, artificial concavity, molecular hosts, carbon nanotubes and spheres, and proteins.