Sustainable All-Cellulose Biocomposites from Renewable Biomass Resources Fabricated in a Water-Based Processing System by the Vacuum-Filtration-Assisted Impregnation Method.

The increasing awareness of global ecological concerns and the rising sustainability consciousness associated with the manufacturing of non-renewable and non-biodegradable composite materials have led to extensive research on product and process developments of more sustainable, environmentally friendly, and fully biodegradable biocomposites for higher-value end-use applications. All-cellulose composites (ACCs) are an emerging class of biocomposites, which are produced utilizing solely cellulose as a raw material that is derived from various renewable biomass resources, such as trees and plants, and are assessed as fully biodegradable. In this study, sustainable ACCs were fabricated for the first time based on the full dissolution of commercially available sulfite dissolving (D) pulps as a matrix with concentrations of 1.5 wt.% and 2.0 wt.% in an aqueous NaOH-urea solvent, and they were then impregnated on/into the pre-fabricated birch (B), abaca (A), and northern softwood (N) fiber sheets as reinforcements by the vacuum-filtration-assisted impregnation approach. This research aimed to investigate the effects of the impregnated cellulose matrix concentrations and types of the utilized cellulose fiber reinforcements (B, A, N) on the morphological, crystalline, structural, and physio-mechanical properties of the ACCs. The highest degrees of improvements were achieved for tensile strength (+532%, i.e., from 9.24 MPa to 58.04 MPa) and strain at break of the B fiber-reinforced ACC B1.5 (+446%, i.e., from 1.36% to 4.62%) fabricated with vacuum impregnation of the 1.5 wt.% cellulose matrix. Noticeably, the greatest improvements were attained in strain at break of the A and N fiber-reinforced ACCs A2.0 (+218%, i.e., from 4.44 % to 14.11%) and N2.0 (+466%, i.e., 2.59% to 14.65%), respectively, produced with vacuum impregnation of the 2.0 wt.% cellulose matrix. The study highlights the diverse properties of the all-cellulose biocomposite materials that could, expectedly, lead to further development and research for upscaled production of the ACCs.

Correction: Sorsak et al. Design and Investigation of Optical Properties of N-(Rhodamine-B)-Lactam-Ethylenediamine (RhB-EDA) Fluorescent Probe. Sensors 2018, 18, 1201.

In the published publication [...].

Superparamagnetic Spinel-Ferrite Nano-Adsorbents Adapted for Hg2+, Dy3+, Tb3+ Removal/Recycling: Synthesis, Characterization, and Assessment of Toxicity.

In the present work, superparamagnetic adsorbents based on 3-aminopropyltrimethoxy silane (APTMS)-coated maghemite (γFe2O3@SiO2-NH2) and cobalt ferrite (CoFe2O4@SiO2-NH2) nanoparticles were prepared and characterized using transmission-electron microscopy (TEM/HRTEM/EDXS), Fourier-transform infrared spectroscopy (FTIR), specific surface-area measurements (BET), zeta potential (ζ) measurements, thermogravimetric analysis (TGA), and magnetometry (VSM). The adsorption of Dy3+, Tb3+, and Hg2+ ions onto adsorbent surfaces in model salt solutions was tested. The adsorption was evaluated in terms of adsorption efficiency (%), adsorption capacity (mg/g), and desorption efficiency (%) based on the results of inductively coupled plasma optical emission spectrometry (ICP-OES). Both adsorbents, γFe2O3@SiO2-NH2 and CoFe2O4@SiO2-NH2, showed high adsorption efficiency toward Dy3+, Tb3+, and Hg2+ ions, ranging from 83% to 98%, while the adsorption capacity reached the following values of Dy3+, Tb3+, and Hg2+, in descending order: Tb (4.7 mg/g) > Dy (4.0 mg/g) > Hg (2.1 mg/g) for γFe2O3@SiO2-NH2; and Tb (6.2 mg/g) > Dy (4.7 mg/g) > Hg (1.2 mg/g) for CoFe2O4@SiO2-NH2. The results of the desorption with 100% of the desorbed Dy3+, Tb3+, and Hg2+ ions in an acidic medium indicated the reusability of both adsorbents. A cytotoxicity assessment of the adsorbents on human-skeletal-muscle derived cells (SKMDCs), human fibroblasts, murine macrophage cells (RAW264.7), and human-umbilical-vein endothelial cells (HUVECs) was conducted. The survival, mortality, and hatching percentages of zebrafish embryos were monitored. All the nanoparticles showed no toxicity in the zebrafish embryos until 96 hpf, even at a high concentration of 500 mg/L.

Removal of Pb2+, CrT, and Hg2+ Ions from Aqueous Solutions Using Amino-Functionalized Magnetic Nanoparticles.

In this paper, a circular economy approach with the adsorption and desorption of heavy metal (HM) ions­i.e., lead (Pb2+), chromium (CrT), and mercury (Hg2+)­from aqueous solutions was studied. Specific and selective binding of HM ions was performed on stabilized and amino-functionalized iron oxide magnetic nanoparticles (γ-Fe2O3@NH2 NPs) from an aqueous solution at pH 4 and 7. For this purpose, γ-Fe2O3@NH2 NPs were characterized by thermogravimetric analysis (TGA), Fourier-transform infrared spectroscopy (FTIR), specific surface area (BET), transmission electron microscopy (TEM), EDXS, and zeta potential measurements (ζ). The effects of different adsorbent amounts (mads = 20/45/90 mg) and the type of anions (NO3−, Cl−, SO42−) on adsorption efficiency were also tested. The desorption was performed with 0.1 M HNO3. The results showed improvement of adsorption efficiency for CrT, Pb2+, and Hg2+ ions at pH 7 by 45 mg of g-Fe2O3@NH2 NPs, and the sequence was as follows: CrT > Hg2+ > Pb2+, with adsorption capacities of 90.4 mg/g, 85.6 mg/g, and 83.6 mg/g, respectively. The desorption results showed the possibility for the reuse of γ-Fe2O3@NH2 NPs with HNO3, as the desorption efficiency was 100% for Hg2+ ions, 96.7% for CrT, and 91.3% for Pb2+.

Enzymatic Hydrolysis of Textile and Cardboard Waste as a Glucose Source for the Production of Limonene in Escherichia coli.

Cellulose containing textiles (cotton) and cardboard/carton waste represent a large reservoir of untapped organic carbon. These wastes have enormous potential for use as carbon feedstock in industrial biotechnological processes. Essentially, cotton/cardboard (CC) waste is pure cellulose (with some additives) in the form of polymerised glucose consisting of ß-(1→4)-linked D-glucose subunits. One of the largest and most diverse classes of natural chemicals that can be produced from glucose are terpenes with a wide range of applications as flavours, fragrances, pharmaceuticals, biopesticides, and biofuels. Here we have investigated the bioconversion of CC waste into the exemplary terpene limonene as a proof of concept. Six different CC waste streams were enzymatically hydrolysed and used to produce limonene using the Escherichia coli (E. coli) microbial cell factory. The D-glucose content in the CC hydrolysate (glucose juice) was determined and then metabolised by E. coli via a manipulated heterogeneous biolipid synthesis pathway (the mevalonate pathway) to produce limonene. This study represents an important proof of concept for the production of terpenes from hydrolysed CC waste streams.

Adsorption of rare earth metals from wastewater by nanomaterials: A review.

Rare earth elements are widely used in chemical engineering, the nuclear industry, metallurgy, medicine, electronics, and computer technology because of their unique properties. To fulfil ever increasing demands for these elements, recycling of rare-earth-element-containing products as well as their recovery from wastewater is quite important. In order to recover rare earth elements from wastewater, their adsorption from low-concentration aqueous solutions, by using nanomaterials, is investigated due to technological simplicity and high efficiency. This paper is a review of the state-of-the-art adsorption technologies of rare earth elements from diluted aqueous solutions by using various nanomaterials. Furthermore, desorption and reusability of rare earth metals and nanomaterials are discussed. On the basis of this review it can be concluded that laboratory testing indicates promising adsorption capacities, which depend significantly on nanomaterial type and adsorption conditions. The adsorption process, which mostly follows the Langmuir, Freundlich, Sips, and Temkin isotherms, is typically endothermic and spontaneous. Furthermore, pseudo-second order, pseudo-first order, and intra-particle diffusion models are the best models to describe the kinetics of adsorption. The dominant adsorption mechanisms are surface complexation and ion exchange. More investigation, however, will be required in order to synthesize appropriate, environmentally friendly, and efficient nanomaterials for adsorption of rare earth elements from real wastewater.

Synthesis and characterization of novel γ-Fe2O3-NH4OH@SiO2(APTMS) nanoparticles for dysprosium adsorption.

This paper deals with synthesis and characterization of novel γ-Fe2O3-NH4OH@SiO2(APTMS) nanoparticles formed from magnetic γ-Fe2O3 core, stabilized electrostatically in basic media NH4OH, doped with SiO2 shell and functionalized with 3-aminopropyltrimethoxysilane. The gradually synthesized nanoparticles are characterized in order to analyze their structural, morphology, thermogravimetry, surface area and charge, and magnetic properties. The novel synthesized γ-Fe2O3-NH4OH@SiO2(APTMS) nanoparticles are suitable to adsorb dysprosium ions (Dy3+), as one of the most critical rare earth elements, from aqueous solution. The Dy3+ adsorption from aqueous solution follows a pseudo-second order kinetic model and the adsorption equilibrium data fits well to the Temkin isotherm. Thermodynamic studies imply that the adsorption process is endothermic and spontaneous in nature. The maximum adsorption efficiency for Dy3+ from aqueous solution with 2·10-6M concentration of Dy3+ is over 90% at pH 7.

Terbium Ion Adsorption from Aqueous Solution by Using Magnetic γFe2O3-NH4OH@SiO2 Nanoparticles Functionalized with Amino Groups.

New magnetic stabilized and functionalized core@shell nanoparticles (NPs) were synthesized in a simple way and characterized in order to adsorb Tb3+ from aqueous solution with a very low Tb3+ concentration. For the fluorescence determination of adsorption efficiency and capacity, tiron monohydrate as a ligand was used. The obtained results confirm the potential of the synthesized magnetic γ-Fe2O3-NH4OH@SiO2 NPs, functionalized with (3-Aminopropyl) trimethoxysilane (APTMS), to be used for adsorption of Tb3+ from aqueous solution, with the possibility of its removal from aqueous solution via an external magnet. The endothermic and spontaneous adsorption follows a pseudo-second-order kinetic model, and the adsorption equilibrium data fit the Temkin isotherm well. The maximum adsorption efficiency from aqueous solution with a 2 × 10-6 M concentration of Tb3+ is over 90% at pH 7.

Indicator Layers Based on Ethylene-Vinyl Acetate Copolymer (EVA) and Dicyanovinyl Azobenzene Dyes for Fast and Selective Evaluation of Vaporous Biogenic Amines.

The article presents naked-eye methods for fast, sensitive, and selective detection of isopentylamine and cadaverine vapours based on 4-N,N-dioctylamino-4'-dicyanovinylazobenzene (CR-528) and 4-N,N-dioctylamino-2'-nitro-4'-dicyanovinylazobenzene (CR-555) dyes immobilized in ethylene-vinyl acetate copolymer (EVA). The reaction of CR-528/EVA and CR-555/EVA indicator layers with isopentylamine vapours caused a vivid colour change from pink/purple to yellow/orange-yellow. Additionally, CR-555/EVA showed colour changes upon exposure to cadaverine. The colour changes were analysed by ultraviolet⁻visible (UV/VIS) molecular absorption spectroscopy for amine quantification, and the method was partially validated for the detection limit, sensitivity, and linear concentration range. The lowest detection limits were reached with CR-555/EVA indicator layers (0.41 ppm for isopentylamine and 1.80 ppm for cadaverine). The indicator layers based on EVA and dicyanovinyl azobenzene dyes complement the existing library of colorimetric probes for the detection of biogenic amines and show great potential for food quality control.

Design and Investigation of Optical Properties of N-(Rhodamine-B)-Lactam-Ethylenediamine (RhB-EDA) Fluorescent Probe.

This study presents chemical modification of a Rhodamine B (RhB) sensor probe by ethylenediamine (EDA), and investigation of its spectral as well as sensor properties to the various metals. The synthesised N-(Rhodamine-B)-lactam-ethylenediamine (RhB-EDA) fluorescent probe shows interesting optical sensor properties, and high sensitivity and selectivity to Ag⁺ ions among all the tested metal ions (K⁺, Mg2+, Cu2+, Ni2+, Fe2+, Pb2+, Na⁺, Mn2+, Li⁺, Al3+, Co2+, Hg2+, Sr2+, Ca2+, Ag⁺, Cd2+ and Zn2+), while the well-known Rhodamine B (RhB) fluorescent probe shows much less sensitivity to Ag⁺ ions, but high sensitivity to Fe2+ ions. The novel fluorescent sensor probe RhB-EDA has the capabilities to sense Ag⁺ ions up to µM ranges by using the fluorescence quenching approach. The probe displayed a dynamic response to Ag⁺ in the range of 0.43 × 10-3-10-6 M with a detection limit of 0.1 µM. The sensing system of an RhB-EDA novel fluorescent probe was optimised according to the spectral properties, effect of pH and buffer, photostability, incubation time, sensitivity, and selectivity. Since all the spectral and sensing properties were tested in green aqueous media, although many other similar sensor systems rely on organic solvent solutions, the RhB-EDA sensing probe may be a good candidate for measuring Ag⁺ ions in real-life applications.

Design and Characterization of Dicyanovinyl Reactive Dyes for the Colorimetric Detection of Thiols and Biogenic Amines.

The synthesis of two new azobenzene dyes, namely CR-528 and CR-555, and their spectral properties in ethanol solution are described. The recognition of sulfur-containing analytes (2-mercaptoethanol (2-ME), sodium hydrosulfide (NaHS)), and biogenic amines (spermine, spermidine, ethanolamine) bestowed significant spectral changes with color changes from pink/purple to pale yellow/orange-yellow. The nitro acceptor group in the dicyanovinyl reactive dye contributes to higher sensitivity and lower detected analyte concentrations. The absorption maxima of both the dyes are at wavelengths compatible with low-cost light sources and detectors, making them excellent candidates for optical probes that are economic, simple to use, and do not require well-trained personnel.

Coumarin meets fluorescein: a Förster resonance energy transfer enhanced optical ammonia gas sensor.

This study focuses on the development of an optical ammonia gas sensor, the sensing mechanism of which is based on Förster resonance energy transfer (FRET) between coumarin and fluorescein. The dyes were immobilized into an organically modified silicate matrix during polymerizing methyltriethoxysilane with trifluoropropyltrimethoxysilane on a poly(methyl methacrylate) substrate. The resulting dye-doped xerogel films were exposed to different gaseous ammonia concentrations. A logarithmic decrease of the coumarin fluorescence emission band at 442 nm was observed with increasing gaseous ammonia concentrations, which was due to enhanced FRET between coumarin and fluorescein. The coumarin/fluorescein composition was optimized in order to obtain the best ammonia sensitivity. First experiments in a flow cell gas sensor setup demonstrated a sensitive and reversible response to gaseous ammonia.

His6-OPH enzyme-based bio-hybrid material for organophosphate detection.

In this work, we report on the development of a bio-sensing film for the detection of organophosphorous compounds using sol-gel technology. A novel sol-gel immobilization method employing tetraethoxysilane/3-glycidoxypropyltrimethoxysilane/water hybrid material was developed and used to immobilize the hexahistidine-tagged organophosphorous hydrolase enzyme (His(6)-OPH). Bio-sensing layers with encapsulated His(6)-OPH of various structures (water/silane, precursor ratios) have been prepared. The optimal (P = 5:1, R = 188) bio-sensing layers retained 90% of the initial enzyme activity. Furthermore, the bio-sensing layer prepared by this method was able to maintain its activity at or above 80% of its initial activity for 2 weeks. The bio-hybrid film also showed excellent reusability and improved activity at neutral pH in comparison to the same enzyme in solution.

Microtiterplate phosphate assay based on luminescence quenching of a terbium complex amenable to decay time detection.

We describe a terbium-ligand complex (TbL) for a microtiterplate assay for phosphate (P) in the 0.3-100 micromol L(-1) range based on luminescence quenching. As the pH optimum is at neutral pH (7.4) the probe is quenched by both, primary (H(2)PO(4)(-)) and secondary phosphate (HPO(4)(2-)). The LOD is 110 nmol L(-1). A Stern-Volmer study revealed that quenching is mostly static. Due to the ms-decay time of TbL, the first luminescence lifetime assay for phosphate could also be developed. The lifetime-based calibration plot is linear between 0.5 and 5 micromol L(-1) of P. The effect of various surfactants on assay performance and a study on interferents are presented. The probe was successfully applied to determination of P in commercial plant fertilizers and validated against the molybdenum blue test. The probe is the most sensitive lanthanide-based probe for phosphate.

Detection of nanomolar concentrations of copper(II) with a Tb-quinoline-2-one probe using luminescence quenching or luminescence decay time.

We present a time-resolved (gated) luminescence-based method for determination of Cu2+ ions in microtiterplate format in the nanomolar concentration range using the novel long-lived terbium-[1-methyl-4-hydroxy-3-(N-2-ethyl-5-aminothiadiazolyl-)-carbamoyl-quinoline-2-one] (TbL) complex. The probe works best in Tb:L = 1:2 stoichiometry at neutral pH. The dynamic range is from 10 to 300 nmol L(-1) of Cu2+ and the limit of detection is 4.3 nmol L(-1). This is the lowest limit of detection achieved so far for luminescent lanthanide-based probes for copper. It is shown that gating can efficiently suppress intense, short decaying background fluorescence e.g. that of Rhodamine 6G. The assay can be performed by measurement of luminescence decay time, as well. Stern-Volmer studies indicate that static quenching dominates over dynamic quenching. TbL2 was tested for the effect of some relevant interferents and the assay was applied to the determination of copper in tap water samples. The results achieved were in good agreement with those of a reference method.

Sol-gel-based optical sensor for the detection of aqueous amines.

We present an optical sensor for the detection of aqueous amines obtained by incorporating chromoionophore XV (ETH(T) 4001) into sol-gel thin films. Acid- and base-catalyzed sol-gel processes were studied to prepare stable ormosil layers using various amounts of organically modified sol-gel precursor such as methyltriethoxysilane (MTriEOS). The sensor layers were coated with a protective layer of microporous white polytetrafluoroethylene (PTFE) in order to prevent interference from ions and ambient light. The measurements were carried out in a flow-through cell in the reflection mode. Acid-catalyzed ormosil layers (pH 1) based on the copolymerization of tetraethoxysilane (TEOS) and MTriEOS did not show any change in signal upon exposure to aqueous amine solutions, while base-catalyzed sensor layers (pH 3 and 13) showed significant changes in signal. The response time (t (100)) for the base-catalyzed sensor layer L3 (pH 13) upon exposure to different solutions containing 0-608 mmol L(-1) aqueous propylamine was 20-30 s, the regeneration time was 70 s and the detection limit was 0.1 mmol L(-1). The sensor response was reproducible and reversible. The porous ormosil layers permit dry sensor storage conditions.