Food-borne bacteria analysis using a diatomite bioinspired SERS platform.

Rapid and sensitive detection of food-borne bacteria has remained challenging over the past few decades. We propose a surface-enhanced Raman scattering sensing strategy based on a novel bioinspired surface-enhanced Raman scattering substrate, which can directly detect dye molecular residues and food-borne pathogen microorganisms in the environment. The surface-enhanced Raman scattering platform consists of a natural diatomite microporous array decorated with a metal-phenolic network that enables the in situ reduction of gold nanoparticles. The as-prepared nanocomposites display excellent surface-enhanced Raman scattering activity with the lowest limit of detection and the maximum Raman enhancement factor of dye molecules up to 10-11 M and 1.18 × 107, respectively. For food-borne bacterial detection, a diatomite microporous array decorated with a metal polyphenol network and gold nanoparticle-based surface-enhanced Raman scattering analysis is capable of distinguishing the biochemical fingerprint information of Staphylococcus aureus and Escherichia coli, indicating the great potential for strain identification.

Osteoblast responsive biosilica-enriched gelatin microfibrillar microenvironments.

Engineering of scaffolds for bone regeneration is often inspired by the native extracellular matrix mimicking its composite fibrous structure. In the present study, we used low loadings of diatomite earth (DE) biosilica to improve the bone regeneration potential of gelatin electrospun fibrillar microenvironments. We explored the effect of increasing the DE content from 1 % to 3 % and 5 %, respectively, on the physico-chemical properties of the fibrous scaffolds denoted FG_DE1, FG_DE3, FG_DE5, regarding the aqueous media affinity, stability under simulated physiological conditions, morphology characteristics, and local mechanical properties at the surface. The presence of biosilica generated composite structures with lower swelling degrees and higher stiffness when compared to gelatin fibers. Increasing DE content led to higher Young modulus, while the stability of the protein matrix in PBS, at 37 °C, over 21 was significantly decreased by the presence of diatomite loadings. The best preosteoblast response was obtained for FG_DE3, with enhanced mineralization during the osteogenic differentiation when compared to the control sample without diatomite. 5 % DE in FG_DE5 proved to negatively influence cells' metabolic activity and morphology. Hence, the obtained composite microfibrillar scaffolds might find application as osteoblast-responsive materials for bone tissue engineering.

Preparation and sustained release of diatomite incorporated and Eudragit L100 coated hydroxypropyl cellulose/chitosan aerogel microspheres.

The drug encapsulation efficiency, release rate and time, sustained release, and stimulus-response of carriers are very important for drug delivery. However, these always cannot obtained for the carrier with a single component. To improve the comprehensive performance of chitosan-based carriers for 5-Fu delivery, diatomite-incorporated hydroxypropyl cellulose/chitosan (DE/HPC/CS) composite aerogel microspheres were fabricated for the release of 5-fluorouracil (5-Fu), and the release performance was regulated with the content of diatomite, pH value, and external coating material. Firstly, the 5-Fu loaded DE/HPC/CS composite aerogel microspheres and Eudragit L100 coated microspheres were prepared with cross-linking followed by freeze-drying, and characterized by SEM, EDS, FTIR, XRD, DSC, TG, and swelling. The obtained aerogel microspheres have a diameter of about 0.5 mm, the weight percentage of F and Si elements on the surface are 0.55 % and 0.78 % respectively. The glass transition temperature increased from 179 °C to 181 °C and 185 °C with the incorporation of DE and coating of Eudragit, and the equilibrium swelling percentage of DE/HPC/CS (1.5:3:2) carriers are 101.52 %, 45.27 %, 67.32 % at pH 1.2, 5.0, 7.4, respectively. Then, the effect of DE content on the drug loading efficiency of DE/HPC/CS@5-Fu was investigated, with the increase of DE content, the highest encapsulation efficiency was 82.6 %. Finally, the release behavior of DE incorporated and Eudragit L100 Coated microspheres were investigated under different pH values, and evaluated with four kinetic models. The results revealed that the release rate of 5-Fu decreased with the increase of DE content, sustained release with extending time and pH-responsive were observed for the Eudragit-coated aerogel microspheres.

Comprehensive enhancement of flame retardant starch/cellulose/diatomite composite foams via metal-organic coordination.

In recent years, considerable attention has been given to the utilization of biomass for producing bio-based foams, such as starch-based foams. Despite their renewability and widespread availability, these foams still present certain drawbacks regarding their poor mechanical properties and flammability. To tackle these concerns, a metal ion cross-linking strategy was employed by incorporating calcium ions (Ca2+) solution into foamed starch/cellulose slurry. Followed by ambient drying, starch/cellulose composite foam was successfully fabricated with a remarkable enhancement in various properties. Specifically, compared to the control sample, the compressive strength and modulus increased by 26.2 % and 123.0 %, respectively. Additionally, the Ca2+ cross-linked starch/cellulose composite foam exhibited excellent heat resistance, water stability, and flame retardancy. The limiting oxygen index (LOI) reached 52 %, with a vertical combustion rating of V-0. Along with the addition of 2 phr diatomite, it demonstrated a significant enhancement on flame retardancy with a LOI of 65 %, although the apparent density of the composite foam was not low enough. This study indicated a green and simple method to obtain starch-based composite foams with enhanced comprehensive properties including thermal, water stability, mechanical, and flame retardancy, expanding their potential applications in areas such as building materials and rigid packaging.

High-temperature CO2 sorption over Li4SiO4 synthesized from diatomite: study of sorption heat and isotherm modeling.

The Li4SiO4 seems to be an excellent sorbent for CO2 capture at post-combustion. Our work contributes to understanding the effect of the natural Algerian diatomite as a source of SiO2 in the synthesis of Li4SiO4 for CO2 capture at high temperature. For this purpose, we use various molar % (stoichiometric and excess) of calcined natural diatomite and pure SiO2. To select the best composition, CO2 sorption isotherms at 500 °C on the prepared Li4SiO4 are obtained using TGA measurements under various flows of CO2 in N2. The sorbent having 10% molar SiO2 in diatomite (10%ND-LS) exhibits the best CO2 uptake, probably due to various factors such as the content of the different secondary phases. A comparative study was performed at 400 to 500 °C on this selected 10%ND-LS and those with stoichiometric composition obtained with diatomite and pure SiO2. The obtained isotherms show the endothermic character of CO2 sorption. In addition, the evolution of isosteric heat highlights the nature of the involved CO2/Li4SiO4 interactions, by considering the double-shell mechanism. Finally, the experimental sorption isotherms are confronted with some well-known adsorption models to explain the phenomenon occurring over our prepared sorbents. Freundlich and Jensen-Seaton models present a better correlation with the experimental results.

Tailored chitosan integration in diatomaceous earth particles as a scaffold for fructosyltransferase immobilization in fructo-oligosaccharide production.

BACKGROUND: Fructo-oligosaccharide (FOS) belongs to the group of short inulin-type fructans and is one of the most important non-digestible bifid-oligosaccharides capable of biotransforming sucrose using fructosyltransferase (FTase). However, there are no immobilized FTase products that can be successfully used industrially. In this study, diatomite was subjected to extrusion, sintering and granulation to form diatomaceous earth particles that were further modified via chitosan aminomethylation for modification. FTase derived from Aspergillus oryzae was successfully immobilized on the modified support via covalent binding. RESULTS: The immobilized enzyme activity was 503 IU g-1 at an enzyme concentration of 0.6 mg mL-1, immobilization pH of 7.0 and contact time of 3 h. Additionally, the immobilization yield was 56.91%. Notably, the immobilized enzyme was more stable under acidic conditions. Moreover, the half-life of the immobilized enzyme was 20.80 and 10.96 times as long as that of the free enzyme at 45 and 60 °C, respectively. The results show good reusability, as evidenced by the 84.77% retention of original enzyme activity after eight cycles. Additionally, the column transit time of the substrate was 35.56 min when the immobilized enzyme was applied in a packed-bed reactor. Furthermore, a consistently high FOS production yield of 60.68% was achieved and maintained over the 15-day monitoring period. CONCLUSIONS: Our results suggest that immobilized FTase is a viable candidate for continuous FOS production on an industrial scale. © 2024 Society of Chemical Industry.

A spherical adsorbent produced from a bagasse biochar chitosan assembly for selective adsorption of platinum-group metals from wastewater.

This study addresses the challenge of platinum-group metal scarcity by exploring the adsorption of these metals from industrial wastewater. An inexpensive adsorbent with selective platinum-group metal adsorption capacity, named chitosan/citric acid@diatomaceous earth-sugarcane bagasse (CTS/CA@DE-SBS), was newly synthesized. The material features a double coating of chitosan and diatomite on bagasse biochar, and it exhibits an excellent adsorption performance for platinum-group metals due to the synergistic effects of the biochar and chitosan-diatomaceous earth intercross-linked coatings. CTS/CA@DE-SBS achieved an 81 % adsorption efficiency and a static saturated adsorption capacity of 217 mg/g for Pt (IV) in water. Notably, the material exhibited selective adsorption properties for platinum-group metals dissolved in diverse aqueous solutions. The potential for the secondary recovery of platinum-group metals in complex aqueous bodies further underscores the significance of this adsorbent. In conclusion, this research introduces a promising solution for platinum-group metal shortages, offering a cost-effective and selective adsorbent with potential applications in the secondary recovery of these metals from industrial wastewater.

Modified Diatomaceous Earth in Heparin Recovery from Porcine Intestinal Mucosa.

Heparin, a highly sulfated glycosaminoglycan, is a naturally occurring anticoagulant that plays a vital role in various physiological processes. The remarkable structural complexity of heparin, consisting of repeating disaccharide units, makes it a crucial molecule for the development of commercial drugs in the pharmaceutical industry. Over the past few decades, significant progress has been made in the development of cost-effective adsorbents specifically designed for the adsorption of heparin from porcine intestinal mucosa. This advancement has been driven by the need for efficient and scalable methods to extract heparin from natural sources. In this study, we investigated the use of cationic ammonium-functionalized diatomaceous earth, featuring enhanced porosity, larger surface area, and higher thermal stability, to maximize the isolated heparin recovery. Our results showed that the higher cationic density and less bulky quaternary modified diatomaceous earth (QDADE) could adsorb up to 16.3 mg·g-1 (31%) of heparin from the real mucosa samples. Additionally, we explored the conditions of the adsorbent surface for recovery of the heparin molecule and optimized various factors, such as temperature and pH, to optimize the heparin uptake. This is the introductory account of the implementation of modified diatomaceous earth with quaternary amines for heparin capture.

Selective separation of dye/salt mixture using diatomite-based sandwich-like membrane.

A novel nanofiltration membrane was developed by entrapping a layer of modified diatomaceous earth between two layers of electrospun polysulfone (E-PSf) nanofibers. The diatomaceous earth particles and the fabricated membrane were characterized using FTIR, SEM, EDS, zeta potential, and water contact angle techniques. The static adsorption and dynamic separation of pristine E-PSF and sandwich-like membranes for methylene blue (MB) with/without salt were investigated under different operating conditions. The Langmuir model suited the MB adsorption isotherm data with a linear regression correlation coefficient (R2) >0.9955. As pH increased, both flux and MB rejection of the sandwich-like membrane improved by up to 183.8 LMH and 99.7%, respectively, when operated under gravity. The water flux of the sandwich-like membrane was sharply increased by increasing the pressure up to 19,518.2 LMH at 4.0 bar. However, this came at the expense of MB rejection (10.93%) and reduced its practical impact. At a high salt concentration, the sandwich-like membrane also indicated remarkable dye/salt separation with a higher permeation of salt (<0.2% NaCl rejection) and MB rejection (>99%). The performance of the regenerated diatomaceous material and membrane was maintained during five cycles of operation compared to that of the original ones.

Comparison of host cell protein removal by depth filters with diatomaceous earth and synthetic silica filter aids using model proteins.

A number of studies have demonstrated that depth filtration can provide significant adsorptive removal of host cell proteins (HCP), but there is still considerable uncertainty regarding the underlying factors controlling HCP binding. This study compared the binding characteristics of two fine grade depth filters, the X0SP (polyacrylic fiber with a synthetic silica filter aid) and X0HC (cellulose fibers with diatomaceous earth (DE) as a filter aid), using a series of model proteins with well-defined physical characteristics. Protein binding to the X0SP filter was dominated by electrostatic interactions with greatest capacity for positively-charged proteins. In contrast, the X0HC filter showed greater binding of more hydrophobic proteins although electrostatic interactions also played a role. In addition, ovotransferrin showed unusually high binding capacity to the X0HC, likely due to interactions with metals in the DE. Scanning Electron Microscopy with Energy Dispersive Spectroscopy was used to obtain additional understanding of the binding behavior. These results provide important insights into the physical phenomena governing HCP binding to both fully synthetic and natural (cellulose + DE) depth filters.

The catalytic aerial oxidation of As(III) in alkaline solution by Mn-loaded diatomite.

The oxidization of As(III) to As(V) is necessary for both the detoxification of arsenic and the removal of arsenic by solidification. In order to achieve high efficiency and low cost As(III) oxidation, a novel process of catalytic aerial oxidation of As(III) is proposed, using air as oxidant and Mn-loaded diatomite as a catalyst. Through systematic characterization of the reaction products, the catalytic oxidation reaction law of Mn-loaded diatomite for As(III) was found out, and its reaction mechanism was revealed. Results show that Mn-loaded diatomite achieved a good catalytic effect for aerial oxidation of As(III) and maintained high performance over multiple cycles of reuse, which was directly related to the structure of diatomite and the behavior of manganese. Under the conditions of a catalyst concentration of 20 g/L, an air flow rate of 0.3 m3/h, a reaction temperature of 50 °C and an initial pH of 12.6, 96.04% As(III) oxidation was achieved after 3 h. Furthermore, the efficiency of As(III) oxidation did not change significantly after ten cycles of reuse. XPS analysis of the reaction products confirmed that the surface of the catalyst was rich in Mn(III), Mn(IV) and adsorbed oxygen(O-H), which was the fundamental reason for the excellent performance of Mn-loaded diatomite in the catalytic oxidation of As(III).

Diatomaceous Earth for Arthropod Pest Control: Back to the Future.

Nowadays, we are tackling various issues related to the overuse of synthetic insecticides. Growing concerns about biodiversity, animal and human welfare, and food security are pushing agriculture toward a more sustainable approach, and research is moving in this direction, looking for environmentally friendly alternatives to be adopted in Integrated Pest Management (IPM) protocols. In this regard, inert dusts, especially diatomaceous earths (DEs), hold a significant promise to prevent and control a wide range of arthropod pests. DEs are a type of naturally occurring soft siliceous sedimentary rock, consisting of the fossilized exoskeleton of unicellular algae, which are called diatoms. Mainly adopted for the control of stored product pests, DEs have found also their use against some household insects living in a dry environment, such as bed bugs, or insects of agricultural interest. In this article, we reported a comprehensive review of the use of DEs against different arthropod pest taxa, such as Acarina, Blattodea, Coleoptera, Diptera, Hemiptera, Hymenoptera, Ixodida, Lepidoptera, when applied either alone or in combination with other techniques. The mechanisms of action of DEs, their real-world applications, and challenges related to their adoption in IPM programs are critically reported.

Design of Gelatin-Capped Plasmonic-Diatomite Nanoparticles with Enhanced Galunisertib Loading Capacity for Drug Delivery Applications.

Inorganic diatomite nanoparticles (DNPs) have gained increasing interest as drug delivery systems due to their porous structure, long half-life, thermal and chemical stability. Gold nanoparticles (AuNPs) provide DNPs with intriguing optical features that can be engineered and optimized for sensing and drug delivery applications. In this work, we combine DNPs with gelatin stabilized AuNPs for the development of an optical platform for Galunisertib delivery. To improve the DNP loading capacity, the hybrid platform is capped with gelatin shells of increasing thicknesses. Here, for the first time, full optical modeling of the hybrid system is proposed to monitor both the gelatin generation, degradation, and consequent Galunisertib release by simple spectroscopic measurements. Indeed, the shell thickness is optically estimated as a function of the polymer concentration by exploiting the localized surface plasmon resonance shifts of AuNPs. We simultaneously prove the enhancement of the drug loading capacity of DNPs and that the theoretical modeling represents an efficient predictive tool to design polymer-coated nanocarriers.

Facile Fabrication of Diatomite-Supported ZIF-8 Composite for Solid-Phase Extraction of Benzodiazepines in Urine Samples Prior to High-Performance Liquid Chromatography.

A novel diatomite-supported zeolitic imidazolate framework-8 sorbent (ZIF-8@Dt-COOH) was in situ fabricated and developed for solid-phase extraction of three benzodiazepines (triazolam, midazolam and diazepam) in urine followed by high-performance liquid chromatography. ZIF-8@Dt-COOH was easily prepared by coating ZIF-8 on the surface of Dt-COOH and characterized by Fourier transform infrared spectra, X-ray powder diffractometry and scanning electron microscopy. Compared with bare Dt-COOH, the extraction efficiency of ZIF-8@Dt-COOH for the target was significantly increased from 20.1-39.0% to 100%. Main extraction parameters, including ionic strength and pH of solution, loading volume, washing solution, elution solvent and elution volume, were optimized in detail. Under optimum conditions, the developed method gave linearity of three BZDs in 2-500 ng/mL (r ≥ 0.9995). Limits of detection (S/N = 3), and limits of quantification (S/N = 10) were 0.3-0.4 ng/mL and 1.0-1.3 ng/mL, respectively. In addition, the average recoveries at three spiked levels (5, 10 and 20 ng/mL) varied from 80.0% to 98.7%, with the intra-day and inter-day precisions of 1.4-5.2% and 1.5-8.2%, respectively. The proposed method provided an effective purification performance and gave the enrichment factors of 24.0-29.6. The proposed method was successfully employed for the accurate and sensitive determination of benzodiazepines in urine.

Understanding the effects of copolymerized cellulose nanofibers and diatomite nanocomposite on blend chitosan films.

Chitosan films lack various important physicochemical properties and need to be supplemented with reinforcing agents to bridge the gap. Herein, we have produced chitosan composite films supplemented with copolymerized (with polyacrylonitrile monomers) cellulose nanofibers and diatomite nanocomposite at different concentrations. The incorporation of CNFs and diatomite enhanced the physicochemical properties of the films. The mechanical characteristics and hydrophobicity of the films were observed to be improved after incorporating the copolymerized CNFs/diatomite composite at different concentrations (CNFs: 1%, 2% and 5%; diatomite: 10% and 30%). The antioxidant activity gradually increased with an increasing concentration (1-5% and 10-30%) of copolymerized CNFs/diatomite composite in the chitosan matrix. Moreover, the water solubility decreased from 30% for chitosan control film (CH-0) to 21.06% for films containing 30% diatomite and 5% CNFs (CNFs-D30-5). The scanning electron micrographs showed an overall uniform distribution of copolymerized CNFs/diatomite composite in the chitosan matrix with punctual agglomerations.

Immobilization of recombinant Escherichia coli cells expressing glucose isomerase using modified diatomite as a carrier for effective production of high fructose corn syrup in packed bed reactor.

To improve the operational stability of glucose isomerase in E. coli TEGI-W139F/V186T, the immobilized cells were prepared with modified diatomite as a carrier and 74.1% activity of free cells was recovered after immobilization. Results showed that the immobilized cells still retained 86.2% of the initial transformational activity after intermittent reused 40 cycles and the yield of D-fructose reached above 42% yield at 60 °C. Moreover, the immobilized cells were employed in the continuous production of High Fructose Corn Syrup (HFCS) in a recirculating packed bed reactor for 603 h at a constant flow rate. It showed that the immobilized cells exhibited good operational stability and the yield of D-fructose retained above 42% within 603 h. The space-time yield of high fructose corn syrup reached 3.84 kg L-1 day-1. The investigation provided an efficient immobilization method for recombinant cells expressing glucose isomerase with higher stability, and the immobilized cells are a promising biocatalyst for HFCS production.

Combination of Adsorption and Cellulose Derivative Membrane Coating for Efficient Immobilization of Laccase.

Immobilization of enzyme based on combination of adsorption and cellulose derivative membrane coating was established in this work for the first time. Laccase, a commonly used enzyme in varied fields, was chosen as the model enzyme to demonstrate this method. After investigating operational conditions, the optimal process was obtained as follows: diatomite or HPD-417 as the adsorption carrier, 0.5% (w/v) methylcellulose (40,000~50,000) acetone solution as the coating solution, 0.75% (w/v) polyethylene glycol or maltose as the protective agent, and drying at 4 °C for 9 h. Under the optimal conditions, the residual activities of diatomite and HPD-417 immobilized laccase reached 99.33% and 94.15%, respectively. The study on properties showed that the immobilized laccases held high pH tolerance and thermal stability. The immobilized laccases were further applied to the indigo decolorization and 2, 4-dichlorophenol degradation. They showed high catalytic efficiency and could be reused for several batches. On the whole, the immobilization method developed in this work can effectively avoid the inactivation of laccase during immobilization and improve the stability of immobilized laccase. The laccase immobilized by this method shows obvious potential for environmental governance.

Tetracycline Removal by Activating Persulfate with Diatomite Loading of Fe and Ce.

Persulfate (PS)-based oxidation technology is efficient in removing refractory organics from water. A novel diatomite (DIA) support Fe and Ce composite (Fe-Ce/DIA) was prepared for activating persulfate to degrade tetracycline in water. The Fe and Ce were uniformly loaded on DIA, and the total pore size of Fe-Ce/DIA was 6.99 × 10-2 cm3/g, and the average pore size was 12.06 nm. Fe-Ce/DIA presented a good catalytic activity and 80% tetracycline was removed under the persulfate system. The Fe-Ce/DIA also had photocatalytic activity, and the corresponding tetracycline removal efficiency was 86% under UV irradiation. Fe-Ce/DIA exhibited less iron dissolution rate compared with Fe-DIA. The tetracycline degradation rate was enhanced when the temperature increased. The optimal tetracycline removal efficiency was obtained when the conditions were of persulfate 10 mM, Fe-Ce/DIA dosage 0.02 g/L, and tetracycline concentration 50 mg/L. In addition, Fe-Ce/DIA showed a wide pH application and good reusability and stability.

Dimethyl 3,3'-dithiobispropionimidate-functionalized diatomaceous earth particles for efficient biomolecule separation.

The early diagnosis and monitoring of cancers are key factors in effective cancer treatment. Particularly, the separation of biomolecules is an essential step for both diagnostic and analytical purposes. However, the current techniques used to isolate biomolecules are intensive, laborious, and require multiple instruments as well as repeated sample preparations to separate each biomolecule. Thus, an efficient separation system that can simultaneously separate biomolecules from scarce samples is highly desirable. Hence, in this study, we developed a biosilica-based syringe filtration system for the efficient separation of biomolecules from cancer samples using amine-modified diatomaceous earth (AD) with dimethyl 3,3'-dithiobispropionimidate (DTBP). The syringe filter can be an efficient and rapid tool for use in various procedures without complex instruments. The DTBP-based AD system was combined with the syringe filter system for nucleic acid and protein separation from various cancer cells. We demonstrated the efficacy of the DTBP-based AD in a single-filter system for the efficient separation of DNA and proteins within 40 min. This DTBP-based AD syringe filter system showed good rapidity, efficiency, and affordability in the separation of biomolecules from single samples for the early diagnosis and clinical analysis of cancers.

Effectiveness of host cell protein removal using depth filtration with a filter containing diatomaceous earth.

The increased cell density and product titer in biomanufacturing have led to greater use of depth filtration as part of the initial clarification of cell culture fluid, either as a stand-alone unit operation or after centrifugation. Several recent studies have shown that depth filters can also reduce the concentration of smaller impurities like host cell proteins (HCP) and DNA, decreasing the burden on subsequent chromatographic operations. The objective of this study was to evaluate the HCP removal properties of the Pall PDH4 depth filter media, a model depth filter containing diatomaceous earth, cellulose fibers, and a binder. Experiments were performed with both cell culture fluid (CCF) and a series of model proteins with defined pI, molecular weight, and hydrophobicity chosen to match the range of typical HCP. The location of adsorbed (fluorescently labeled) proteins within the depth filters was determined using confocal scanning laser microscopy. Protein binding was greater for proteins that were positively charged and more hydrophobic, consistent with adsorption to the negatively charged diatomaceous earth. The lowest degree of binding was seen with proteins near their pI, which were poorly removed by this filter. These results provide new mechanistic insights into the factors governing the filter capacity and performance characteristics of depth filters containing diatomaceous earth that are widely used in the clarification of CCF.