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  1. Article ; Online: Natural Deep Eutectic Solvents as Rust Removal Agents from Lithic and Cellulosic Substrates.

    Gabriele, Francesco / Casieri, Cinzia / Spreti, Nicoletta

    Molecules (Basel, Switzerland)

    2024  Volume 29, Issue 3

    Abstract: The peculiar physicochemical features of deep eutectic solvents (DESs), in particular their tunability, make them ideal media for various applications. Despite their ability to solubilize metal oxides, their use as rust removers from valuable substrates ... ...

    Abstract The peculiar physicochemical features of deep eutectic solvents (DESs), in particular their tunability, make them ideal media for various applications. Despite their ability to solubilize metal oxides, their use as rust removers from valuable substrates has not yet been thoroughly investigated. In this study, we chose three known DESs, consisting of choline chloride and acetic, oxalic or citric acid for evaluating their ability to remove corrosion products from a cellulose-based material as linen fabric and two different lithotypes, as travertine and granite. The artificial staining was achieved by placing a rusty iron grid on their surfaces. The DESs were applied by means of cellulose poultice on the linen fabrics, while on the rusted stone surfaces with a cotton swab. Macro- and microscopic observations, colorimetry and SEM/EDS analysis were employed to ascertain the cleaning effectiveness and the absence of side effects on the samples after treatment. Oxalic acid-based DES was capable of removing rust stains from both stone and cellulose-based samples, while choline chloride/citric acid DES was effective only on stone specimens. The results suggest a new practical application of DESs for the elimination of rust from lithic and cellulosic substrates of precious and artistic value.
    Language English
    Publishing date 2024-01-28
    Publishing country Switzerland
    Document type Journal Article
    ZDB-ID 1413402-0
    ISSN 1420-3049 ; 1431-5165 ; 1420-3049
    ISSN (online) 1420-3049
    ISSN 1431-5165 ; 1420-3049
    DOI 10.3390/molecules29030624
    Database MEDical Literature Analysis and Retrieval System OnLINE

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  2. Article ; Online: A combined experimental and computational approach for the rationalization of the catalytic activity of lipase B from Candida antarctica in water–organic solvent mixtures

    Vetrano, Alice / Daidone, Isabella / Spreti, Nicoletta / Capone, Matteo

    Journal of Chemical Technology & Biotechnology. 2023 Oct., v. 98, no. 10 p.2429-2436

    2023  

    Abstract: BACKGROUND: The addition of organic solvents to an aqueous medium for enzymatic reactions offers several advantages, as they can increase the solubility of substrates but can also lead to enzyme inactivation and/or aggregation. RESULTS: The effect of ... ...

    Abstract BACKGROUND: The addition of organic solvents to an aqueous medium for enzymatic reactions offers several advantages, as they can increase the solubility of substrates but can also lead to enzyme inactivation and/or aggregation. RESULTS: The effect of adding 30% of several water‐soluble organic solvents on the catalytic activity of lipase B from Candida antarctica (CalB) was studied and the results showed that the highest activity was obtained with the addition of t‐butanol. t‐Butanol and acetonitrile were selected and the kinetic parameters, determined to deepen their effect on CalB activity, showed that the addition of acetonitrile improved the enzyme–substrate affinity, while water–t‐butanol mixtures led to a more than ninefold increase in kcₐₜ. To rationalize at a molecular level the kinetic results, molecular dynamic simulations were performed. Analysis of the accessibility of the active‐site cavity, solvent occupancy in the site and in the oxyanion hole, and the stability of the catalytic triad in the two solvent mixtures, provided insight into their effects on the catalytic properties of CalB. CONCLUSION: The lower occupancy in the oxyanion hole of water molecules and a shorter residence time in the active site of acetonitrile molecules in the acetonitrile–water mixture contribute to the higher enzyme–substrate affinity found experimentally. Conversely, the higher kcₐₜ in the t‐butanol mixture is explained by the higher stability of the catalytic triad and by an increase in the nucleophilicity of the catalytic serine due to the persistent presence of t‐butanol molecules in the active site. © 2023 The Authors. Journal of Chemical Technology and Biotechnology published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry (SCI).
    Keywords Lewis bases ; Pseudozyma antarctica ; acetonitrile ; active sites ; biotechnology ; carboxylic ester hydrolases ; catalytic activity ; enzyme inactivation ; enzyme substrates ; oxyanions ; serine ; solvents ; water solubility
    Language English
    Dates of publication 2023-10
    Size p. 2429-2436.
    Publishing place John Wiley & Sons, Ltd.
    Document type Article ; Online
    Note JOURNAL ARTICLE
    ZDB-ID 1479465-2
    ISSN 1097-4660 ; 0268-2575
    ISSN (online) 1097-4660
    ISSN 0268-2575
    DOI 10.1002/jctb.7467
    Database NAL-Catalogue (AGRICOLA)

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  3. Article ; Online: Prevention of Swelling Phenomenon of Alginate Beads To Improve the Stability and Recyclability of Encapsulated Horse Liver Alcohol Dehydrogenase.

    Vetrano, Alice / Gabriele, Francesco / Spreti, Nicoletta

    Chembiochem : a European journal of chemical biology

    2023  Volume 24, Issue 19, Page(s) e202300456

    Abstract: Horse Liver Alcohol Dehydrogenase (HLADH) has been immobilized on calcium-alginate beads and used for both oxidation and reduction reactions. To avoid swelling of the beads and their subsequent breakage, calcium ions were added to both reaction and ... ...

    Abstract Horse Liver Alcohol Dehydrogenase (HLADH) has been immobilized on calcium-alginate beads and used for both oxidation and reduction reactions. To avoid swelling of the beads and their subsequent breakage, calcium ions were added to both reaction and storage solutions, allowing the beads to maintain the initial structural features. The techniques used for this purpose revealed that 2 mM Ca
    MeSH term(s) Horses ; Animals ; Enzymes, Immobilized/metabolism ; Alcohol Dehydrogenase ; Calcium/chemistry ; Alginates/chemistry ; Liver ; Ions ; Hexuronic Acids/chemistry ; Hydrogen-Ion Concentration ; Enzyme Stability
    Chemical Substances Enzymes, Immobilized ; Alcohol Dehydrogenase (EC 1.1.1.1) ; Calcium (SY7Q814VUP) ; Alginates ; Ions ; Hexuronic Acids
    Language English
    Publishing date 2023-08-11
    Publishing country Germany
    Document type Journal Article ; Research Support, Non-U.S. Gov't
    ZDB-ID 2020469-3
    ISSN 1439-7633 ; 1439-4227
    ISSN (online) 1439-7633
    ISSN 1439-4227
    DOI 10.1002/cbic.202300456
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  4. Article ; Online: Biodeterioration of stone monuments: Studies on the influence of bioreceptivity on cyanobacterial biofilm growth and on the biocidal efficacy of essential oils in natural hydrogel

    Gabriele, Francesco / Ranaldi, Roberta / Bruno, Laura / Casieri, Cinzia / Rugnini, Lorenza / Spreti, Nicoletta

    Science of the Total Environment. 2023 Apr., v. 870 p.161901-

    2023  

    Abstract: An important field of research is devoted to the development of innovative, sustainable, and safe methodologies to counteract biodeterioration of stone monuments due to the growth of microbial communities. However, besides the biocide's efficacy, it is ... ...

    Abstract An important field of research is devoted to the development of innovative, sustainable, and safe methodologies to counteract biodeterioration of stone monuments due to the growth of microbial communities. However, besides the biocide's efficacy, it is crucial to consider the features of substrates on which biocides must be applied, to define the so-called bioreceptivity of the lithic faces. In this research five different lithotypes, namely Lecce stone, Travertine, Peperino, Serena stone, and Granite, have been used as substrates for the growth of cyanobacterial biofilms. Open porosity, hygroscopic properties, and roughness parameters have been investigated for each lithotype and correlated to the photosynthetic yields of the biofilms colonizing the different stones to propose an easy method to estimate stone bioreceptivity. Different levels of coverage of the stone surfaces have been accomplished in relation to the typology of lithotypes. To develop innovative restoration methodologies against biodeterioration of stone monuments, a hydrogel-biocide system has been optimized by using a polysaccharide dispersion as a matrix where to embed T. vulgaris essential oil (at 0.25 % or 0.1 %) or its main component thymol (at 0.18 % or 0.07 %). The efficacy and the effect of the innovative biocide have been evaluated combining microscopy, photosynthetic measurements, and colorimetric analyses and both the biocides (with T. vulgaris EO or thymol) showed to be highly effective against the cyanobacterial biofilms for at least six months from the treatment without inducing any significant alteration to the lithic surfaces. The efficacy of thymol alone allows to treat colonized surfaces with a single active ingredient, or at least a mixture thereof, much cheaper and reproducible. The results obtained in this work pave the way to develop a sustainable cleaning protocol to counteract the biodeterioration of stone monuments or historic buildings induced by the presence of phototrophic biofilms that endangered their conservation.
    Keywords active ingredients ; biocides ; biodegradation ; biofilm ; colorimetry ; environment ; essential oils ; hydrogels ; microscopy ; photosynthesis ; polysaccharides ; porosity ; protocols ; roughness ; thymol ; Stone biocolonization ; Lithotypes ; Cyanobacterial biofilms ; Hydrogel-biocides ; Bioreceptivity
    Language English
    Dates of publication 2023-04
    Publishing place Elsevier B.V.
    Document type Article ; Online
    ZDB-ID 121506-1
    ISSN 1879-1026 ; 0048-9697
    ISSN (online) 1879-1026
    ISSN 0048-9697
    DOI 10.1016/j.scitotenv.2023.161901
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  5. Article ; Online: In situ application of alginate hydrogels containing oxidant or natural biocides on Fortunato Depero's mosaic (Rome, Italy)

    Bruno, Laura / Casieri, Cinzia / Gabriele, Francesco / Ranaldi, Roberta / Rugnini, Lorenza / Spreti, Nicoletta

    International Biodeterioration & Biodegradation. 2023 Sept., v. 183 p.105641-

    2023  

    Abstract: Stone monuments in outdoor environments are subjected to biodeterioration due to the growth on their surfaces of biofilms responsible of aesthetic, physical and chemical damages. In recent years, the encapsulation of antimicrobial agents into inert ... ...

    Abstract Stone monuments in outdoor environments are subjected to biodeterioration due to the growth on their surfaces of biofilms responsible of aesthetic, physical and chemical damages. In recent years, the encapsulation of antimicrobial agents into inert matrices has aroused considerable interest thanks to the drastic reduction of the biocide amount needed to counteract the growth of biopatinas. In this study, two biocidal hydrogels containing thyme essential oil (thyme EO) or sodium dichloroisocyanurate (NaDCC), previously tested in the laboratory, were applied on three selected areas of the Depero's mosaic located in the EUR district of Rome (Italy). A simple method to prepare the biocidal hydrogels directly in situ and their easy application on large and vertical surfaces were developed. Before and after the treatment, photographic, colorimetric, and microscopic analyses were performed to highlight the hydrogels' biocidal effectiveness in removing all colonizers. Only one treatment was enough to completely remove the microbial patina constituted of various prokaryotic and eukaryotic microorganisms. This paper is dedicated to the memory of Laura Bruno, who passed away during the peer-reviewed.
    Keywords aesthetics ; alginates ; biocides ; biodegradation ; biofilm ; colorimetry ; encapsulation ; essential oils ; hydrogels ; oxidants ; sodium dichloroisocyanurate ; thyme ; Italy ; Biodeterioration ; Hydrogel ; Cleaning ; Mosaic
    Language English
    Dates of publication 2023-09
    Publishing place Elsevier Ltd
    Document type Article ; Online
    ISSN 0964-8305
    DOI 10.1016/j.ibiod.2023.105641
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  6. Article ; Online: Biodeterioration of stone monuments: Studies on the influence of bioreceptivity on cyanobacterial biofilm growth and on the biocidal efficacy of essential oils in natural hydrogel.

    Gabriele, Francesco / Ranaldi, Roberta / Bruno, Laura / Casieri, Cinzia / Rugnini, Lorenza / Spreti, Nicoletta

    The Science of the total environment

    2023  Volume 870, Page(s) 161901

    Abstract: An important field of research is devoted to the development of innovative, sustainable, and safe methodologies to counteract biodeterioration of stone monuments due to the growth of microbial communities. However, besides the biocide's efficacy, it is ... ...

    Abstract An important field of research is devoted to the development of innovative, sustainable, and safe methodologies to counteract biodeterioration of stone monuments due to the growth of microbial communities. However, besides the biocide's efficacy, it is crucial to consider the features of substrates on which biocides must be applied, to define the so-called bioreceptivity of the lithic faces. In this research five different lithotypes, namely Lecce stone, Travertine, Peperino, Serena stone, and Granite, have been used as substrates for the growth of cyanobacterial biofilms. Open porosity, hygroscopic properties, and roughness parameters have been investigated for each lithotype and correlated to the photosynthetic yields of the biofilms colonizing the different stones to propose an easy method to estimate stone bioreceptivity. Different levels of coverage of the stone surfaces have been accomplished in relation to the typology of lithotypes. To develop innovative restoration methodologies against biodeterioration of stone monuments, a hydrogel-biocide system has been optimized by using a polysaccharide dispersion as a matrix where to embed T. vulgaris essential oil (at 0.25 % or 0.1 %) or its main component thymol (at 0.18 % or 0.07 %). The efficacy and the effect of the innovative biocide have been evaluated combining microscopy, photosynthetic measurements, and colorimetric analyses and both the biocides (with T. vulgaris EO or thymol) showed to be highly effective against the cyanobacterial biofilms for at least six months from the treatment without inducing any significant alteration to the lithic surfaces. The efficacy of thymol alone allows to treat colonized surfaces with a single active ingredient, or at least a mixture thereof, much cheaper and reproducible. The results obtained in this work pave the way to develop a sustainable cleaning protocol to counteract the biodeterioration of stone monuments or historic buildings induced by the presence of phototrophic biofilms that endangered their conservation.
    MeSH term(s) Oils, Volatile ; Thymol ; Hydrogels ; Biofilms ; Cyanobacteria ; Disinfectants/pharmacology
    Chemical Substances Oils, Volatile ; Thymol (3J50XA376E) ; Hydrogels ; Disinfectants
    Language English
    Publishing date 2023-02-02
    Publishing country Netherlands
    Document type Journal Article
    ZDB-ID 121506-1
    ISSN 1879-1026 ; 0048-9697
    ISSN (online) 1879-1026
    ISSN 0048-9697
    DOI 10.1016/j.scitotenv.2023.161901
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  7. Article ; Online: Evidence for a high pK

    Capone, Matteo / Zanetti-Polzi, Laura / Leonzi, Ilenia / Spreti, Nicoletta / Daidone, Isabella

    Journal of biomolecular structure & dynamics

    2022  Volume 41, Issue 11, Page(s) 4949–4956

    Abstract: ... Candida ... ...

    Abstract Candida antarctica
    MeSH term(s) Aspartic Acid ; Catalytic Domain ; Fungal Proteins/chemistry ; Lipase/chemistry
    Chemical Substances lipase B, Candida antarctica (EC 3.1.1.3) ; Aspartic Acid (30KYC7MIAI) ; Fungal Proteins ; Lipase (EC 3.1.1.3)
    Language English
    Publishing date 2022-05-20
    Publishing country England
    Document type Journal Article ; Research Support, Non-U.S. Gov't
    ZDB-ID 49157-3
    ISSN 1538-0254 ; 0739-1102
    ISSN (online) 1538-0254
    ISSN 0739-1102
    DOI 10.1080/07391102.2022.2077834
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  8. Article: Plant essential oils suspended into hydrogel: Development of an easy-to-use protocol for the restoration of stone cultural heritage

    Ranaldi, Roberta / Rugnini, Lorenza / Gabriele, Francesco / Spreti, Nicoletta / Casieri, Cinzia / Di Marco, Gabriele / Gismondi, Angelo / Bruno, Laura

    International biodeterioration & biodegradation. 2022 Aug., v. 172

    2022  

    Abstract: The development of phototrophic biofilms deteriorating stone cultural heritage is a well-known phenomenon that causes not only discoloration but also micro-decohesion of substrates. Recently, essential oils (EOs) have resulted as successful natural ... ...

    Abstract The development of phototrophic biofilms deteriorating stone cultural heritage is a well-known phenomenon that causes not only discoloration but also micro-decohesion of substrates. Recently, essential oils (EOs) have resulted as successful natural biocides to be used for the restoration of cultural heritage as an alternative to chemicals. In a first experiment EOs of Lavandula angustifolia Mill. and Thymus vulgaris L. at 5% concentration were tested against cyanobacterial biofilms. Moreover, to develop a suitable protocol for in situ application, diverse concentrations (0.5% - 0.25% - 0.1%) of T. vulgaris EO were encapsulated within an alginate hydrogel and applied for different times on cyanobacterial biofilms. Chemical profiles of the two EOs were investigated via GC-MS, to identify the main plant compounds underlying the biocidal effects. Results showed that T. vulgaris EO, rich in thymol, had the greatest inhibitory effect of photosynthetic efficiency compared to essential oil of L. angustifolia, especially if suspended into hydrogel. The development of such innovative protocol allowed the concentration of the tested essential oil to be 0.1% (v/v), maintaining antimicrobial efficacy against cyanobacteria and reducing the volatility of the terpene components. This innovative method will facilitate the application also on vertical surfaces and the removal of the biofilm.
    Keywords Lavandula angustifolia ; Thymus vulgaris ; alginates ; antimicrobial properties ; biocides ; biodegradation ; biofilm ; cultural heritage ; discoloration ; essential oils ; hydrogels ; photosynthesis ; thymol
    Language English
    Dates of publication 2022-08
    Publishing place Elsevier Ltd
    Document type Article
    ISSN 0964-8305
    DOI 10.1016/j.ibiod.2022.105436
    Database NAL-Catalogue (AGRICOLA)

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  9. Article: New oxidative alginate-biocide hydrogels against stone biodeterioration

    Gabriele, Francesco / Vetrano, Alice / Bruno, Laura / Casieri, Cinzia / Germani, Raimondo / Rugnini, Lorenza / Spreti, Nicoletta

    International biodeterioration & biodegradation. 2021 Sept., v. 163

    2021  

    Abstract: To address the problem of the biodeterioration of stone monuments by developing innovative methodologies, two new alginate hydrogels were obtained by using titanium dioxide as photoactivatable biocide and sodium dichloroisocyanurate as reservoir of ... ...

    Abstract To address the problem of the biodeterioration of stone monuments by developing innovative methodologies, two new alginate hydrogels were obtained by using titanium dioxide as photoactivatable biocide and sodium dichloroisocyanurate as reservoir of hypochlorous acid. The effectiveness of both hydrogels in removing the biological patina on artificially colonized Lecce stones without altering the properties of the treated substrates was demonstrated by measurements of light microscopy, colorimetry, SEM/EDS analyses and ¹H-NMR relaxometry. The biocidal activity of the new developed hydrogels has been also tested on natural cyanobacterial biofilms collected in Roman Catacombs and grown on agar medium and on calcareous stones. The results are very promising with the complete inhibition of cyanobacterial photosynthesis and without any side effects on the substrates tested.
    Keywords agar ; alginates ; biocides ; biodegradation ; biofilm ; colorimetry ; hydrogels ; light microscopy ; photosynthesis ; sodium dichloroisocyanurate ; titanium dioxide
    Language English
    Dates of publication 2021-09
    Publishing place Elsevier Ltd
    Document type Article
    ISSN 0964-8305
    DOI 10.1016/j.ibiod.2021.105281
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  10. Article: Ionic and covalent crosslinking in chitosan-succinic acid membranes: Effect on physicochemical properties

    Gabriele, Francesco / Donnadio, Anna / Casciola, Mario / Germani, Raimondo / Spreti, Nicoletta

    Carbohydrate polymers. 2021 Jan. 01, v. 251

    2021  

    Abstract: In this work, chitosan-succinic acid membranes were prepared by casting method and the physicochemical and mechanical properties of non-neutralized and neutralized with NaOH films were compared. Mechanical strength, flexibility, thermal stability and ... ...

    Abstract In this work, chitosan-succinic acid membranes were prepared by casting method and the physicochemical and mechanical properties of non-neutralized and neutralized with NaOH films were compared. Mechanical strength, flexibility, thermal stability and water-vapor permeability of chitosan membranes are significantly improved after neutralization. These improvements could be partly ascribed to the use of a dicarboxylic acid, which decreases the spacing between chitosan chains as a consequence of ionic crosslinking. Moreover, the addition of the strong base to the hydrogel promotes the formation of amide bonds, as suggested by FTIR analysis and demonstrated by acid-base titration. The favorable features of chitosan-succinic acid films as well as the possibility to easily incorporate drugs, enzymes, essential oils or other additives in the hydrogel, make such membranes suitable for many applications.
    Keywords chitosan ; crosslinking ; dicarboxylic acids ; hydrogels ; neutralization ; permeability ; strength (mechanics) ; thermal stability ; titration ; water vapor
    Language English
    Dates of publication 2021-0101
    Publishing place Elsevier Ltd
    Document type Article
    ZDB-ID 1501516-6
    ISSN 1879-1344 ; 0144-8617
    ISSN (online) 1879-1344
    ISSN 0144-8617
    DOI 10.1016/j.carbpol.2020.117106
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