The Essential Oil of Thymbra capitata and its Application as A Biocide on Stone and Derived Surfaces

Many chemicals used nowadays for the preservation of cultural heritage pose a risk to both human health and the environment. Thus, it is desirable to find new and eco-friendly biocides that can replace the synthetic ones. In this regard, plant essential oils represent effective alternatives to synthetic substances for the preservation of historical monuments. Thymbra capitata (syn. Thymus capitatus) is a medicinal and aromatic plant growing in the Mediterranean area and endowed with important pharmacological properties related to its essential oil. Among them, the antimicrobial ones make the T. capitata essential oil an ideal candidate for industrial applications; for instance, as biocide for the inhibition and elimination of biological patinas of cyanobacteria and green algae on historical monuments. In the present work, we studied the chemical composition of the essential oil from T. capitata growing in Malta by gas chromatography-mass spectrometry (GC/MS). The major volatile component is the phenolic monoterpene carvacrol (73.2%), which is capable of damaging the cytoplasmic membrane and to interfere both in the growth curve and in the invasive capacity, though the contribution of minor components γ-terpinene and p-cymene cannot be disregarded. For the oil application on the stone surface, Pickering emulsions systems were prepared with an essential oil/water 1:3 mass ratio stabilized with kaolinite at 4 mass% in the presence of Laponite®; this allowed to limit the fast volatility of the oil and guaranteed a better application and an easier removal from the artefacts attacked by biodeteriogens both indoor and outdoor. This formulation caused the elimination of biodeteriogens from treated surfaces without residuals or films on artworks surface, and the effect was retained up to four months.

[1]  Yunqi Li,et al.  Recent advances on food-grade particles stabilized Pickering emulsions: Fabrication, characterization and research trends , 2016 .

[2]  Julia Frankfurter,et al.  Cornucopia A Source Book Of Edible Plants , 2016 .

[3]  M. Uyttendaele,et al.  Inhibitory effect of thyme and basil essential oils, carvacrol, thymol, estragol, linalool and p-cymene towards Shigella sonnei and S. flexneri , 2004 .

[4]  R. Croteau,et al.  gamma-Terpinene synthetase: a key enzyme in the biosynthesis of aromatic monoterpenes. , 1978, Archives of biochemistry and biophysics.

[5]  J. Vukojevic,et al.  Antifungal activity of selected essential oils and biocide benzalkonium chloride against the fungi isolated from cultural heritage objects , 2014 .

[6]  U. P. Hedrick,et al.  Sturtevant's Edible Plants of the World , 1972 .

[7]  S. Dallali,et al.  Comparison of Chemical Composition, Antioxidant and Antimicrobial Activities of Thymus capitatus L. essential Oils from two Tunisian localities (Sousse and Bizerte) , 2013 .

[8]  Giulia Caneva,et al.  Natural biocides for the conservation of stone cultural heritage: A review , 2019, Journal of Cultural Heritage.

[9]  N. Botsoglou,et al.  The antimicrobial effect of thyme essential oil, nisin and their combination against Escherichia coli O157:H7 in minced beef during refrigerated storage. , 2008, Meat science.

[10]  R. Schmid,et al.  Botanica the Illustrated A-z Of Over 10,000 Garden Plants and How to Cultivate Them , 1999 .

[11]  M. Mansour Proactive Investigation using Bioagents and Fungicide for Preservation of Egyptian Stone Sarcophagus , 2013 .

[12]  S. Mohamed,et al.  Antibacterial Activity of Essential Oils of Some Algerian Aromatic Plants Against Multidrug Resistant Bacteria , 2010 .

[13]  G. Cavallaro,et al.  Halloysite Nanotubes for Cleaning, Consolidation and Protection. , 2018, Chemical record.

[14]  A. Paškevičius,et al.  Fungi in Water-Damaged Buildings of Vilnius Old City and Their Susceptibility Towards Disinfectants and Essential Oils , 2013 .

[15]  B. Murray,et al.  In vitro digestion of Pickering emulsions stabilized by soft whey protein microgel particles: influence of thermal treatment. , 2016, Soft matter.

[16]  T. Shibamoto,et al.  Identification of volatile components in basil Ocimum basilicum L and thyme leaves Thymus vulgaris L and their antioxidant properties , 2005 .

[17]  S. Bouzid,et al.  Chemical composition, weed killer and antifungal activities of Tunisian thyme (Thymus capitatus Hoff. et Link.) essential oils , 2013 .

[18]  G. Arras,et al.  Fungitoxic activity of 12 essential oils against four postharvest citrus pathogens: chemical analysis of thymus capitatus oil and its effect in subatmospheric pressure conditions. , 2001, Journal of food protection.

[19]  P. Klouček,et al.  Antimicrobial properties of selected essential oils in vapour phase against foodborne bacteria , 2009 .

[20]  P. Chalier,et al.  Antimicrobial activity of carvacrol related to its chemical structure , 2006, Letters in applied microbiology.

[21]  Eric Dickinson,et al.  Use of nanoparticles and microparticles in the formation and stabilization of food emulsions , 2012 .

[22]  T. R. Téllez,et al.  Chemical composition and antioxidant activity of the essential oil of Thymbra capitata (L.) Cav. in Spain , 2010 .

[23]  M. Barzegar,et al.  Antifungal activity of thyme, summer savory and clove essential oils against Aspergillus flavus in liquid medium and tomato paste , 2007 .

[24]  E. Stahl-Biskup 3Essential oil chemistry of the genus Thymus - a global view , 2002 .

[25]  B. Lavédrine,et al.  Screening for antifungal activity of essential oils and related compounds to control the biocontamination in libraries and archives storage areas , 2005 .

[26]  L. Tommasi,et al.  Essential oil variability in Thymbra capitata (L.) Cav. growing wild in Southern Apulia (Italy) , 2006 .

[27]  Maurizio Bruno,et al.  Influence of harvesting time on composition of the essential oil of Thymus capitatus (L.) Hoffmanns. & Link. growing wild in northern Sicily and its activity on microorganisms affecting historical art crafts , 2015, Arabian Journal of Chemistry.

[28]  F. Senatore,et al.  Volatile constituents of Dianthus rupicola Biv. from Sicily: activity against microorganisms affecting cellulosic objects , 2014, Natural product research.

[29]  B. Murray,et al.  Water-In-Oil Pickering Emulsions Stabilized by Water-Insoluble Polyphenol Crystals. , 2018, Langmuir : the ACS journal of surfaces and colloids.

[30]  T. Ruiz,et al.  Thymbra capitata Essential Oil Prevents Cell Death Induced by 4-Hydroxy-2-Nonenal in Neonatal Rat Cardiac Myocytes , 2014, Planta Medica.

[31]  M. Mulas Traditional uses of Labiatae in the Mediterranean area , 2006 .

[32]  A. Figueiredo,et al.  Antibacterial and antioxidant activities of essential oils isolated from Thymbra capitata L. (Cav.) and Origanum vulgare L , 2005 .

[33]  M. Viuda‐Martos,et al.  Effect of adding citrus waste water, thyme and oregano essential oil on the chemical, physical and sensory characteristics of a bologna sausage , 2009 .

[34]  F. Senatore,et al.  Activity against Microorganisms Affecting Cellulosic Objects of the Volatile Constituents of Leonotis nepetaefolia from Nicaragua , 2014, Natural product communications.

[35]  Orlin D. Velev,et al.  Pickering stabilization of foams and emulsions with particles of biological origin , 2014 .

[36]  M. Faleiro,et al.  Portuguese Thymbra and Thymus species volatiles: chemical composition and biological activities. , 2008, Current pharmaceutical design.

[37]  Friedrich E. W. Eckhardt,et al.  Solubilization, Transport, and Deposition of Mineral Cations by Microorganisms - Efficient Rock Weathering Agents , 1985 .

[38]  C. Georgescu,et al.  Activity of some essential oils against common spoilage fungi of buildings. , 2010 .

[39]  F. Napolitano,et al.  Chemical Composition and Antimicrobial Activity of the Essential Oils from Two Species of Thymus Growing Wild in Southern Italy , 2009, Molecules.

[40]  A. Allameh,et al.  Ultrastructural studies on antimicrobial efficacy of thyme essential oils on Listeria monocytogenes. , 2006, International journal of infectious diseases : IJID : official publication of the International Society for Infectious Diseases.

[41]  A. Farah,et al.  Activité antifongique des huiles essentielles de Thymus bleicherianus Pomel et Thymus capitatus (L.) Hoffm. & Link contre les champignons de pourriture du bois d'oeuvre , 2008 .

[42]  F. Senatore,et al.  Chemical composition of the essential oil of Moluccella spinosa L. (Lamiaceae) collected wild in Sicily and its activity on microorganisms affecting historical textiles , 2015, Natural product research.

[43]  Filippo Parisi,et al.  Microemulsion Encapsulated into Halloysite Nanotubes and their Applications for Cleaning of a Marble Surface , 2018, Applied Sciences.

[44]  A. Bose,et al.  Release of surfactant cargo from interfacially-active halloysite clay nanotubes for oil spill remediation. , 2014, Langmuir : the ACS journal of surfaces and colloids.

[45]  M. Miguel,et al.  Biological activities of extracts of plants grown in Portugal , 2011 .

[46]  R. Morales The history, botany and taxonomy of the genus Thymus , 2002 .

[47]  M. Hudaib,et al.  Chemical Composition of the Essential Oil from Flowers, Flower Buds and Leaves of Thymus capitatus Hoffmanns. & Link from Jordan , 2012 .

[48]  R. Schomäcker,et al.  Halloysites Stabilized Emulsions for Hydroformylation of Long Chain Olefins , 2017 .

[49]  R. Pagán,et al.  Antimicrobial efficacy of Thymbra capitata (L.) Cav. essential oil loaded in self-assembled zein nanoparticles in combination with heat , 2019, Industrial Crops and Products.

[50]  J. Paolini,et al.  Antifungal activity of essential oils of three aromatic plants from western Algéria against five fungal pathogens of tomato (Lycopersicon esculentum Mill) , 2014 .

[51]  O. Sağdıç,et al.  Antibacterial activity and composition of essential oils from Origanum, Thymbra and Satureja species with commercial importance in Turkey , 2004 .

[52]  R. Croteau,et al.  Biosynthesis of aromatic monoterpenes: Conversion of γ-terpinene to p-cymene and thymol in Thymus vulgaris L , 1978 .

[53]  S. Cosentino,et al.  In‐vitro antimicrobial activity and chemical composition of Sardinian Thymus essential oils , 1999, Letters in applied microbiology.

[54]  J. Bouajila,et al.  Relation between chemical composition or antioxidant activity and antihypertensive activity for six essential oils. , 2012, Journal of food science.

[55]  G. Curcuruto,et al.  Screening of the essential oil composition of wild Sicilian thyme , 2010 .

[56]  Ana Maria Carvalho,et al.  Lamiaceae often used in Portuguese folk medicine as a source of powerful antioxidants: vitamins and phenolics. , 2010 .

[57]  G. Lazzara,et al.  Aqueous laponite clay dispersions in the presence of poly(ethylene oxide) or poly(propylene oxide) oligomers and their triblock copolymers. , 2008, The journal of physical chemistry. B.

[58]  G. Cavallaro,et al.  Pickering Emulsion Gels Based on Halloysite Nanotubes and Ionic Biopolymers: Properties and Cleaning Action on Marble Surface , 2019, ACS Applied Nano Materials.

[59]  M. Viuda‐Martos,et al.  Chemical composition and in vitro antibacterial properties of essential oils of four Thymus species from organic growth , 2013 .

[60]  N. Mimica-Dukić,et al.  Characterization of the volatile composition of essential oils of some lamiaceae spices and the antimicrobial and antioxidant activities of the entire oils. , 2006, Journal of agricultural and food chemistry.