Publications by authors named "Svetlana Zilberstein"

12 Publications

  • Page 1 of 1

New baits for fishing in cultural heritage's Mare Magnum.

J Proteomics 2021 03 14;235:104113. Epub 2021 Jan 14.

Spectrophon Ltd, Oppenheimer 7, Rehovot 7670107, Israel.

We describe here a modern tool for exploring documents pertaining to the world Cultural Heritage while avoiding their contamination or damage. Known under the acronym EVA, it consists of a plastic foil of Ethylene Vinyl Acetate studded with strong cation and anion resins admixed with C and C hydrophobic beads. When applied to any surface such foils can harvest any type of surface material, which is then eluted and analyzed via standard means, such as GS/MS (typically for metabolites), MS/MS (for peptide and protein analysis), X-ray (for elemental analysis). We briefly review here a number of past data, such as screening of original documents by Bulgakov, Chekov, Casanova, Kepler, while dealing in extenso with very recent data, pertaining to Orwell and Stalin and analysis of the skin of an Egyptian mummy. The technique was also successfully applied to paintings, such as the Donna Nuda at the Hermitage in St. Petersburg, attributed to Leonardo and his school. This novel methodology represents a formidable tool for exploring the past life of famous authors, scientist and literates in that it can detect traces of their pathologies and even drug consumption left by saliva and sweat traces on their original hand-written documents.
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http://dx.doi.org/10.1016/j.jprot.2021.104113DOI Listing
March 2021

Stalin's "black dog": a postmortem diagnosis.

Anal Bioanal Chem 2020 Nov 2;412(28):7701-7708. Epub 2020 Sep 2.

Department of Chemistry, Materials and Chemical Engineering "Giulio Natta", Politecnico di Milano, Via Mancinelli 7, 20131, Milan, Italy.

Undoubtedly, the two leaders who were under enormous pressure during World War II (WWII) were Winston Churchill and Joseph Stalin' since their respective countries had to sustain most of the war weight, at least in Europe. Lord Moran recounted in his memoir Winston Churchill: The Struggle for Survival that he had diagnosed a middle-aged Churchill with bipolar disorder. Churchill himself often referred to his periods of intense and prolonged depression as his "black dog." On the contrary, not much is known about Stalin's mental conditions, although in 1927 the neurologist V. M. Bekhterev, the day prior to his sudden death, upon a long examination of the leader's mental status, declared that he had found him affected by paranoia. No chemical evidence via clinical chemistry analyses was provided for the two leaders, though. We have had access to the collection of books (stored in the Russian Government Archive of Social and Political History, RGASPI, of the former Institute of Marxism and Leninism under the Central Committee of the USSR Communist Party) that Stalin was reading during WWII, with pages containing personal annotations on the margins. Upon harvesting surface material via EVA disks (ethylene-vinyl acetate studded with strong cation and anion exchangers and C-C resins) and instrumental analysis via X-ray photoelectron spectroscopy, we detected lithium levels (~ 100 ± 8 ng/cm) compatible with those present in the sweat and/or saliva of patients treated with lithium salts for curing bipolarity and paranoia or probably gout. These data are the first clear indication that Stalin was under cure for this pathology.Graphical abstract.
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http://dx.doi.org/10.1007/s00216-020-02914-zDOI Listing
November 2020

Surface analysis of ancient parchments via the EVA film: The Aleppo Codex.

Anal Biochem 2020 09 7;604:113824. Epub 2020 Jul 7.

Department of Chemistry, Materials and Chemical Engineering ''Giulio Natta'', Politecnico di Milano, Via Mancinelli 7, Milano, 20131, Italy. Electronic address:

The margins of several pages of the Aleppo codex have been found to be corroded and contaminated by diffuse maculae. In order to understand the origin of this decay these margins have been analysed by applying EVA (ethylene vinyl acetate plastic embedded with strong cation and anion exchangers and mixed with C and C hydrophobic resins) diskettes for harvesting surface material. The captured compounds have been eluted, digested with trypsin and analysed by nano-HPLC-MS. Three major strains of Aspergillus have been identified, namely Aspergillus fumigatus, Aspergillus pseudoglaucus, Aspergillus amstelodami, together with a lactobacillus strain and human keratins. The novelty of this investigation is that for the first time the EVA technology has been applied to ancient parchments in the absence of mechanical deformation or distortion that could be induced if there had been water exchange between the EVA diskettes and the parchment. These findings should help curators to find suitable restoration protocols for these precious documents belonging to the world Cultural Heritage.
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http://dx.doi.org/10.1016/j.ab.2020.113824DOI Listing
September 2020

"1984": What Orwell could not predict. Proteomic analysis of his scripts.

Electrophoresis 2020 11 9;41(21-22):1931-1940. Epub 2020 Jun 9.

Department of Chemistry, Materials and Chemical Engineering, Milano, Italy.

George Orwell, fighter for the Republican Army during the Spanish Civil War, was shot through the throat by a sniper on 20th May 1937 and nearly killed. After receiving only a summary external treatment, on the 29th, he was cured in a Barcelona hospital where he was infected by the Koch bacillus. After fleeing from Spain on 23rd June 1937, he repaired to his cottage in Wallington, Hertfordshire, wherefrom he wrote a letter to Sergey Dynamov, Editor of Soviet journal "Foreign Literature." This typewritten letter was analyzed by application of five EVA strips (ethylene vinyl acetate studded with strong cation and anion and with C and C resins; four on the corners and one over his signature), searching for biological traces. Upon elution of the captured biologicals, trypsin digestion and Orbitrap Fusion trihybrid mass spectrometer analyses, three of the five strips yielded clear traces of six unique proteins (via proteotypic peptides) of the tuberculosis bacterium. Additionally, MALDI TOF analysis of saliva of a tuberculosis patient and the EVA strip eluates gave a spectrum of 14 peptide bands (Mr 2700 to 6700 Da range) coincident between the two samples, thus, fully confirming Orwell's pathology. These results are attributed to saliva traces on Orwell's fingertips and to the fact that the letter was written on 2nd July 1937, when Orwell's pathology was at its peak.
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http://dx.doi.org/10.1002/elps.202000063DOI Listing
November 2020

EVA Technology and Proteomics: A Two-Pronged Attack on Cultural Heritage.

J Proteome Res 2020 08 17;19(8):2914-2925. Epub 2020 Jun 17.

Spectrophon Ltd., Oppenheimer 7, Rehovot 7670107, Israel.

A novel way for exploring the world's cultural heritage in the absence of damage or contamination (such as removing pigments in paintings or chipping away pieces of bones) of the items under investigation is here reported, called the EVA technique. It is based on films of ethylene vinyl acetate (EVA) impregnated with strong anion and cation exchangers, admixed with hydrophobic resins, C and C. When in contact with any surface these films can harvest nanomoles of macromolecules (proteins and DNA) as well as metabolites, which can then be identified by standard instrumentation. Some important applications are reported, such as the findings of the renal pathology and assumption of morphine in the original manuscript of Master I Margarita by Bulgakov, the presence of TBC bacterium in Chekhov's shirt and in a letter by Orwell, the and anthrax bacteria in the death registries of Milan's lazaretto in the 1630 plague bout, as well as ample traces of five metals in Kepler's manuscripts, suggesting his potential practice of alchemy. Also, in the pages of the Memoirs of Casanova, although the gonorrhea bacterium could not be found, spots of HgS could be measured, suggesting its use for curing the disease. A family of EVA films is described, enlarging its use to dedicated applications, such as the capture of drugs of abuse in the pages of famous writers and even in the paintings of fauvists. It is hoped that the present methodology could open the doors of museums, state archives, and private collections for detecting biological traces left by artists, literates, and men of culture in their masterpieces.
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http://dx.doi.org/10.1021/acs.jproteome.0c00080DOI Listing
August 2020

De re metallica. Johannes Kepler and alchemy.

Talanta 2019 Nov 26;204:82-88. Epub 2019 May 26.

Department of Chemistry, Materials and Chemical Engineering ''Giulio Natta'', Politecnico di Milano, Via Mancinelli 7, Milano, 20131, Italy. Electronic address:

The application of analytical chemistry to the exploration of the World Cultural Heritage represents a major challenge in that most protocols and strategies are invasive and require micro-sampling. We report a novel methodology for harvesting material deposited on the surface of ancient documents while avoiding their damage or contamination. The technology here described relates to the capture of metals on these specimens. It is based on the use of plastic films (ethylene vinyl acetate, EVA) impregnated with different metal chelators (sodium 2,3-dimercapto-1-propanesulfonate, DMPS, meso-2,3-dimercaptosuccinic acid, DMSA and ethylene diamino tetra acetic acid, EDTA, as calcium salt), for harvesting from surfaces of different supports potential traces of metals therein deposited. The EVA film technology has been used to explore the pages of a manuscript written by Kepler concerning the movements of the moon and catalogued under the title "Hipparchus" at the Archives of the Russian Academy of Sciences (St. Petersburg branch). The EVA-based chelating diskettes were able to capture very significant amounts of different metals, namely: Au, Ag, Hg, As, Pb, suggesting that Kepler, well known as astronomer, astrologist, mathematician and Lutheran theologian, might have started practicing alchemy, a pseudo-chemical science he had learned from his colleague Tycho Brahe in Prague.
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http://dx.doi.org/10.1016/j.talanta.2019.05.094DOI Listing
November 2019

Leonardo's Donna Nuda unveiled.

J Proteomics 2019 09 16;207:103450. Epub 2019 Jul 16.

Department of Chemistry, Materials and Chemical Engineering "Giulio Natta", Politecnico di Milano, Via Mancinelli 7, Milano 20131, Italy. Electronic address:

The painting "Donna Nuda" by Leonardo was acquired by Catherine II (the Great) from the R. Walpole collection, Houghton Hall, England, in 1779 for the Hermitage in St. Petersburg. By exploiting the EVA film technology (ethylene vinyl acetate polymer embedded with strong cation and anion exchangers and with C and/or C resins) we have explored the surface of the painting in order to ascertain the techniques used in its drawing. Five EVA films were affixed on the body and on the landscape for 60 min. Upon elution from the recovered films, the harvested material was analyzed by gas-chromatography/mass spectrometry as well as by liquid chromatography/mass spectrometry. "Tempera grassa" (consisting of linseed oil admixed with egg yolk) was used in the entire painting. The surface was then protected by a layer of conifer resin. It is hypothesized that access to the layer underneath the protective layer was obtained via micro-cracks on the conifer resin itself. Rosemary oil was used as diluent to slow down the drying process and so to perform the glazing technique, thus obtaining the "aerial perspective" in correspondence of the landscape. To our reckoning, this is the first time in which a Leonardo painting is analyzed in depth but also in which his artistic technique is deciphered via modern techniques for exploring Cultural Heritage. The EVA film technology might be used for ascertaining the authenticity of paintings and uncover frauds. SIGNIFICANCE STATEMENT: Leonardo da Vinci was the most famous Italian polymath of the Renaissance and one of the most important innovators of his time. He was the author of several important artworks such as "La Gioconda", but he also painted the "Donna Nuda" conserved at the Hermitage Museum. Although some attempts permitted the identification of part of the materials used by Leonardo, to date no analytical investigations were able to fully characterize and decipher the recipes. We explored the surface of the "Donna Nuda" painting through a non-invasive approach that uses a functionalized film to adsorb nano-scopic amounts of materials that were then analyzed by mass spectrometry. This method has the potential to revolutionize the approaches used to analyze cultural heritage.
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http://dx.doi.org/10.1016/j.jprot.2019.103450DOI Listing
September 2019

Il n'y a pas d'amour heureux pour Casanova: Chemical- and bio-analysis of his Memoirs.

Electrophoresis 2019 12 15;40(23-24):3050-3056. Epub 2019 Apr 15.

Department of Chemistry, Materials and Chemical Engineering ''Giulio Natta'', Politecnico di Milano, Milano, Italy.

The original manuscript of Casanova's Memoirs is stored at the Bibliothèque Nationale de France in Paris. We have gained access to it and explored the surfaces of chapters one and two (via the ethylene vinyl acetate [EVA] film technology, i.e., of diskettes of ethylene vinyl acetate with embedded strong cation and anion exchangers and C8 resins) in search of potential diseases of the author, especially of the gonorrhea bacterium, since Casanova reported that he had several bouts of this pathology along his adventurous life. Although the bacterium was not found, we have detected high levels of HgS as red spots along the lines of the manuscript, suggesting that Casanova was using this chemical as a cure for his venereal disease. Additionally, among the several bacteria identified on the surface via mass spectrometry, we could detect traces of Streptococcus uberis, a typical animal infection, found also in humans, together with a few strains of Lactobacilli, probably present in his saliva. The EVA film technology appears to open new horizons for investigating the world Cultural Heritage.
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http://dx.doi.org/10.1002/elps.201800505DOI Listing
December 2019

Anton Chekhov and Robert Koch Cheek to Cheek: A Proteomic Study.

Proteomics 2018 05;18(9):e1700447

Department of Chemistry, Materials and Chemical Engineering ''Giulio Natta'', Politecnico di Milano, Milano, Italy.

Five different letters and post cards as well as the shirt worn by Anton Chekhov on his death bed, stored in the State Literary-Memorial Museum-Reserve A. P. Chekhov Melikhovo (nearby Moscow), have been analyzed by applying EVA (an ethyl vinyl acetate foil studded with crushed strong anion and cation exchangers and with C resins) diskettes to these surfaces. Three different eluates (under acidic and basic conditions and with acetonitrile) were analyzed by high resolution mass spectrometry. The environmental microbiota present on samples and the Mycobacterium tuberculosis strain were described by a meta-proteomics approach. Eight identified M. tuberculosis proteins confirmed the presence of the bacterium and the cause of Chekhov's death, in addition to several sequenced peptides belonging to other bacterial species. The human plasma proteins and human keratins, detected on a tiny blood spot on the shirt, demonstrated the power of the combined approach.
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http://dx.doi.org/10.1002/pmic.201700447DOI Listing
May 2018

Of mice and men: Traces of life in the death registries of the 1630 plague in Milano.

J Proteomics 2018 05 3;180:128-137. Epub 2018 Jan 3.

Department of Chemistry, Materials and Chemical Engineering "Giulio Natta", Politecnico di Milano, Via Mancinelli 7, Milano 20131, Italy. Electronic address:

The death registries of the plague epidemic of 1630, stored at the Archivio di Stato of Milano, have been interrogated via the EVA film technology (ethyl vinyl acetate film studded with crushed strong anion and cation exchangers as well as C resins). The EVA diskettes have been left in contact with the lower right margins of 11 different pages pertaining to the peak months of the raging disease (June through end of September) for 60-90min and then the captured material, after elution and digestion, analysed by mass spectrometry. The main findings: 17 Yersiniaceae family proteins, 31 different human keratins, 22 unique mouse keratins, about 400 peptides from different bacterial strains, 58 human tissue proteins and 130 additional mouse and rat tissue proteins. In addition, >60 plant proteins (notably potato, corn, rice, carrot and chickpeas), likely representing the meagre meals of the scribes, contaminating the pages, were detected. The significance of these unique findings is amply illustrated in the body of the article.

Significance: Archivists, historians, librarians usually explore the texts of ancient and modern manuscript in order to extract the meaning of the writing and understand the mood, feelings, political, philosophical and/or religious ideas therein expressed by the authors. With the present EVA methodology (the only one, at present, able to access our Cultural Heritage without damaging or contaminating it) we interrogate, instead, the support, be it paper, parchment, wood panel, cloth, canvas and the like, in order to extract invisible data, such as the presence of drugs, medicaments, infectious pathogens, human and environmental contaminants. Metabolites, proteins and peptides thus captured are then analysed via mass spectrometry. The unique data mined by this technology should considerably enlarge the (so far) restricted horizon of the writing exploration and add new insight on the environmental conditions in which such documents were produced as well as, importantly, on the health/pathological conditions of the authors. It is believed that the present technology, as here reported, will become the officially accepted one for exploring the world Cultural Heritage.
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http://dx.doi.org/10.1016/j.jprot.2017.11.028DOI Listing
May 2018

A miniaturized sensor for detection of formaldehyde fumes.

Electrophoresis 2017 09 20;38(17):2168-2174. Epub 2017 Jun 20.

Department of Chemistry, Materials and Chemical Engineering ''Giulio Natta'', Politecnico di Milano, Milano, Italy.

A miniaturized chemical sensor is here described for the analysis of environmental pollutants (VOC: volatile organic chemicals). It is used for remote detection of formaldehyde (FA) fumes in the atmosphere, and is based on the redox reaction between FA and silver nitrate. The sensor is worn as a bracelet and the data acquired are transferred via a Bluetooth channel to a smartphone. A dedicated software transforms the signal from a grey to a color scale. The signal response has been assessed over low (20 to 120 ppb) as well as higher (1-15 ppm range) levels. The sensor has been applied to monitor potential FA fumes of some artwork in the Summer Palace in Beijing and the modifications induced by FA treatment on a precious Stradivarius violin. The performance of this novel sensor is compared with a commercial apparatus widely adopted, namely the Honeywell MultiRAE Lite wireless portable multi-gas monitor (pumped model).
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http://dx.doi.org/10.1002/elps.201600559DOI Listing
September 2017

Method for Noninvasive Analysis of Proteins and Small Molecules from Ancient Objects.

Anal Chem 2017 03 3;89(6):3310-3317. Epub 2017 Mar 3.

Department of Chemistry, Materials and Chemical Engineering "'Giulio Natta"', Politecnico di Milano , Via Mancinelli 7, Milano 20131, Italy.

Proteins and small molecules from ancient objects and cultural heritage can provide key information and contribute to study the context of objects and artists. However, all present-day protocols and strategies for the analysis of ancient samples are often invasive and require microsampling. Here, we present a new method for the noninvasive analysis of proteins and small molecules: the technique uses a special ethyl-vinyl acetate film functionalized with strong cation/anion exchange and C resins, for interacting with both proteins and small molecules present on the surface of the objects, followed by LC-MS/MS analysis. The new method was fully validated for the determination of both proteins and small molecules on several types of supports, showing excellent analytical performances such as, for example, R of the calibration curve of 0.98 and 0.99 for proteins and small molecules, low but very repeatable recoveries, particularly adequate for investigations on precious ancient samples that must not be altered by the analytical procedure. ESEM images and LED multispectral imaging confirmed that no damages or alterations occurred onto the support surfaces and no residues were left from the extractive film. Finally, the new method was applied for the characterization of the binders of a historical fresco of the XVI century from the Flemish painter Paul Brill and of a recently discovered fresco from Isidoro Bianchi (XVII century). Moreover the method was employed for the identification of the colorant used by Pietro Gallo (XIV century) on a wood panel. The method here reported can be easily applied to any other research on ancient precious objects and cultural heritage, since it does not require microsampling and the proteins/small molecules extraction can be performed directly in situ, leaving the object unchanged and intact.
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http://dx.doi.org/10.1021/acs.analchem.6b03722DOI Listing
March 2017