Vincent van Gogh's painting, Country Huts Among Trees , was executed in 1883. The painting underwent restoration likely in the second half of the 20th century; however, the specifics of this treatment are not documented. The painting's state of preservation was thoroughly examined to inform a conservation treatment consisting of solvent cleaning to remove the unwanted varnish. Optical Coherence Tomography (OCT) and reflection FTIR spectroscopy provided insight into the painting's stratigraphy and identified surface layers across various regions. OCT revealed the presence of multiple varnish layers, while FTIR-ATR, Raman, and reflection FTIR spectroscopy allowed the identification of the upper varnish layer as an acrylic resin. The combined use of FTIR and OCT enabled a non-invasive, in situ assessment of solvent cleaning procedures aimed at the selective removal of the upper varnish layer. Analyses were performed during the cleaning tests to carefully assess the condition of the painted surface and the original varnish. The results of these cleaning tests informed and refined the varnish removal procedure during the restoration process. (c) 2025 Published by Elsevier Masson SAS.
Obiektem badań była rzeźba z drewna lipowego przedstawiająca Madonnę z Dzieciątkiem (120 × 55 × 38 cm) pochodząca z klasztoru Dominikanów w Krakowie. Figura została wykonana w pierwszej ćwierci XVI wieku przez rzeźbiarza znającego dzieła powstałe w warsztacie Wita Stwosza w Norymberdze, na co wskazuje charakterystyczny dla dzieł tego mistrza układ szat. Badania historyczne sugerują, że figura Madonny z Dzieciątkiem pierwotnie była obiektem indywidualnego kultu, prawdopodobnie wisiała swobodnie pośrodku kościoła. Rzeźba nie przetrwała w swej pierwotnej formie, na przestrzeni stuleci ulegała licznym przekształceniom. Prawdopodobnie w XIX wieku zmieniono jej funkcję, umieszczając ją na drewnianej podstawie jako feretron do noszenia w procesjach. Renowacje obejmowały przemalowania karnacji i ponowne złocenie szat wraz z lokalnymi zmianami w drewnianej formie. Znaczna grubość wtórnie nałożonych gruntów oraz niska wartość artystyczna nieoryginalnej polichromii zniekształciły późnogotycki charakter rzeźby. W wyniku prac konserwatorskich odsłonięto częściowo zachowane karnacje oraz szczątkowo zachowaną polichromię szat. Zabytek został poddany analizom fizyko-chemicznym, dzięki czemu zidentyfikowano wtórne i pierwotnie zastosowane materiały. Badania wizualne z udziałem radiografii cyfrowej oraz obserwacja mikroskopowa przekrojów pozwoliły na określenie stratygrafii obiektu. Przekroje poprzeczne badano za pomocą skaningowej mikroskopii elektronowej połączonej ze spektroskopią rentgenowską z dyspersją energii (SEM-EDS). Warstwy malarskie analizowano przy użyciu spektrometrii fluorescencji mikro-rentgenowskiej (XRF). Do identyfikacji związków organicznych obecnych w podłożu i warstwach farby wykorzystano spektroskopię w podczerwieni z transformacją Fouriera (FTIR). Uzyskane wyniki prac konserwatorskich i badawczych uzupełniły aktualny stan wiedzy o rzeźbie i praktykach warsztatowych początku XVI wieku.
Amber has been used to create decorative items for centuries, but its degradation presents challenges for conservators. This study identifies substances historically used to protect amber objects, especially those from 17th and 18th century Gdansk workshops. Despite their historical value, information on amber conservation is scarce. Traditional substances are noted, but their exact compositions and effects on amber remain unclear. Synthetic resins, introduced in the late 19th century, also degrade, complicating conservation due to their removal difficulty and interference with amber identification. This research aimed to develop methods for detecting and analyzing protective coatings on amber objects using macroscopic and microscopic techniques. Initial methods included analytical photography under visible and UV light and reflectance imaging spectroscopy (RIS) to assess the surface. Raman spectroscopy (RS) and X-ray fluorescence spectroscopy (XRF) were used for detailed analysis. RS provided precise layer-specific information but was sensitive to surface conditions, while XRF quickly identified inorganic compounds but not organic materials. Examining amber objects from Polish collections using this methodology revealed various protective substances, including synthetic resins and nitrocellulose varnishes. This research contributes to amber conservation by proposing a comprehensive material analysis approach, essential for developing effective conservation strategies for these historic objects.
W ramach przygotowań do nowej ekspozycji Muzeum Książąt Czartoryskich – Oddziału Muzeum Narodowego w Krakowie konieczne było przeprowadzenie konserwacji części należących do muzealnej kolekcji miniatur Wincentego Lesseura, co wykorzystano jako sposobność do rozpoznania i analizy warsztatu artysty. W tym celu grupę portretów poddano badaniom specjalistycznym: wykonano pomiary za pomocą spektroskopii fluoroscencji rentgenowskiej (makro-XRF) i spektroskopii Ramana (RS) oraz fotografie w światłach analitycznych, prowadzono obserwacje mikroskopowe. W wyniku badań zidentyfikowano kilkanaście pigmentów i ziarna skrobi na powierzchni obiektów. Szczególnie interesujące jest odkrycie, że artysta stosował błękit kobaltowy już w 1796 r., zanim pigment ten zdobył szerszą popularność w pierwszej połowie XIX wieku. Na podstawie ujawnionych sposobów nanoszenia i łączenia poszczególnych pigmentów opracowano technologię malarską Lesseura. Należy podkreślić, że badania zespołu miniatur, które wyszły spod jednej i tak znakomitej ręki to okoliczność wyjątkowa, zwłaszcza jeśli chodzi o warsztat miniaturzysty tworzącego na terenie Polski.
ABSTRACTThe study explores drawing materials from the 17th century to the present using noninvasive techniques like Raman spectroscopy in selected cases supplemented by x‐ray fluorescence (XRF) spectroscopy. This publication is an effort to expand knowledge across diverse periods and materials. A collection of six drawings spanning from 1700 to 1899 from the National Museum in Krakow and a 20th‐century birch bark artifact were analyzed. Noninvasive techniques facilitated the systematic analysis of drawing materials, providing insights into diverse substances over centuries. Identified materials include hematite, calcite, graphite, bister, sepia, iron gall ink, and crystal violet dye. Understanding the chemical composition aids conservation and is a reference for future art history and preservation studies.
A multi-disciplinary research campaign was conducted on the painting Country Huts Among Trees by Vincent van Gogh. The painting belongs to the John Paul II Collection and is currently on deposit at the Museum of John Paul II and Primate Wyszy nski, owned by the Archdiocese of Warsaw. The painting, considered a significant work from Van Gogh's early Dutch period, reflects his mastery of oil technique and his fascination with rural life. It is characterized by a specific, dark and subdued palette that conveys the expressive and dramatic mood of the landscape from the early 1880s. This contribution presents the findings from the scientific research campaign carried out on the painting during 2021-2024. The analyses included technical photography in visible, infrared, and ultraviolet ranges, followed by spectroscopic and microscopic analyses. These investigations revealed the presence of pigments such as bone black, carbon black, chrome yellow, iron-based earth pigments, lead white, Prussian blue, and vermilion. This investigation has been very challenging due to the absence of any work by Vincent van Gogh in Polish museum collections. However, analysis of the painting has provided an interesting opportunity to study Van Gogh's materials and techniques within a broader context of art history and painting technology. The results have provided support to art historical research related to the painting's authenticity and significance. (c) 2024 Consiglio Nazionale delle Ricerche (CNR). Published by Elsevier Masson SAS. All rights are reserved, including those for text and data mining, AI training, and similar technologies.
ABSTRACTThe multidisciplinary, noninvasive analysis of baroque amber artworks is part of a research project that deals with the most valuable objects from the Museum of Gdansk (Poland). The two most interesting objects will be presented here: a Baroque Gdansk wardrobe‐shaped amber cabinet (made by Johann Georg Zernebach, Gdansk, 1724) and a crucifix (Gdansk, 17th century). Macro‐ (UV, IR, and X‐radiography) and micro‐ (XRF and Raman spectroscopy) analytical methods were applied to reveal traces of old conservation treatments and uncover the techniques of the 17th and 18th century amber masters. UV photography shows the differences between the amber plates that are not so easily detected under visible light, while XRF spectrometry detects elements atypical for amber objects, suggesting previous conservation treatments. Confocal Raman measurements, especially Raman depth profiling, were performed for the amber artworks and allowed to detect areas of previous conservation treatments. Single‐point scans were collected from the surface (0 μm) to a depth of −200 μm, with a step of 50 μm. The results allowed us to identify three different types of zones: where the amber was preserved without any protective layer, places where the amber was covered with a thin layer of a protective substance, and places where amber elements were compensated for loss using a binding agent and filler. The presented project allowed the development of a comprehensive methodology for the analysis of amber objects, especially to optimize the capabilities of confocal Raman microscopy. The combination of macro‐ and microanalytical techniques made it possible to obtain a broad overview of such complex artworks while optimizing the time and effort spent on the investigations.
Artefacts made of and from untypical materialswith the use of sophisticated techniques preserved in museumsconstitute an exceptional challenge to museum curators. Suchis the case of two letters described in the paper, written onbirch bark by someone signed as the female: Janka and Jaśkadispatched to her mother from the Soviet Polovinka Gulag inthe Urals in 1946 and 1947. Currently, the artefacts are in thecollection of the Museum of Rev. Józef Jarzębowski in LicheńStary, while their history was explained only in the 2010s. In2022, the letters underwent museum conservation, whichallowed to find out what material they were written on andwhat technique was used for the execution, following whichthey were appropriately preserved so that they can last thelongest possible minimizing their deterioration.
Wokół zespołu nowożytnych miniatur malowanych na pergaminie z daru Kon stantego Schmidt-Ciążyńskiego w zbiorach Muzeum Narodowego w Krakowie W 1885 roku Konstanty Schmidt-Ciążyński przekazał Muzeum Narodowemu w Krakowie (MNK) czternaście miniatur malowanych na pergaminie. Mimo wielu oczywistych różnic historia przypisała autorstwo jednemu artyście, Willemowi van Bemmelowi. W trakcie prac konserwatorskich podjęto próbę uzyskania argumentów mogących potwierdzić lub zanegować warsztatowe pokrewieństwo miniatur. Analizowano technologię, cechy stylistyczne oraz charakter zniszczeń. Przeprowadzono nieniszczące badania warstw malarskich, analizy mikroskopowe powierzchni, wykonano fotografie w światłach analitycznych. Niniejszy artykuł stanowi podsumowanie tych badań oraz próbę postawienia tez sumarycznych. Okazało się, że dla niektórych obiektów można wskazać analogie i odnaleźć odniesienia ikonograficzne. Udało się również dokonać podziału analizowanych miniatur pod kątem podobieństw w użyciu pigmentów zidentyfikowanych w warstwie malarskiej. Cechy stylistyczne i warsztatowe wskazują na wspólne autorstwo nielicznych miniatur z tego zbioru.
This study focuses on the analysis of Japanese woodblock prints from the Taisho period, specifically copies of renowned artists such as U. Hiroshige, recently donated to the Far Eastern Art Department of the National Museum in Kraków by Jens Wiebel. The aim of this research is to investigate the paper production methods employed for these woodblocks by comparing them with the original works from the Feliks Jasieński collection, previously donated to the National Museum in Kraków in 1920. Advanced analytical techniques including Fourier transform infrared spectroscopy (FTIR), X-ray fluorescence spectrometry (XRF), scanning electron microscopy (SEM), and Raman spectroscopy were utilized for the analysis. These methods facilitated the identification of chemical compounds, such as silicon, chalk, mica, talc, gypsum, starch, cellulose, and protein, as well as elements like Ca, Si, Mg, Al, K, S, and Na, present in the paper structure or acting as fillers. The results revealed notable differences between the papers from the two collections and identified distinct features associated with prints from the Taisho period. Notably, the presence of rice flour and silicate fillers was observed in all examined items. Supplementary data obtained from this analysis can be utilized not only to establish the chronology and estimate the production time of the papers but also to enhance the current knowledge of papermaking methods, additives, and fillers employed during the era in question.
The chosen object from the National Museum in Kraków collection (the Amber Altar of the Lord’s Passion) was examined by Raman spectroscopy (RS) and reflectance imaging spectroscopy (RIS) in short wavelength infrared (SWIR) spectral range. These studies allowed to identify the type of amber used and to assess the existence of a degraded layer. Based on the analysis of the reflection spectra and using the NMF (Nonnegative Matrix Factorization) algorithm, the amber of the Altar were assigned to two different classes. It may be associated with the use of different technologies for the preparation of amber plates. Moreover, as a result of the PCA (Principal Component Analysis) dimension reduction algorithm, an initial classification of the object’s amber into succinite (both native and German) and/or gedan-succinite and/or glessite was performed. Analysis of Raman spectra obtained by deep profiling method allowed to state the existence of a degraded layer on the surface of the amber figures of Saints Peter and Paul. The change in the spectrum profile depending on the depth of the signal collection indicates, among others, changes in the structure related to the exomethylene group and changes in the CH $$_{2}$$ and CH $$_{3}$$ groups. Thanks to the analysis of reflectance imaging spectroscopy and Raman spectroscopy, it was possible to identify the places of occurrence of amber imitations. The bands distinguished in the Raman spectra indicate the use of an epoxy resin.
A multi-disciplinary project focusing on the non-invasive analysis of the early painting of Sofonisba Anguissola (1532–1625), “Self-portrait at an Easel” (Museum-Castle in Łańcut, Poland) was implemented out applying macro- and micro-analytical techniques. Technical photography using UV radiation and X-radiography were used along with macro-XRF to better understand the materials and techniques of this painting. Then, microscopic non-invasive techniques like single-point micro-XRF, micro-Raman and optical coherence tomography (OCT) were used as complementary methods to enhance the level of detail of results obtained with macro-techniques. The pigments used by Sofonisba Anguissola include: vermilion, lead white, smalt with indigo, goethite with impurities like jarosite and anatase, vegetable and bone carbon black, a copper green pigment, and massicot. Macro-XRF technique detected the presence of Ca and Pb in the ground of the painting suggesting the application of an oil-gypsum ground layer with addition of lead white. The palette used for “Self-portrait at an Easel” was compared to another painting from the same period, “The Game of Chess” (National Museum in Poznan, Poland) showing similarities in the techniques.
This study focused on the use of non-invasive analytical techniques to increase the knowledge of painting methods of Jan Cybis (1897-1972), who was a leader of the Colorists, a group of Polish painters of the 1930s. Jan Cybis developed his own style characterized by high color values, varied texture and expressive stain. The aim of this study was to assess the technology, painting technique and materials used by Jan Cybis. Eight oil paintings from the collection of the National Museum in Krakow were studied. For each painting, a series of images were recorded using various ranges of electromagnetic radiation including near infrared, visible, ultraviolet, and X-ray. In order to characterize the pigments present in the paint layer, measurements of elemental composition by X-ray fluorescence spectrometry (XRF) were carried out. Additionally, samples were analyzed with optical microscopy (OM), Raman spectroscopy (RS) and scanning electron microscopy coupled with energy dispersive X-ray microanalysis (SEM-EDS). In this publication, the results of detailed analyses of four paintings characteristic of different periods of the artist's work are discussed. This study allowed to identify the artist`s painting technique through an analysis of how the paintings were executed and of the present pigments.
A depth profile-scanning study of an 18th-century gun-powder horn as well as reference Baltic amber samples was performed using a Raman confocal microscope equipped with a 785-nm laser. It was found that spectra collected from the surface are different than those from the bulk. The main changes are observed in the 1,700-1,400 cm(-1)range and are caused by degradation of the amber. The degraded layer was characterized mainly by an increase of the 1,615 cm(-1)band ascribed to the nu(C(sic)C) characteristic of aromatic rings and a decrease of the 1,645 cm(-1)band ascribed to the nu(C(sic)C) of nonconjugated structures. The degraded layer is estimated at 100-150 mu m, where the spectra gradually resembled the spectrum of nondegraded amber. Analogous changes were observed both for the reference samples and for the abovementioned historical object. The observed spectral changes suggest that this technique could be utilized for studying the degradation of amber artifacts in museum collections.
A new type of aggregate, formed in human red blood cells (RBCs) in response to glutaraldehyde treatment, was discovered and analyzed with the classical and advanced biomolecular imaging techniques. Advanced Heinz body-like aggregates (AHBA) formed in a single human RBC are characterized by a higher level of hemoglobin (Hb) degradation compared to typical Heinz bodies, which consist of hemichromes. The complete destruction of the porphyrin structure of Hb and the aggregation of the degraded proteins in the presence of Fe3+ ions are observed. The presence of such aggregated, highly degraded proteins inside RBCs, without cell membrane destruction, has been never reported before. For the first time the spatial differentiation of two kinds of protein mixtures inside a single RBC, with different phenylalanine (Phe) conformations, is visualized. The non-resonant Raman spectra of altered RBCs with AHBA are characterized by the presence of a strong band located at 1037 cm-1, which confirms that glutaraldehyde interacts strongly with Phe. The shape-shifting of RBCs from a biconcave disk to a spherical structure and sinking of AHBA to the bottom of the cell are observed. Results reveal that the presence of AHBA should be considered when fixing RBCs and indicate the analytical potential of Raman spectroscopy, atomic force microscopy and scanning near-field optical microscopy in AHBA detection and analysis.
Summary Eosinophils are acidophilic granulocytes that develop in the bone marrow. Although their population contributes only to approximately 1–6% of all leucocytes present in the human blood, they possess a wide range of specific functions. They play a key role in inflammation‐regulating processes, when their numbers can increased to above 5 × 10 9 /l of peripheral blood. Their characteristic feature is the presence of granules containing eosinophil peroxidase ( EPO ), the release of which can trigger a cascade of events promoting oxidative stress, apoptosis or necrosis, leading finally to cell death. Raman spectroscopy is a powerful technique to detect EPO , which comprises a chromophore protoporphyrin IX . Another cell structure associated with inflammation processes are lipid bodies (lipid‐rich organelles), also well recognized and imaged using high resolution confocal Raman spectroscopy. In this work, eosinophils isolated from the blood of a human donor were analysed versus their model, EoL‐1 human eosinophilic leukaemia cell line, by Raman spectroscopic imaging. We showed that EPO was present only in primary cells and not found in the cell line. Eosinophils were activated using phorbol 12‐myristate 13‐acetate, which resulted in lipid bodies formation. An effect of cells stimulation was studied and compared for eosinophils and EoL‐1.
Three non-destructive and complementary techniques, Raman imaging, Atomic Force Microscopy and Scanning Near-field Optical Microscopy were used simultaneously to show for the first time chemical and structural differences of carotenoid crystals. Spectroscopic and microscopic scanning probe measurements were applied to the released crystals or to crystals accumulated in a unique, carotenoids rich callus tissue growing in vitro that is considered as a new model system for plant carotenoid research. Three distinct morphological crystal types of various carotenoid composition were identified, a needle-like, rhomboidal and helical. Raman imaging using 532 and 488 nm excitation lines provided evidence that the needle-like and rhomboidal crystals had similar carotenoid composition and that they were composed mainly of β-carotene accompanied by α-carotene. However, the presence of α-carotene was not identified in the helical crystals, which had the characteristic spatial structure. AFM measurements of crystals identified by Raman imaging revealed the crystal topography and showed the needle-like and rhomboidal crystals were planar but they differed in all three dimensions. Combining SNOM and Raman imaging enabled indication of carotenoid rich structures and visualised their distribution in the cell. The morphology of identified subcellular structures was characteristic for crystalline, membraneous and tubular chromoplasts that are plant organelles responsible for carotenoid accumulation in cells.
Endothelial dysfunction is recognized as a critical condition in the development of cardiovascular disorders. This multifactorial process involves changes in the biochemical and mechanical properties of endothelial cells leading to disturbed release of vasoprotective mediators. Hypercholesterolemia and increased stiffness of the endothelial cortex are independently shown to result in reduced release of nitric oxide and thus endothelial dysfunction. However, direct evidence linking these parameters to each other is missing. Here, a novel method combining Raman spectroscopy for biochemical analysis and Atomic Force Microscopy (AFM) for analyzing the endothelial nanomechanics was established. Using this dual approach, the same areas of native ex vivo aortas were investigated, either derived from mice with endothelial dysfunction (ApoE/LDLR−/−) or wild type mice. In particular an increased intracellular lipid content and elevated cortical stiffness/elasticity were shown in ApoE/LDLR−/− aortas, demonstrating a direct link between endothelial dysfunction, the biochemical composition and the nanomechanical properties of endothelial cells.
The scanning near-field optical microscopy (SNOM) shows a potential to study details of biological samples, since it provides the optical images of objects with nanometric spatial resolution (50-200 nm) and the topographic information at the same time. The goal of this work is to demonstrate the capabilities of SNOM in transmission configuration to study human endothelial cells and their morphological changes, sometimes very subtle, upon inflammation. Various sample preparations were tested for SNOM measurements and promising results are collected to show: 1) the influence of α tumor necrosis factor (TNF-α) on EA.hy 926 cells (measurements of the fixed cells); 2) high resolution images of various endothelial cell lines, i.e. EA.hy 926 and HLMVEC (investigations of the fixed cells in buffer environment); 3) imaging of live endothelial cells in physiological buffers. The study demonstrate complementarity of the SNOM measurements performed in air and in liquid environments, on fixed as well as on living cells. Furthermore, it is proved that the SNOM is a very useful method for analysis of cellular morphology and topography. Changes in the cell shape and nucleus size, which are the symptoms of inflammatory reaction, were noticed in TNF-α activated EA.hy 926 cells. The cellular structures of submicron size were observed in high resolution optical images of cells from EA.hy 926 and HLMVEC lines.
Subsequent to publication, an error was identified in the affiliation of the last author of this article.1 This should appear as Malgorzata Baranskaa,b. The corrected affiliations are shown below. Katarzyna M. Marzec,a* Anna Rygula,a,b Bayden R. Wood,c Stefan Chlopickia,d and Malgorzata Baranskaa,b a. Jagiellonian Centre for Experimental Therapeutics (JCET), Jagiellonian University, Bobrzynskiego 14, 30-348 Krakow, Poland b. Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Krakow, Poland c. Centre for Biospectroscopy, School of Chemistry, Monash University, Clayton, VIC, 3800 Australia d. Department of Experimental Pharmacology, Chair of Pharmacology, Jagiellonian University, Medical College, Grzegorzecka 16, 31-531 Krakow, Poland