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Identifying the fibres in historical textiles presents a complex challenge due to the wide variety of plant, animal and early synthetic materials that have been used. Traditionally, this identification process involves sampling followed by either microscopic examination or ATR-FTIR spectroscopy. However, there are instances when sampling is restricted due to the good condition or significant value of the object under analysis. Additionally, the presence of leather components alongside textiles can further complicate the identification. This paper proposes a novel non-invasive method for fibre identification based on External Reflection (ER) FTIR spectroscopy, which has been rarely applied to textiles or leather. The current research demonstrates that ER-FTIR spectrum is a viable tool for fibre identification on both recent and historical textiles. The non-invasiveness of the analytical approach enables a comprehensive investigation without compromising the number or position of samples. Respect to ATR-FTIR spectra, the ER-FTIR spectra frequently exhibit an amplification of certain diagnostic bands, facilitating the identification of the various fibres examined in this study (cotton, hemp, viscose, silk, wool, leather, polyamide, acrylic, polyester). The extended spectral range (7500-375 cm -1 ) which is provided by ER-FTIR spectrometry also contains extra bands in the near infrared region, which can provide key information for the discrimination due to the lack of distortion phenomena. The technique was applied to the characterisation of textile materials coming from a collection of 10 traditional Japanese samurai armours spanning from the 16th to the 20th century (Museo delle Culture, Lugano, Switzerland). For the first time, the results provided a comprehensive overview of the textiles utilized in Japanese armours across various historical periods. Overall, the appearance of materials in samurai armours reflects the evolution of armour-making techniques and the influence of socio-cultural factors throughout Japanese history. Synthetic and semi-synthetic materials were easily detected, revealing the occurrence of a past conservation treatment or the early adoption of modern man-made materials in the manufacturing of traditional armours. The approach outlined in this case study can be applied to textile collections of various kinds, offering a reliable mean to discern the yarn composition and detect non-original components. The method also appears as a valuable prescreening tool for designing a less intrusive yet more informative sampling strategy, should additional details about fibre type and dyeing be necessary., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier B.V. All rights reserved.)

To correctly manage a collection of historical silks, it is important to detect if the yarn has been originally subjected to degumming. This process is generally applied to eliminate sericin; the obtained fiber is named soft silk, in contrast with hard silk which is unprocessed. The distinction between hard and soft silk gives both historical information and useful indications for informed conservation. With this aim, 32 samples of silk textiles from traditional Japanese samurai armors (15th-20th century) were characterized in a non-invasive way. ATR-FTIR spectroscopy has been previously used to detect hard silk, but data interpretation is challenging. To overcome this difficulty, an innovative analytical protocol based on external reflection FTIR (ER-FTIR) spectroscopy was employed, coupled with spectral deconvolution and multivariate data analysis. The ER-FTIR technique is rapid, portable, and widely employed in the cultural heritage field, but rarely applied to the study of textiles. The ER-FTIR band assignment for silk was discussed for the first time. Then, the evaluation of the OH stretching signals allowed for a reliable distinction between hard and soft silk. Such an innovative point of view, which exploits a "weakness" of FTIR spectroscopy-the strong absorption from water molecules-to indirectly obtain the results, can have industrial applications too.

The synthesis of monomeric octahedral complexes constructed around a TiO 4 N 2 core bearing neocuproine derivatives is detailed. These architectures follow the [Ti( 1 ) 2 ( N-N )] general formulas, where 1 is the 6,6'-diphenyl-2,2'-biphenolato ligand and N-N is a 1,10-phenanthroline derivative. Single-crystal analysis revealed that the neocuproine-based ligands within these architectures adopt a nonplanar geometry. The distortion of these aromatic diimine systems has been quantified through measurement of a torsion angle (α) and a dihedral angle (β) defined by two planes within the aromatic diimine molecule (π 1 and π 2 ), permitting one to evaluate the twisting and bending of a coordinated nitrogen ligand, respectively. Next, the scope of this investigation was extended to the synthesis of a dimeric architecture, [Ti 2 ( 1 ) 4 ( 3 )], where 3 is the 5,5'-bis(neocuproine) ligand. Again, a strong distortion of the neocuproine fragments was characterized in the crystalline state for such a complex. The UV-visible properties of these complexes were interpreted with the help of time-dependent density functional theory calculations. The solution behavior as well as good hydrolytic stability of these species has been established.

Merkel cell carcinomas are very rare (80 cases up to 1986) and very malignant; they have been known for 20 years only as "trabecular carcinomas". They do not rise from neural crests, and therefore are not apudomas, but from a staminal cell of the skin with neuroendocrine evolution. Merkel cell carcinomas must be distinguished from undifferentiated carcinomas of the skin, lymphomas, and oat cell carcinomas. Eight patients (46 to 86 years old) are presented, 4 males and 4 females, with 1 gluteal (the younger female patient), 3 head and 4 limb localizations of Merkel cell carcinoma. Radiotherapy was carried out after surgery in 7 patients and after biopsy in 1; local recurrences were already present in 3 cases, and lymph node metastases in 5; tumor doses were 36-65 Gy, administered with different techniques, i.e. roentgen therapy, telecobalt therapy, 192Ir curietherapy. Chemotherapy was used in 2 metastatic patients only. Four patients are alive and free of disease and 4 are dead; 3 of the living patients have been followed 3-26 months. The high risk of radiation damage (1 necrosis, 2 giant edemas, 1 severe fibrosis) recommends that large fields and high single and/or total radiation doses be avoided. In conclusion, surgery is diagnostic but not curative on account of the high risk of recurrence; radiotherapy is important because Merkel cell carcinomas are very radiosensitive. Due to easy lymphatic spread of this type of cancer, radiotherapy must include the regional lymph nodes (dose: 40-50 Gy). The role of chemotherapy is still to be assessed but many antiblastic drugs are effective.