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Cultural heritage objects present a special set of challenges for chemical analysis. Often micro-sampling or even contacting the object is deemed an unacceptable risk to the object. This study examined if specular reflection FTIR, a non-sampling and non-contact analytical technique, can provide insight into chemical composition of the layered coatings on Frédéric Flachéron’s paper negatives (1848–1852) in the Harrison D. Horblit Collection of Early Photography, in Houghton Library, at Harvard University. Specular reflection FTIR data confirmed the identification of beeswax and sandarac as the transparentizing media on Flachéron’s paper negatives, as previously published by Lee Ann Daffner. However, specular reflection FTIR analysis also indicated that some negatives had additional localized coatings of orange shellac in specific areas of the images. To understand why Flachéron retouched his negatives with orange shellac, modern experimental replications of the paper negative process were performed. Through modern experimentation with the paper negative technique, it was found that Flachéron’s coatings of shellac served as an integral part of his image-altering technique. The color of the orange shellac subtly alters contrast and density, but it does not mask an area the way an opaque watercolor or highly pigmented paint might. The fine adjustments to the negatives with orange shellac were an attempt to perfect the contrast in the print, and better render depth and detail. These discoveries add to a growing body of recent research that points to the historic and art historic importance of negatives and coatings in photography. The specificity with which specular reflection FTIR was able to nondestructively identify the chemical composition of the local coating, and specifically target the analysis on the areas in which it appeared, allowed for an understanding of Flachéron’s use of local coatings as a retouching method rather than a protective coating.

Paper materials and works of art on paper such as drawings, watercolors, prints, books, and manuscripts represent a large portion of museum, archive, and library collections. However, paper materials are infrequently the subject of technical studies due to inherent limitations in their analysis such as the fragility of the paper substrate, a lack of suitable sampling opportunities, and the presence of mixed, but chemically similar cellulosic materials. The application of principal component analysis (PCA) modeling to specular reflection FTIR data has the potential to provide a non-invasive means of analysis for major and minor components in paper materials. Using known study collection objects, PCA models distinguishing paper sizing materials and fiber types based on specular reflection FTIR data were successfully demonstrated thus providing a plausible alternative method for the identification of paper materials in collection objects without the need for destructive testing or sampling of the object.

Abstract Natural teeth are supported by connective tissue collagen fibers that insert perpendicularly in the tooth cementum. Perpendicular insertion plays an important role in the maintenance of the junction between the oral epithelium and the periodontal connective tissue. Most titanium dental implant surfaces have no micro or macro structure to support perpendicularly oriented collagen attachment. Without this tight biologic seal to resist bacterial invasion and epithelial downgrowth, progressive bone loss in peri-implantitis is seen around dental implants. The purpose of this study was to establish the perpendicularly oriented collagen attachment to titanium oxide nanotube (TNT), and to assess its binding stability. TNT was prepared on the titanium-surface by anodization. Scanning electron microscopy (SEM) showed a regularly aligned TNT with an average 67 nm-diameter when anodized at 30 V for 3 h. Subsequently, collagen type I (CoI) was electrophoretically fused to anodic TNT in native polyacrylamide gel system where negatively charged CoI-C term was perpendicularly navigated to TNT. SEM and atomic force microscopy (AFM) were used to analyze CoI on the TiO2 and TNT surface. Several tens of nanometers of CoI protrusion were recorded by AFM. These protrusions may be long enough to be priming sites for cell-secreted CoI. CoI laid parallel to the titanium surface when fused by a chemical linker. Binding resistance of CoI against drastic ultrasonication was measured by Fourier-transform infrared spectroscopy attenuated total reflection (FTIR-ATR). The electrophoretically fused CoI in the titanium nanotube (TNT–CoIEPF) showed the significantly greatest binding resistance than the other groups (P

Sum frequency generation vibrational spectroscopy (SFG-VS) has been applied to investigate the selective crystallization of two forms of acetaminophen (ACM) on polymer surfaces. To our knowledge, this is the first account of SFG-VS being applied to study a polymer−crystal interface. SFG elucidates the molecular-level interactions governing phase selection at this buried interface, providing insight into the process of polymer-induced heteronucleation (PIHn) in solution as well as from the vapor phase. ACM heteronucleates from supersaturated aqueous solution in the metastable orthorhombic crystal form on poly(methyl methacrylate) (PMMA) surfaces, whereas the thermodynamically stable monoclinic crystal form is observed to form on poly(n-butyl methacrylate) (PBMA) surfaces. When the ACM crystals were grown by sublimation, only the monoclinic form was observed on both PMMA and PBMA. SFG-VS results indicate that hydrogen bonds are formed between PMMA CO groups and the orthorhombic ACM crystals at the PMMA−ACM interface. At PBMA−monoclinic ACM interfaces, no hydrogen bond formation was observed. This research demonstrates that SFG-VS can be used to probe molecular interactions at polymer−crystal interfaces. Understanding the interfacial molecular interactions will ultimately provide a rational basis for improving methods for polymorph discovery and selection based on heteronucleation on polymer surfaces. [ABSTRACT FROM AUTHOR]

Sum frequency generation vibrational spectroscopy (SFG) has been applied to study two-dimensional (2D) crystals formed by an isophthalic acid diester on the surface of highly oriented pyrolytic graphite, providing complementary measurements to scanning tunneling microscopy (STM) and computational modeling. SFG results indicate that both aromatic and CO groups in the 2D crystal tilt from the surface. This study demonstrates that a combination of SFG and STM techniques can be used to gain a more complete picture of 2D crystal structure, and it is necessary to consider solvent−2D crystal interactions and dynamics in the computer models to achieve an accurate representation of interfacial structure. [ABSTRACT FROM AUTHOR]

Cataract is one of the most prevalent protein aggregation disorders and still the most common cause of vision loss worldwide. The metabolically quiescent core region of the human lens lacks cellular or protein turnover; it has therefore evolved remarkable mechanisms to resist light-scattering protein aggregation for a lifetime. We now report that one such mechanism involves an unusually abundant lens metabolite, myo-inositol, suppressing aggregation of lens crystallins. We quantified aggregation suppression using our previously well-characterized in vitro aggregation assays of oxidation-mimicking human γD-crystallin variants and investigated myo-inositol’s molecular mechanism of action using solution NMR, negative-stain TEM, differential scanning fluorometry, thermal scanning Raman spectroscopy, turbidimetry in redox buffers, and free thiol quantitation. Unlike many known chemical chaperones, myo-inositol’s primary target was not the native, unfolded, or final aggregated states of the protein; rather, we propose that it was the rate-limiting bimolecular step on the aggregation pathway. Given recent metabolomic evidence that it is severely depleted in human cataractous lenses compared to age-matched controls, we suggest that maintaining or restoring healthy levels of myo-inositol in the lens may be a simple, safe, and globally accessible strategy to prevent or delay lens opacification due to age-onset cataract.

Two-dimensional hybrid organic-inorganic perovskites with chiral spin texture are emergent spin-optoelectronic materials. Despite the wealth of chiro-optical studies on these materials, their charge-to-spin conversion efficiency is unknown. We demonstrate highly efficient electrically driven charge-to-spin conversion in enantiopure chiral perovskites (R/S-MB) 2 (MA) 3 Pb 4 I 13 (〈 n 〉 = 4), where MB is 2-methylbutylamine, MA is methylamine, Pb is lead, and I is iodine. Using scanning photovoltage microscopy, we measured a spin Hall angle θ sh of 5% and a spin lifetime of ~75 picoseconds at room temperature in 〈 n 〉 = 4 chiral perovskites, which is much larger than its racemic counterpart as well as the lower 〈 n 〉 homologs. In addition to current-induced transverse spin current, the presence of a coexisting out-of-plane spin current confirms that both conventional and collinear spin Hall conductivities exist in these low-dimensional crystals.

Natural killer (NK) cell kill infected, transformed and stressed cells when an activating NK cell receptor is triggered 1 . Most NK cells and some innate lymphoid cells express the activating receptor NKp46, encoded by NCR1, the most evolutionarily ancient NK cell receptor 2,3 . Blockage of NKp46 inhibits NK killing of many cancer targets 4 . Although a few infectious NKp46 ligands have been identified, the endogenous NKp46 cell surface ligand is unknown. Here we show that NKp46 recognizes externalized calreticulin (ecto-CRT), which translocates from the endoplasmic reticulum (ER) to the cell membrane during ER stress. ER stress and ecto-CRT are hallmarks of chemotherapy-induced immunogenic cell death 5,6 , flavivirus infection and senescence. NKp46 recognition of the P domain of ecto-CRT triggers NK cell signalling and NKp46 caps with ecto-CRT in NK immune synapses. NKp46-mediated killing is inhibited by knockout or knockdown of CALR, the gene encoding CRT, or CRT antibodies, and is enhanced by ectopic expression of glycosylphosphatidylinositol-anchored CRT. NCR1)-deficient human (and Nrc1-deficient mouse) NK cells are impaired in the killing of ZIKV-infected, ER-stressed and senescent cells and ecto-CRT-expressing cancer cells. Importantly, NKp46 recognition of ecto-CRT controls mouse B16 melanoma and RAS-driven lung cancers and enhances tumour-infiltrating NK cell degranulation and cytokine secretion. Thus, NKp46 recognition of ecto-CRT as a danger-associated molecular pattern eliminates ER-stressed cells., (© 2023. The Author(s), under exclusive licence to Springer Nature Limited.)

Surface tension provides microbubbles (MB) with a perfect spherical shape. Here, we demonstrate that MB can be engineered to be nonspherical, endowing them with unique features for biomedical applications. Anisotropic MB were generated via one-dimensionally stretching spherical poly(butyl cyanoacrylate) MB above their glass transition temperature. Compared to their spherical counterparts, nonspherical polymeric MB displayed superior performance in multiple ways, including i) increased margination behavior in blood vessel-like flow chambers, ii) reduced macrophage uptake in vitro, iii) prolonged circulation time in vivo, and iv) enhanced blood-brain barrier (BBB) permeation in vivo upon combination with transcranial focused ultrasound (FUS). Our studies identify shape as a design parameter in the MB landscape, and they provide a rational and robust framework for further exploring the application of anisotropic MB for ultrasound-enhanced drug delivery and imaging applications.

A robust understanding of phloem functioning in tall trees evades us because current methods for collecting phloem sap do not lend themselves to measuring actively photosynthesizing canopy leaves. We show that Raman spectroscopy can be used as a quantitative tool to assess sucrose concentration in leaf samples. Specifically, we found that Raman spectroscopy can predict physiologically relevant sucrose concentrations (adjusted R 2 of 0.9) in frozen leaf extract spiked with sucrose. We then apply this method to estimate sieve element sucrose concentration in rapidly frozen petioles of canopy red oak (Quercus rubra) trees and found that sucrose concentrations are > 1100 mM at midday and midnight. This concentration is predicted to generate a sieve element turgor pressure high enough to generate bulk flow through the phloem, but is potentially too high to allow for sucrose diffusion from photosynthetic cells. Our findings support the Münch hypothesis for phloem transport once the carbon is in the phloem and challenge the passive-loading hypothesis for carbon movement into the phloem for red oak. This study provides the first ˜in-situ (frozen in the functioning state) source sieve element sucrose concentration characterization in any plant, opening a new avenue for investigation of phloem functioning., (© 2021 The Authors. New Phytologist © 2021 New Phytologist Foundation.)

We describe the coupled straintronic-photothermic effect where coupling between bandgap of the 2D layered semiconductor under localized strains, optical absorption and the photo-thermal effect results in a large chromatic mechanical response in TMD-nanocomposites. Under the irradiation of visible light (405 nm to 808 nm), such locally strained atomic thin films based on 2H-MoS 2 embedded in an elastomer such as poly (dimethyl) siloxane matrix exhibited a large amplitude of photo-thermal actuation compared to their unstrained counterparts. Moreover, the locally strain engineered nanocomposites showed tunable mechanical response giving rise to higher mechanical stress at lower photon energies. Scanning photoluminescence spectroscopy revealed a change in bandgap of 30 meV between regions encompassing highly strained compared to the unstrained few layers. For 1.6% change in the bandgap, the macroscopic photo-thermal response increased by a factor of two. Millimeter scale bending actuators based on the locally strained 2H-MoS 2 resulted in significantly enhanced photo-thermal actuation displacements compared to their unstrained counterparts at lower photon energies and operated up to 30 Hz. Almost 1 mN photo-activated force was obtained at 50 mW and provided long-term stability. This study demonstrates a new mechanism in TMD-nanocomposites that would be useful for developing broad range of transducers.

Asphaltenes are an important class of compounds in crude oil whose surface activity is important for establishing reservoir rock wettability which impacts reservoir drainage. While many phenomenological interfacial studies with crude oils and asphaltenes have been reported, there is very little known about the molecular level interactions between asphaltenes and mineral surfaces. In this study, we analyze Langmuir-Blodgett films of asphaltenes and related model compounds with sum frequency generation (SFG) vibrational spectroscopy. In SFG, the polarization of the input (vis, IR) and output (SFG) beams can be varied, which allows the orientation of different functional groups at the interface to be determined. SFG clearly indicates that asphaltene polycyclic aromatic hydrocarbons (PAHs) are highly oriented in the plane of the interface and that the peripheral alkanes are transverse to the interface. In contrast, model compounds with oxygen functionality have PAHs oriented transverse to the interface. Computational quantum chemistry is used to support corresponding band assignments, enabling robust determination of functional group orientations.

Polymer surface properties are controlled by the molecular surface structures. Sum frequency generation (SFG) vibrational spectroscopy has been demonstrated to be a powerful technique to study polymer surface structures at the molecular level in different chemical environments. In this research, SFG has been used to study the surface segregation of biocide moieties derived from triclosan (TCS) and tetradecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride (C-14 QAS) that have been covalently bound to a poly(dimethylsiloxane) (PDMS) matrix. PDMS materials are being developed as coatings to control biofouling. This SFG study indicated that TCS-moieties segregate to the surface when the bulk concentration of TCS-moieties exceeds 8.75% by weight. Surface segregation of C-14 QAS moieties was detected after 5% by weight incorporation into a PDMS matrix. SFG results were found to correlate well with antifouling activity, providing a molecular interpretation of such results. This research showed that SFG can aid in the development of coatings for controlling biofouling by elucidating the chemical structure of the coating surface.

Time-resolved second-harmonic generation (SHG) was used to study the hot-carrier dynamics and nonlinear optical properties of S-terminated and Cl-terminated Ge(111) interfaces on the femtosecond time scale. The hot-carrier second-order nonlinear optical susceptibilities were determined to be 720 +/- 50 times greater than the valence-band second-order nonlinear optical susceptibilities for the Ge(111)-S system and 880 +/- 100 times greater in the Ge(111)-Cl system. Furthermore, the ground- and excited-state second-order nonlinear optical susceptibilities are suggested to be out of phase for Ge(111)-S and Ge(111)-Cl systems, leading to a pump-induced decrease in the SHG signal as opposed to the increase in the SHG signal observed in the Ge(111)-GeO2 system. Although the SHG response reaches a steady state in 415 +/- 90 fs in the Ge(111)-GeO2 system, a faster response is observed in the Ge(111)-S system, 220 +/- 85 fs, and in the Ge(111)-Cl system, 172 +/- 50 fs. This suggests significantly faster carrier cooling at the Ge(111)-Cl and Ge(111)-S interfaces, with significant implications for hot-carrier mediated device degradation, and migration to high-K dielectrics.