Non-Invasive Raman Classification Comparison with pXRF of Monochrome and Related Qing Porcelains: Lead-Rich-, Lead-Poor-, and Alkali-Based Glazes.

Chinese porcelain with an optically clear colored glaze, imported to Europe from the Kangxi period (1662-1722, Qing Dynasty) onwards was highly collected by the French Elite of the 18th century. The bright colors with a clear, shiny glaze were unlike anything produced in Europe at that time. The colors of enamelled artifacts (on biscuits or already glazed porcelain) can be fully monochrome or consist of associations of large monochromatic areas with or without application of gilding.

Human-induced metals accumulation in sediments of an industrialized bay of northern Chile. An enrichment and ecological risk assessment based on preindustrial values.

Environmental assessment in marine systems is difficult because most of the time their preindustrial characteristics are not available. Four sediment cores taken in Mejillones bay (northern Chile) were used to establish preindustrial metals concentrations, and to assess the environmental status of this industrialized zone. According to historical documents, the beginning of the industrial era start in 1850 CE.

Quantum tailoring of electronic properties in covalently functionalized graphene: application to ammonia gas detection.

Functionalized graphene offers great potential in the field of rapid detection of gases at room temperature. We performed first-principles calculations to study the suitability of 4-sulfobenzenediazonium salts (4SBD) as bandgap modifier in graphene. The signature of unpaired spins is evidenced near the Fermi level owing to the symmetry breaking of graphene sublattices.

DFT exchange: sharing perspectives on the workhorse of quantum chemistry and materials science.

In this paper, the history, present status, and future of density-functional theory (DFT) is informally reviewed and discussed by 70 workers in the field, including molecular scientists, materials scientists, method developers and practitioners. The format of the paper is that of a roundtable discussion, in which the participants express and exchange views on DFT in the form of 302 individual contributions, formulated as responses to a preset list of 26 questions. Supported by a bibliography of 777 entries, the paper represents a broad snapshot of DFT, anno 2022.

Ferrocifen stealth LNCs and conventional chemotherapy: A promising combination against multidrug-resistant ovarian adenocarcinoma.

Ovarian cancer is one of the deadliest epithelial malignancies in women, owing to the multidrug resistance that restricts the success of conventional chemotherapy, carboplatin and paclitaxel. High grade serous ovarian carcinoma can be classified into two subtypes, the chemosensitive High OXPHOS and the Low OXPHOS tumour, less sensitive to chemotherapy. This difference of treatment efficacy could be explained by the redox status of these tumours, High OXPHOS exhibiting a chronic oxidative stress and an accumulation of reactive oxygen species.

Quantitative Comparison of the Light-to-Heat Conversion Efficiency in Nanomaterials Suitable for Photothermal Therapy.

Functional colloidal nanoparticles capable of converting between various energy types are finding an increasing number of applications. One of the relevant examples concerns light-to-heat-converting colloidal nanoparticles that may be useful for localized photothermal therapy of cancers. Unfortunately, quantitative comparison and ranking of nanoheaters are not straightforward as materials of different compositions and structures have different photophysical and chemical properties and may interact differently with the biological environment.

Heterogeneity of Response to Iron-Based Metallodrugs in Glioblastoma Is Associated with Differences in Chemical Structures and Driven by FAS Expression Dynamics and Transcriptomic Subtypes.

Glioblastoma (GBM) is the most frequent and deadliest primary brain cancer in adults, justifying the search for new treatments. Some members of the iron-based ferrocifen family have demonstrated a high cytotoxic effect on various cancer cell lines via innovative mechanisms of action. Here, we evaluated the antiproliferative activity by wst-1 assay of six ferrocifens in 15 molecularly diverse GBM patient-derived cell lines (PDCLs).

Metal-Free Deoxygenation of Amine N-Oxides: Synthetic and Mechanistic Studies.

We report herein an unprecedented combination of light and P(III)/P(V) redox cycling for the efficient deoxygenation of aromatic amine N-oxides. Moreover, we discovered that a large variety of aliphatic amine N-oxides can easily be deoxygenated by using only phenylsilane. These practically simple approaches proceed well under metal-free conditions, tolerate many functionalities and are highly chemoselective.

Experimental measurement of local high temperature at the surface of gold nanorods using doped ZnGaO as a nanothermometer.

Heat measurement induced by photoexcitation of a plasmonic metal nanoparticle assembly under environmental conditions is of primary importance for the further development of applications in the fields of (photo)catalysis, nanoelectronics and nanomedicine. Nevertheless, the fine control of the rise in temperature remains difficult and limits the use of this technology due to the lack of local temperature measurement tools working under environmental conditions. Luminescence nanothermometers are an alternative solution to the limitations of conventional contact thermometers since they are able to give an absolute temperature value with high spatial resolution using common optical equipment.

PEAI-Based Interfacial Layer for High-Efficiency and Stable Solar Cells Based on a MACl-Mediated Grown FAMAPbI Perovskite.

Among the three-dimensional (3D) organic-inorganic hybrid perovskites (OIHPs), mixed formamidinium and methylammonium cation lead iodide is one of the most promising for solar cell application. After optimizing the use of a methylammonium chloride (MACl) additive for the preparation of compact, high-quality, and large crystal grain layers made of a pure α-phase perovskite with the FAMAPbI composition, the treatment of the perovskite surface by a 2-phenylethylammonium iodide (PEAI) solution has been performed. This treatment, without any thermal annealing, leads notably to the spontaneous formation of a crystallized (PEA)PbI two-dimensional (2D) perovskite nanolayer at the film surface due to partial organic cation dissolution.

Author Correction: Diffraction-limited ultrabroadband terahertz spectroscopy.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

A Comparative Investigation of the Role of the Anchoring Group on Perylene Monoimide Dyes in NiO-Based Dye-Sensitized Solar Cells.

The anchoring group of a sensitizer may strongly affect the overall properties and stability of the resulting dye-sensitized solar cells (DSSCs) and dye-sensitized photoelectrosynthetic solar cells (DSPECs). The properties of seven perylene monoimide (PMI) dyes have been comprehensively studied for their immobilization on nanocrystalline NiO film. The PMI dyes differ only by the nature of the anchoring group, which are: carboxylic acid (PMI-CO H), phosphonic acid (PMI-PO H ), acetyl acetone (PMI-acac), pyridine (PMI-Py), aniline (PMI-NH ), hydroxyquinoline (PMI-HQ), and dipicolinic acid (PMI-DPA).

Enhanced Stability and Band Gap Tuning of α-[HC(NH)]PbI Hybrid Perovskite by Large Cation Integration.

We report room-temperature synthesis of lead- and iodide-deficient α-[HC(NH)]PbI perovskites (abbreviated d-α-FAPI, FA = formamidinium), with the general formula (A',FA)[PbI] (with A' = hydroxyethylammonium (HEA) or thioethylammonium (TEA) cations, 0.04 ≤ x ≤ 0.15).

The mechanism of cyclic electron flow.

Apart from the canonical light-driven linear electron flow (LEF) from water to CO, numerous regulatory and alternative electron transfer pathways exist in chloroplasts. One of them is the cyclic electron flow around Photosystem I (CEF), contributing to photoprotection of both Photosystem I and II (PSI, PSII) and supplying extra ATP to fix atmospheric carbon. Nonetheless, CEF remains an enigma in the field of functional photosynthesis as we lack understanding of its pathway.

Maximal cyclic electron flow rate is independent of PGRL1 in Chlamydomonas.

Cyclic electron flow (CEF) is defined as a return of the reductants from the acceptor side of Photosystem I (PSI) to the pool of its donors via the cytochrome bf. It is described to be complementary to the linear electron flow and essential for photosynthesis. However, despite many efforts aimed to characterize CEF, its pathway and its regulation modes remain equivocal, and its physiological significance is still not clear.

Relevance of treated cocaine users' retrospective memory of first cocaine use.

Little is known regarding between-subject variability in the subjective effects of first cocaine use. This study retrospectively assesses the subjective effects of first cocaine use in 160 current treatment-seeking cocaine use disorder patients. Subjective effects of first cocaine use were evaluated with an ad-hoc questionnaire used for cannabis effects.

Characterization of CyrI, the hydroxylase involved in the last step of cylindrospermopsin biosynthesis: Binding studies, site-directed mutagenesis and stereoselectivity.

Cylindrospermopsin, a cytotoxin from cyanobacteria, is biosynthesized by a complex pathway, which involves CyrI, an iron and 2-oxoglutarate dependent hydroxylase that transforms 7-deoxy-cylindrospermopsin into cylindrospermopsin and its epimer, 7-epi-cylindrospermopsin, in the last step. The activity of CyrI from Oscillatoria sp. PCC 7926 depends on Fe(II) (K = 2.

Site-isolated manganese carbonyl on bipyridine-functionalities of periodic mesoporous organosilicas: efficient CO photoreduction and detection of key reaction intermediates.

Well-defined and fully characterized supported CO reduction catalysts are developed through the immobilization of an earth abundant Mn complex on (bpy = bipyridine; PMO = Periodic Mesoporous Organosilica) platform materials. The resulting isolated Mn-carbonyl centers coordinated to bipyridine functionalities of catalyze the photoreduction of CO into CO and HCOOH with up to 720 TON in the presence of BIH (1,3-dimethyl-2-phenyl-2,3-dihydro-1-benzoimidazole), used as the electron donor. A broad range of photochemical conditions (varying solvents, sacrificial electron donors, photosensitizer type and concentration, catalyst loading as well as the Mn loading within the PMO) are investigated, demonstrating high activity even for simple organic dyes and Zn-porphyrin as photosensitizers.

Co-Binding of Pharmaceutical Compounds at Mineral Surfaces: Molecular Investigations of Dimer Formation at Goethite/Water Interfaces.

The emergence of antibiotic and anti-inflammatory agents in aquatic and terrestrial systems is becoming a serious threat to human and animal health worldwide. Because pharmaceutical compounds rarely exist individually in nature, interactions between various compounds can have unforeseen effects on their binding to mineral surfaces. This work demonstrates this important possibility for the case of two typical antibiotic and anti-inflammatory agents (nalidixic acid (NA) and niflumic acid (NFA)) bound at goethite (α-FeOOH) used as a model mineral surface.

Ruthenium-cobalt dinuclear complexes as photocatalysts for CO reduction.

A series of Ru-Co dinuclear complexes have been synthesized and assayed as photocatalysts for the reduction of CO to CO in organic solvents. The Ru-Co complexes, with tris-diimine coordination at the Co ion, are the best supramolecular photocatalysts for CO reduction with a non-noble metal catalytic center reported so far.

Efficient ferrocifen anticancer drug and Bcl-2 gene therapy using lipid nanocapsules on human melanoma xenograft in mouse.

Metastatic melanoma has been described as a highly aggressive cancer with low sensibility to chemotherapeutic agents. New types of drug, such as metal-based drugs (ferrocifens) have emerged and could represent an alternative for melanoma treatment since they show interesting anticancer potential. Furthermore, molecular analysis has evidenced the role of apoptosis in the low sensibility of melanomas and especially of the key regulator, Bcl-2.

Unveiling the Reactivity of a Synthetic Mimic of the Oxygen Evolving Complex.

We simulated for the first time the oxygen-oxygen bond formation in a synthetic calcium-tetra manganese complex recently developed by Zhang and co-workers. In spite of promising structural similarities to the native oxygen evolving complex (OEC) in Photosystem II, several uncertainties on the mimic stability in water and on its potential catalytic activity still persist. Here, we characterized at density functional theory level the electronic and structural features of the S states of the complex, along with the oxygen-oxygen bond formation reaction, proposing a reasonable model for the hydrate complex.

Chromosomes of Protists: The crucible of evolution.

As early as 1925, the great protozoologist Edouard Chatton classified microorganisms into two categories, the prokaryotic and the eukaryotic microbes, based on light microscopical observation of their nuclear organization. Now, by means of transmission electron microscopy, we know that prokaryotic microbes are characterized by the absence of nuclear envelope surrounding the bacterial chromosome, which is more or less condensed and whose chromatin is deprived of histone proteins but presents specific basic proteins. Eukaryotic microbes, the protists, have nuclei surrounded by a nuclear envelope and have chromosomes more or less condensed, with chromatin-containing histone proteins organized into nucleosomes.