Abstract The interfaces within bones, teeth and other hybrid biomaterials are of paramount importance but remain particularly difficult to characterize at the molecular level because both sensitive selective techniques mandatory. Here, it is demonstrated that unprecedented insights into calcium environments, for example differentiation surface core species hydroxyapatite nanoparticles, can be obtained using solid-state NMR, when combined with dynamic nuclear polarization. Although represents...

While calcium oxalate monohydrate (whewellite: CaC2O4·H2O) kidney stones are related to hyperoxaluria, dihydrate (weddellite: CaC2O4·(2 + x)H2O) ones mainly associated with hypercalciuria. Crystalline conversion from weddellite whewellite introduces a contradiction between Fourier transform infrared (FTIR) spectra which indicate the presence of and fact that bipyramid crystallites, morphology specific weddellite, can be observed. It constitutes thus major problem for clinicians as...

While ball-milling is becoming one of the common tools used by synthetic chemists, an increasing number studies highlight that it possible to further expand nature and products which can be synthesized, heating reaction media during mechanochemical reactions. Hence, developing set-ups enabling milling combined important target, has been looked into in both academic industrial laboratories. Here, we report a new approach for up reactions, using induction (referred as i-BM). Our set-up...

IIn this contribution, we apply our newly developed ball-milling operando platform, which combines Raman spectroscopy, thermal (IR) imaging, as well acoustic and high-speed optical video recordings, to the synthesis transformation of citric acid – isonicotinamide (1 : 2) cocrystal polymorphs in transparent PMMA jars. Particularly, demonstrate how Raman, temperature, data are complementary enable detect connect together chemical physical events happening during a time-resolved manner....

In this contribution, we apply our newly developed ball-milling operando platform, which combines Raman spectroscopy and thermal (IR) imaging, as well acoustic high-speed optical video recordings, to the synthesis transformation of citric acid–isonicotinamide (1:2) cocrystal polymorphs in transparent PMMA jars. Particularly, demonstrate how Raman, temperature, acoustic, data are complementary enable detection connection chemical physical events happening during a time-resolved manner....

The effect of mixing calcium and oxalate precursors by diffusion at miscible liquid interfaces on CaOx crystalline phases is studied using a microfluidic channel.

Abstract The vibrational signatures of the calcium oxalate polyhydrates are investigated using a combination Density Functional Theory‐Dispersion corrected, Fourier Transform‐ Raman and ‐Infrared (IR) spectroscopies. Most bands were assigned theoretical predictions compared with in‐house other experimental data, for both, IR Such an approach allowed more accurate analysis spectra helping in completion band assignments mono, di, tri hydrate (COM, COD, COT). Particular attention has been paid...

We report a multifaceted experimental and computational study of three self-complementary chalcogen-bond donors as well series seven chalcogen bonded cocrystals.

Alumina and aluminosilicates, prepared under various synthesis conditions, play a central role in heterogeneous catalysis with broad range of industrial applications. We report herein the atomic-scale structure alumina layers obtained by atomic layer deposition (ALD) trimethylaluminum onto partially dehydroxylated silica. Such detailed insight into species formed increasing Al content was gained using variety one- two-dimensional solid-state nuclear magnetic resonance (NMR) experiments...

Oxalate ligands are found in many classes of materials, including energy storage materials and biominerals. Determining their local environments at the atomic scale is thus paramount to establishing structure properties numerous phases. Here, we show that high-resolution 17O solid-state NMR a valuable asset for investigating crystalline oxalate systems. First, an efficient 17O-enrichment procedure demonstrated using mechanochemistry. Then, 17O-enriched oxalates were used synthesis...

Pnictogen (or pnicogen) bonding is an attractive interaction between the electrophilic region of group 15 elements (N, P, As, Sb, Bi) and a nucleophile. This for which unique applications in catalysis have recently been uncovered continues to gain popularity. Here, we investigate series pnictogen-bonded cocrystals based on SbF3 SbCl3, prepared via mechanochemical ball milling, with 121/123Sb ( I = 5/2 7/2, respectively) nuclear quadrupole resonance (NQR) spectroscopy. Observed NQR frequency...

The SbF3·4,4′-dipyridyl N,N′-dioxide cocrystal is prepared and characterized via infrared spectroscopy 121Sb 123Sb nuclear quadrupole resonance. Single crystal X-ray analysis proves that a major role in formation played by Sb···O pnictogen bonds, the attractive interactions wherein antimony oxygen act as electrophilic nucleophilic sites, respectively. Molecular electrostatic potential natural bond orbital analyses confirm relevance of this interaction self-assembly process. Dipyridyl dioxide...

Benzylic selenocyanates are versatile anion receptors which operate in solution and the solid state <italic>via</italic> chalcogen bonding interactions.

The description of the formation, structure, and reactivity coordination networks metal-organic frameworks (MOFs) remains a real challenge in number cases. This is notably true for compounds composed Zn2+ ions terephthalate ligands (benzene-1,4-dicarboxylate, BDC) because difficulties isolating them as pure phases and/or presence structural defects. Here, using mechanochemistry combination with operando Raman spectroscopy, observation formation various zinc was rendered possible, allowing...

Oxalate ligands are found in many classes of materials, including energy-storage materials and biominerals like hydrated calcium-oxalates. Determining their local environments at the atomic scale is thus paramount to establishing structure properties numerous phases. Here, we show that high-resolution 17O solid-state NMR a valuable asset for investigating crystalline oxalate systems. First, an efficient 17O-enrichment procedure demonstrated using mechanochemical saponification. Then, use...

We demonstrate that NMR/DNP (Dynamic Nuclear Polarization) allows an unprecedented description of carbonate substituted hydroxyapatite (CHAp). Key structural questions related to order/disorder and clustering carbonates are tackled using distance sensitive DNP experiments 13C–13C recoupling. Such easily implemented due gain (orders magnitude). is efficiently mediated by quasi one-dimensional spin diffusion through the hydroxyl columns present in CHAp structure (thought as "highways" for...

We present a new operando approach for following reactions taking place in mechanochemistry, relying on the analysis of evolution sound during milling.

Abstract. Pseudocontact shifts (PCSs) generated by paramagnetic lanthanide ions provide valuable long-range structural information in nuclear magnetic resonance (NMR) spectroscopic analyses of biological macromolecules such as proteins, but labelling proteins site-specifically with a single ion remains an ongoing challenge, especially for that are not suitable ligation cysteine-reactive complexes. We show specific lanthanide-binding site can be installed on incorporation phosphoserine...

Oxalate ligands are found in many classes of materials, including energy-storage materials and biominerals like hydrated calcium-oxalates. Determining their local environments at the atomic scale is thus paramount to establishing structure properties numerous phases. Here, we show that high-resolution 17O solid-state NMR a valuable asset for investigating crystalline oxalate systems. First, an efficient 17O-enrichment procedure demonstrated using mechanochemical saponification. Then, use...

CaO-based sorbents are cost-efficient materials for high-temperature CO2 capture, yet they rapidly deactivate over carbonation-regeneration cycles due to sintering, hindering their utilization at the industrial scale. Morphological stabilizers such as Al2O3 or SiO2 (e.g., introduced via impregnation) can improve sintering resistance, but still through formation of mixed oxide phases and phase segregation, rendering stabilization inefficient. Here, we introduce a strategy mitigate these...

Abstract A series of fumarate‐based organocobalt(I) [CoCp(CO)(fumarate)] catalysts is synthesized and characterized by X‐ray crystallography, multinuclear ( 13 C 59 Co) solid‐state NMR spectroscopy, Co NQR spectroscopy. Given the dearth studies on I compounds, present work constitutes first systematic characterization electric field gradient chemical shift tensors for a cobalt complexes in this oxidation state. Using molecular geometry about centre found to be nearly identical all compounds...

Beryllium-9 ( 9 Be) quadrupolar coupling and chemical shift tensor data are reported for bis(1-(2,6-diisopropylphenyl)-3,3,5,5-tetramethylpyrrolidine-2-ylidene)beryllium (Be(CAAC) 2 ). These the first such beryllium in a linear dicoordinate environment. The Be constant, 2.36(0.02) MHz, is largest recorded solid state to date this isotope. span of tensor, 22(2) ppm, covers about half known range, isotropic shift, 32.0(0.3) our knowledge. DFT calculations reproduce experimental well. A natural...

Abstract Biological apatites (main constituent of natural bones) correspond to non‐stoichiometric hydroxyapatite HAp, presenting a large variety ions as substituents (CO 3 2− , F − SiO 4 4− Mg 2+ Na + …). The precise location and configuration ionic substitutes in the HAp matrix are generally difficult identify characterize. This contribution details structural characterization based on NMR data particular case substitution by carbonates. For this purpose, all mechanisms proposed our...