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The difficulty in the prediction of the complicated solid-state structure of boronic acid derivatives, resulting from the complex pathway of reversible covalent interactions, represents a significant obstacle to the development of a new generation of advanced supramolecular systems such as covalent organic frameworks of efficient anticancer drugs. In this contribution, various 2D 11B–11B solid-state NMR correlation techniques supported by DFT calculations were explored to formulate a reliable tool for monitoring the covalent assembly of boronic acid residues in the solid state. This way, the self-condensation of bortezomib molecules was investigated, different local constitutions of boroxine motifs were unveiled, and the previously unreported boroxine structures of bortezomib polymorphs exhibiting secondary coordination were discovered and described in detail. The recorded 11B NMR parameters responded sensitively to subtle changes in the local geometries, which were reliably interpreted and directly visualized by the DFT calculations. A uniform 2.6 Å distance in bortezomib 11B–11B spin pairs was conclusively identified by the through-space 11B–11B double-quantum (DQ) coherence build-up curves, whereas distinct 2D 11B–11B DQ correlation patterns revealed unique boroxine structures existing in the crystalline as well as amorphous state. The boroxine rings were found to be internally stabilized through the transformation of the trigonal boron sites toward tetrahedral geometry, as the secondary five-membered rings were formed. This way, the nature of bortezomib polymorphism is disclosed, and an efficient strategy for exploring the assembly of boronic acid derivatives in the solid state, for which no crystallographic data are available, is thus demonstrated. [ABSTRACT FROM AUTHOR]

7Li–7Li correlation MAS NMR spectroscopy, interpreted using periodic DFT including molecular dynamics conformational sampling of Li+ sites, is employed to obtain the siting of Li+ at exchangeable positions of ferrierites and the local structure of these Li+ sites. The former is controlled by the Al siting in the zeolite framework. [ABSTRACT FROM AUTHOR]

Lead-free halide double perovskite (HDP) Cs 2 AgBiBr 6 has set a benchmark for research in HDP photoelectric applications due to its attractive optoelectronic properties. However, its narrow absorption range is a key limitation of this material. Herein, a novel dopant, palladium (Pd), is doped into Cs 2 AgBiBr 6 and significantly extends the absorption to ≈1400 nm. Pd 2+ ions are partially doped in the host lattice, most probably replacing Ag atoms and introducing a sub-bandgap state within the host bandgap, as indicated by the combination of spectroscopical measurements and theoretical calculations. Importantly, this sub-bandgap state extends the photoresponse of Cs 2 AgBiBr 6 up to the NIR-II region of 1300 nm, setting a new record for HDPs. This work demonstrates a novel and efficient dopant for HDPs and highlights the effectiveness of employing a sub-bandgap to broaden the absorption of HDPs, shedding new light on tailoring large bandgap HDPs for NIR optoelectronic applications., (© 2024 The Author(s). Small published by Wiley‐VCH GmbH.)

This study develops and characterizes novel biodegradable soft hydrogels with dual porosity based on N-(2-hydroxypropyl)methacrylamide (HPMA) copolymers cross-linked by hydrolytically degradable linkers. The structure and properties of the hydrogels are designed as scaffolds for tissue engineering and they are tested in vitro with model mesenchymal stem cells (rMSCs). Detailed morphological characterization confirms dual porosity suitable for cell growth and nutrient transport. The dual porosity of hydrogels slightly improves rMSCs proliferation compared to the hydrogel with uniform pores. In addition, the laminin coating supports the adhesion of rMSCs to the hydrogel surface. However, hydrogels modified by heptapeptide RGDSGGY significantly stimulate cell adhesion and growth. Moreover, the RGDS-modified hydrogels also affect the topology of proliferating rMSCs, ranging from single-cell to multicellular clusters. The 3D reconstruction of the hydrogels with cells obtained by laser scanning confocal microscopy (LSCM) confirms cell penetration into the inner structure of the hydrogel and its corresponding microstructure. The prepared biodegradable oligopeptide-modified hydrogels with dual porosity are suitable candidates for further in vivo evaluation in soft tissue regeneration., (© 2023 The Authors. Macromolecular Bioscience published by Wiley-VCH GmbH.)

Porous aluminosilicates are functional materials of paramount importance as Lewis acid catalysts in the synthetic industry, yet the participating aluminum species remain poorly studied. Herein, a series of model aluminosilicate networks containing [L-AlO 3 ] (L = THF, Et 3 N, pyridine, triethylphosphine oxide (TEPO)) and [AlO 4 ] - centers were prepared through nonhydrolytic sol-gel condensation reactions of the spherosilicate building block (Me 3 Sn) 8 Si 8 O 20 with L-AlX 3 (X = Cl, Me, Et) and [Me 4 N] [AlCl 4 ] compounds in THF or toluene. The substoichiometric dosage of the Al precursors ensured complete condensation and uniform incorporation, with the bulky spherosilicate forcing a separation between neighboring aluminum centers. The materials were characterized by 1 H, 13 C, 27 Al, 29 Si, and 31 P MAS NMR and FTIR spectroscopies, ICP-OES, gravimetry, and N 2 adsorption porosimetry. The resulting aluminum centers were resolved by 27 Al TQ/MAS NMR techniques and assigned based on their spectroscopic parameters obtained by peak fitting (δ iso , C Q , η) and their correspondence to the values calculated on model structures by DFT methods. A clear correlation between the decrease in the symmetry of the Al centers and the increase of the observed C Q was established with values spanning from 4.4 MHz for distorted [AlO 4 ] - to 15.1 MHz for [THF-AlO 3 ]. Products containing exclusively [TEPO-AlO 3 centers could be obtained (single-site materials). For L = THF, Et 4 ] - centers could be obtained (single-site materials). For L = THF, Et 3 centers were formed together with the expected [L-AlO 4 ] - centers were formed together with the expected [L-AlO 3 ] species, and a viable mechanism for the unexpected emergence of [AlO 4 ] - was proposed.

Recently, suitably sized polymer-based nanogels containing functional groups for the binding of biologically active substances and ultimately degradable to products that can be removed by glomerular filtration have become extensively studied systems in the field of drug delivery. Herein, we designed and tailored the synthesis of hydrophilic and biodegradable poly[ N -(2-hydroxypropyl) methacrylamide-co- N , N '-bis(acryloyl) cystamine- co- 6-methacrylamidohexanoyl hydrazine] (PHPMA-BAC-BMH) nanogels. The facile and versatile dispersion polymerization enabled the preparation of nanogels with a diameter below 50 nm, which is the key parameter for efficient and selective passive tumor targeting. The effects of the N , N '-bis(acryloyl) cystamine crosslinker, polymerization composition, and medium including H 2 O/MetCel and H 2 O/EtCel on the particle size, particle size distribution, morphology, and polymerization kinetics and copolymer composition were investigated in detail. We demonstrated the formation of a 38 nm colloidally stable PHPMA-BAC-BMH nanogel with a core-shell structure that can be rapidly degraded in the presence of 10 mM glutathione solution under physiologic conditions. The nanogels were stable in an aqueous solution modeling the bloodstream; thus, these nanogels have the potential to become highly important carriers in the drug delivery of various molecules.

Bandgap tunability of lead mixed halide perovskites (LMHPs) is a crucial characteristic for versatile optoelectronic applications. Nevertheless, LMHPs show the formation of iodide-rich (I-rich) phase under illumination, which destabilizes the semiconductor bandgap and impedes their exploitation. Here, it is shown that how I 2 , photogenerated upon charge carrier trapping at iodine interstitials in LMHPs, can promote the formation of I-rich phase. I 2 can react with bromide (Br - ) in the perovskite to form a trihalide ion I 2 Br - (I δ- -I δ+ -Br δ- ), whose negatively charged iodide (I δ- ) can further exchange with another lattice Br - to form the I-rich phase. Importantly, it is observed that the effectiveness of the process is dependent on the overall stability of the crystalline perovskite structure. Therefore, the bandgap instability in LMHPs is governed by two factors, i.e., the density of native defects leading to I 2 production and the Br - binding strength within the crystalline unit. Eventually, this study provides rules for the design of chemical composition in LMHPs to reach their full potential for optoelectronic devices., (© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Borane cluster-based porous covalent networks, named activated borane ( ActB ), were prepared by cothermolysis of decaborane(14) ( nido -B 10 H 14 ) and selected hydrocarbons (toluene, ActB-Tol; cyclohexane, ActB- cy Hx ; and n -hexane, ActB- n Hx ) under anaerobic conditions. These amorphous solid powders exhibit different textural and Lewis acid (LA) properties that vary depending on the nature of the constituent organic linker. For ActB-Tol , its LA strength even approaches that of the commonly used molecular LA, B(C 6 F 5 ) 3 . Most notably, ActB s can act as heterogeneous LA catalysts in hydrosilylation/deoxygenation reactions with various carbonyl substrates as well as in the gas-phase dehydration of ethanol. These studies reveal the potential of ActB s in catalytic applications, showing (a) the possibility for tuning catalytic reaction outcomes (selectivity) in hydrosilylation/deoxygenation reactions by changing the material's composition and (b) the very high activity toward ethanol dehydration that exceeds the commonly used γ-Al 2 O 3 by achieving a stable conversion of ∼93% with a selectivity for ethylene production of ∼78% during a 17 h continuous period on stream at 240 °C., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

It has been recognized that the C-H⋯O structural motif can be present in destabilizing as well as highly stabilizing intermolecular environments. Thus, it should be of interest to describe the strength of the C-H⋯O hydrogen bond for constant structural factors so that this intrinsic strength can be quantified and compared to other types of interactions. This description is provided here for C 2 h -symmetric dimers of acrylic acid by means of the calculations that employ the coupled-cluster theory with singles, doubles, and perturbative triples [CCSD(T)] together with an extrapolation to the complete basis set (CBS) limit. Dimers featuring the C-H⋯O and O-H⋯O hydrogens bonds are carefully investigated in a wide range of intermolecular separations by the CCSD(T)/CBS approach, and also by the symmetry-adapted perturbation theory (SAPT) method, which is based on the density-functional theory (DFT) treatment of monomers. While the nature of these two types of hydrogen bonding is very similar according to the SAPT-DFT/CBS calculations and on the basis of a comparison of the intermolecular potential curves, the intrinsic strength of the C-H⋯O interaction is found to be about a quarter of its O-H⋯O counterpart that is less than one might anticipate.

Composites of polyaniline (PANI) and Zr-based metal-organic frameworks (MOFs), UiO-66 and UiO-66-NH 2 , were synthesized by the oxidative polymerization of aniline in the presence of MOF templates with the MOF content in the resulting materials (78.2 and 86.7 wt %, respectively) close to the theoretical value (91.5 wt %). Scanning electron microscopy and transmission electron microscopy showed that the morphology of the composites was set by the morphology of the MOFs, whose structure was mostly preserved after the synthesis, based on the X-ray diffraction data. Vibrational and NMR spectroscopies pointed out that MOFs participate in the protonation of PANI and conducting polymer chains were grafted to amino groups of UiO-66-NH 2 . Unlike PANI-UiO-66, cyclic voltammograms of PANI-UiO-66-NH 2 showed a well-resolved redox peak at around ≈0 V, pointing at the pseudocapacitive behavior. The gravimetric capacitance of PANI-UiO-66-NH 2 , normalized per mass of the active material, was also found to be higher compared to that of pristine PANI (79.8 and 50.5 F g -1 , respectively, at 5 mV s -1 ). The introduction of MOFs into the composites with PANI significantly improved the cycling stability of the materials over 1000 cycles compared to the pristine conducting polymer, with the residual gravimetric capacitance being ≥100 and 77%, respectively. Thus, the electrochemical performance of the prepared PANI-MOF composites makes them attractive materials for application in energy storage.

A new generation biomass-based filler for natural rubber, 'hydrochar' (HC), was obtained by hydrothermal carbonization of hardwood waste (sawdust). It was intended as a potential partial replacement for the traditional carbon black (CB) filler. The HC particles were found (TEM) to be much larger (and less regular) than CB: 0.5-3 µm vs. 30-60 nm, but the specific surface areas were relatively close to each other (HC: 21.4 m 2 /g vs. CB: 77.8 m 2 /g), indicating a considerable porosity of HC. The carbon content of HC was 71%, up from 46% in sawdust feed. FTIR and 13 C-NMR analyses indicated that HC preserved its organic character, but it strongly differs from both lignin and cellulose. Experimental rubber nanocomposites were prepared, in which the content of the combined fillers was set at 50 phr (31 wt.%), while the HC/CB ratios were varied between 40/10 and 0/50. Morphology investigations proved a fairly even distribution of HC and CB, as well as the disappearance of bubbles after vulcanization. Vulcanization rheology tests demonstrated that the HC filler does not hinder the process, but it significantly influences vulcanization chemistry, canceling scorch time on one hand and slowing down the reaction on the other. Generally, the results suggest that rubber composites in which 10-20 phr of CB are replaced by HC might be promising materials. The use of HC in the rubber industry would represent a high-tonnage application for hardwood waste.

The unprecedented co-thermolysis of decaborane(14) (nido-B 10 H 14 ) and toluene results in a novel porous material (that we have named "activated borane") containing micropores between 1.0 and 1.5 nm in diameter and a specific surface area of 774 m 2  g -1 (Ar, 87 K) that is thermally stable up to 1000 °C. Solid state 1 H, 11 B and 13 C MAS NMR, UV-vis and IR spectroscopies suggest an amorphous structure of borane clusters interconnected by toluene moieties in a ratio of about three toluene molecules for every borane cluster. In addition, the structure contains Lewis-acidic tri-coordinated boron sites giving it some unique properties. Activated borane displays high sorption capacity for pollutants such as sulfamethoxazole, tramadol, diclofenac and bisphenol A that exceed the capacity of commercially-available activated carbon. The consistency in properties for each batch made, and the ease of its synthesis, make activated borane a promising porous material worthy of broad attention., (© 2022 Wiley-VCH GmbH.)

Record power conversion efficiencies (PCEs) of perovskite solar cells (PSCs) have been obtained with the organic hole transporter 2,2',7,7'-tetrakis( N , N -di- p -methoxyphenyl-amine)9,9'-spirobifluorene (spiro-OMeTAD). Conventional doping of spiro-OMeTAD with hygroscopic lithium salts and volatile 4- tert -butylpyridine is a time-consuming process and also leads to poor device stability. We developed a new doping strategy for spiro-OMeTAD that avoids post-oxidation by using stable organic radicals as the dopant and ionic salts as the doping modulator (referred to as ion-modulated radical doping). We achieved PCEs of >25% and much-improved device stability under harsh conditions. The radicals provide hole polarons that instantly increase the conductivity and work function (WF), and ionic salts further modulate the WF by affecting the energetics of the hole polarons. This organic semiconductor doping strategy, which decouples conductivity and WF tunability, could inspire further optimization in other optoelectronic devices.

Radiation resistance of cancer cells represents one of the major challenges in cancer treatment. The novel self-assembled fluoralkylated diselenide nanoparticles (fluorosomes) based on seleno-l-cystine (17FSe 2 ) possess redox-active properties that autocatalytically decompose hydrogen peroxide (H 2 O 2 ) and oxidize the intracellular glutathione (GSH) that results in regulation of cellular oxidative stress. Alkylfluorinated diselenide nanoparticles showed a significant cytotoxic and radiosensitizing effect on cancer cells. The EL-4 tumor-bearing C56BL/6 mice treated with 17FSe 2 followed by fractionated radiation treatment (4 × 2Gy) completely suppressed tumor growth. Our results suggest that described diselenide system behaves as a potent radiosensitizer agent targeting tumor growth and preventing tumor recurrence., (Copyright © 2022 Elsevier Inc. All rights reserved.)

Framework Al FR Lewis sites represent a substantial portion of active sites in H-BEA zeolite catalysts activated at low temperatures. We studied their nature by 27 Al WURST-QCPMG nuclear magnetic resonance (NMR) and proposed a plausible mechanism of their formation based on periodic density functional theory calculations constrained by 1 H MAS, 27 Al WURST-QCPMG, and 29 Si MAS NMR experiments and FTIR measurements. Our results show that the electron-pair acceptor of Al FR Lewis sites corresponds to an Al TRI atom tricoordinated to the zeolite framework, which adsorbs a water molecule. This Al TRI -OH 2 complex is reflected in 27 Al NMR resonance with δ iso = 70 ± 5 ppm and C Q = 13 ± 2 MHz. In addition, the Al TRI atom with adsorbed acetonitrile-d 3 (the probe of Al FR Lewis sites in FTIR spectroscopy) exhibits a similar 27 Al NMR resonance. We suggest that these Al FR Lewis sites are formed from Al-OH-Si-O-Si-O-Si-OH-Al sequences located in 12-rings (i.e., close unpaired Al atoms).

Saponification, resulting from pigment-binder interactions, is one of the most endangering phenomena affecting the appearance and stability of painted works of art. The crystallization of metal carboxylates (soaps) in paint layers is recently assumed as the most critical point for the development of undesirable changes induced by saponification, however, the factors triggering it are not fully understood. The red pigment cinnabar (HgS) has been suspected of contributing to saponification, however, the paucity of reliable reference structural data limited the experimental research of its effect at the molecular level. Within this study we synthesized mercury(II) carboxylates of the formula Hg(C16) x (C18) 2- x ( x = 0.0; 0.2; 0.5; 0.8; 1.0; 1.2; 1.5; 1.8; 2.0) where C16 and C18 are hexadecanoate (palmitate) and octadecanoate (stearate), respectively, and characterize them by combination of X-ray powder diffraction (XRPD) and 13 C and 199 Hg solid state NMR (ssNMR). For a more detailed interpretation of their structural and thermal behavior, Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC) were used. The crystal structure of the studied mercury carboxylates was described on the basis of complementary ssNMR and XRPD measurements, Rietveld refinement and DFT calculations. All the subjected compounds crystallize in a monoclinic lattice of the C 2/ c symmetry. Mercury atoms are arranged in a slightly distorted square antiprismatic geometry and are monodentatically bonded to carboxylate anions. The structural disorder at the aliphatic end of the stearic acid chains was detected in the mixed carboxylates. Within the paper, the structural (dis)similarity with the corresponding lead carboxylates is discussed. The synthesized and characterized mercury carboxylates were applied to describe neo-formed mercury soaps in a model experiment simulating an egg-based paint system.

Bacterial infections and antimicrobial resistance are one of the major public health problems and various strategies to prevent potential threats have been developed. Protonated polymers were proven as efficient agents against several microbial pathogens. Poly[2-(dimethylamino)ethyl methacrylate] (PDMAEMA) linear polymer and its copolymers represent one example of functional materials which inhibit the growth of both harmful Gram-negative and Gram-positive bacteria. However, the antimicrobial effect of positively charged PDMAEMA particles has been never tested. In this report, we deeply studied several parameters of free-radical polymerization, including the effect of crosslinking monomer, medium composition, solvency and polarity, and type and concentration of initiator and stabilizer, to fabricate high-quality poly[2-(dimethylamino)ethyl methacrylate- co -ethylene dimethacrylate] (PDMAEMA-EDMA) nanogel. We successfully found that dispersion polymerization in water/2-methoxyethanol medium (80/20 w/w), initiated with 0.2 wt% potassium persulfate (KPS) and stabilized with 0.5 wt% poly(vinyl alcohol) (PVA), produced a well-defined and sub-micron 167 nm PDMAEMA-EDMA nanogel. Bactericidal activity of the quaternized PDMAEMA-EDMA nanogel was assessed via time-kill curve assay against two Gram-positive and Gram-negative pathogenic bacteria, namely Staphylococcus aureus ( S. aureus ) and Acinetobacter baumannii ( A. baumannii ). The results illustrated that the quaternized PDMAEMA-EDMA nanogel acted as an effective bactericidal agent against both tested bacteria., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Spikelets NMR spectra are very popular as they enable the shortening of experimental time and give the possibility to obtain required NMR parameters for nuclei with ultrawide NMR patterns. Unfortunately, these resulted ssNMR spectra cannot be fitted directly in common software. For this reason, we developed UWNMRSpectralShape (USS) software which transforms spikelets NMR patterns into single continuous lines. Subsequently, these reconstructed spectral envelopes of the (Q)CPMG spikelets patterns can be loaded into common NMR software and automatically fitted, independently of experimental settings. This allows the quadrupole and chemical shift parameters to be accurately determined. Moreover, it makes fitting of spikelets NMR spectra exact, fast and straightforward.

Molecular additives are widely utilized to minimize non-radiative recombination in metal halide perovskite emitters due to their passivation effects from chemical bonds with ionic defects. However, a general and puzzling observation that can hardly be rationalized by passivation alone is that most of the molecular additives enabling high-efficiency perovskite light-emitting diodes (PeLEDs) are chelating (multidentate) molecules, while their respective monodentate counterparts receive limited attention. Here, we reveal the largely ignored yet critical role of the chelate effect on governing crystallization dynamics of perovskite emitters and mitigating trap-mediated non-radiative losses. Specifically, we discover that the chelate effect enhances lead-additive coordination affinity, enabling the formation of thermodynamically stable intermediate phases and inhibiting halide coordination-driven perovskite nucleation. The retarded perovskite nucleation and crystal growth are key to high crystal quality and thus efficient electroluminescence. Our work elucidates the full effects of molecular additives on PeLEDs by uncovering the chelate effect as an important feature within perovskite crystallization. As such, we open new prospects for the rationalized screening of highly effective molecular additives., (© 2021. The Author(s).)

In situ 1 H NMR characterization of copolymerization reactions of various 2-oxazoline monomers at different molar ratios offers detailed insight into the build-up and composition of the polymer chains. Various 2-oxazolines were copolymerized in one single solvent, butyronitrile, with 2-dec-9'-enyl-2-oxazoline, where the double bond allows for post-polymerization modification and can function as a crosslinking unit to form polymer networks. The types of the monomers and their molar ratios in the feed have a strong effect on the microstructure of the forming copolymer chains. Copolymers comprising 2-dec-9'-enyl-2-oxazoline and either 2-ethyl-, 2-isopropyl-, 2-butyl-, 2-heptyl, 2-nonyl- or 2-phenyl-2-oxazoline, show significant differences in sequential structure of copolymers ranging from block to gradient and random ordering of the monomer units. 1 H NMR was found to be a powerful tool to uncover detailed oxazoline copolymerization kinetics and evolution of chain composition., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Although lead-free halide double perovskites are considered as promising alternatives to lead halide perovskites for optoelectronic applications, state-of-the-art double perovskites are limited by their large bandgap. The doping/alloying strategy, key to bandgap engineering in traditional semiconductors, has also been employed to tune the bandgap of halide double perovskites. However, this strategy has yet to generate new double perovskites with suitable bandgaps for practical applications, partially due to the lack of fundamental understanding of how the doping/alloying affects the atomic-level structure. Here, we take the benchmark double perovskite Cs 2 AgInCl 6 as an example to reveal the atomic-level structure of double perovskite alloys (DPAs) Cs 2 AgIn 1- x Fe x Cl 6 ( x = 0-1) by employing solid-state nuclear magnetic resonance (ssNMR). The presence of paramagnetic alloying ions ( e.g. Fe 3+ in this case) in double perovskites makes it possible to investigate the nuclear relaxation times, providing a straightforward approach to understand the distribution of paramagnetic alloying ions. Our results indicate that paramagnetic Fe 3+ replaces diamagnetic In 3+ in the Cs 2 AgInCl 6 lattice with the formation of [FeCl 6 ] 3- ·[AgCl 6 ] 5- domains, which show different sizes and distribution modes in different alloying ratios. This work provides new insights into the atomic-level structure of bandgap engineered DPAs, which is of critical significance in developing efficient optoelectronic/spintronic devices., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Spintronics holds great potential for next-generation high-speed and low-power consumption information technology. Recently, lead halide perovskites (LHPs), which have gained great success in optoelectronics, also show interesting magnetic properties. However, the spin-related properties in LHPs originate from the spin-orbit coupling of Pb, limiting further development of these materials in spintronics. Here, we demonstrate a new generation of halide perovskites, by alloying magnetic elements into optoelectronic double perovskites, which provide rich chemical and structural diversities to host different magnetic elements. In our iron-alloyed double perovskite, Cs 2 Ag(Bi:Fe)Br 6 , Fe 3+ replaces Bi 3+ and forms FeBr 6 clusters that homogenously distribute throughout the double perovskite crystals. We observe a strong temperature-dependent magnetic response at temperatures below 30 K, which is tentatively attributed to a weak ferromagnetic or antiferromagnetic response from localized regions. We anticipate that this work will stimulate future efforts in exploring this simple yet efficient approach to develop new spintronic materials based on lead-free double perovskites., (Copyright © 2020 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).)

The formation of a polycrystalline 3D gallium-imidazole framework (MOF) was closely studied in three steps using ssNMR, XRPD, and TGA. In all steps, the reaction products show relatively high temperature stability up to 500 °C. The final product was examined by structural analysis using NMR crystallography combined with TG and BET analyses, which enabled a detailed characterization of the polycrystalline MOF system on the atomic-resolution level. 71 Ga ssNMR spectra provided valuable structural information on the coexistence of several distinct gallium species, including a tunable liquid phase. Moreover, using an NMR crystallography approach, two structurally asymmetric units of Ga(Im 6 ) 6- incorporated into the thermally stable polycrystalline 3D matrix were identified. Prepared polycrystalline MOF material with polymorphic gallium species is promising for use in catalytic processes.

Lead carboxylates are an extensive group of compounds studied for their promising industrial applications and for their risky behavior when they are formed in oil paintings as corrosion products of lead-based pigments, leading to serious deterioration of paintings. Although the processes leading to the formation of aggregates, protrusions or inclusions, affecting undesirably the appearance of paintings, are assumed to be long term, neo-formed lead carboxylates are detectable in the early stage of paint drying. To uncover the chemical changes in lead pigments during the drying of oil paint films, model systems consisting of minium (Pb3O4) and four common drying oils were studied by X-ray powder diffraction (XRPD), 13C and 207Pb solid state NMR (ssNMR) spectroscopy and Fourier-transformed infrared spectroscopy (FTIR). For the first time, a degradation mechanism of Pb3O4via the crystallization of lead formate (Pb(HCOO)2), at the end of oxidative polymerization of oil paint films, was uncovered. The formation of formic acid in oils was proved by gas chromatography-mass spectrometry (GC-MS). Vapor experiments evidenced the susceptibility of Pb3O4 to react with volatile formic acid released during the autoxidation of oils comparably to the direct pigment-binder interactions in paint films. The investigation of the local environment of lead atoms in the paint film by 207Pb WURST-CPMG NMR spectroscopy showed that Pb(ii) atoms reacted with linseed oil preferentially to form highly crystalline Pb(HCOO)2, while the local chemical environment of Pb(iv) atoms did not change. The results proved the co-existence of (i) highly crystalline Pb(HCOO)2, (ii) a highly mobile amorphous phase corresponding to free carboxylic acids or a nascent lead soap phase and (iii) the remaining Pb3O4 in the polymeric/ionomeric network. Pb(HCOO)2 is assumed to be an intermediate for the conversion of Pb3O4 to lead soaps and/or lead carbonates.

Although perovskite light-emitting diodes (PeLEDs) have recently experienced significant progress, there are only scattered reports of PeLEDs with both high efficiency and long operational stability, calling for additional strategies to address this challenge. Here, we develop perovskite-molecule composite thin films for efficient and stable PeLEDs. The perovskite-molecule composite thin films consist of in-situ formed high-quality perovskite nanocrystals embedded in the electron-transport molecular matrix, which controls nucleation process of perovskites, leading to PeLEDs with a peak external quantum efficiency of 17.3% and half-lifetime of approximately 100 h. In addition, we find that the device degradation mechanism at high driving voltages is different from that at low driving voltages. This work provides an effective strategy and deep understanding for achieving efficient and stable PeLEDs from both material and device perspectives.

Long-chain lead carboxylates, on the one hand, represent compounds for versatile industrial applications in high-tech industries, while on the other hand, they are predominant constituents of secondary products of saponification of paint layers in works of art. Affecting significantly the appearance and stability of painted works of art, saponification is one of the most serious problems of preservation of cultural heritage objects. Despite their versatility as well as hazardousness, there is a paucity of single-crystal X-ray structures of long-chain carboxylates, due to difficulties in preparing single crystals of sufficient quality. We studied the crystal structure of polycrystalline mixed lead carboxylates of the formula Pb(C16) 2-x (C18) x (x = 0; 0.25; 0.5; 0.75; 1; 1.5; 2), where C16 and C18 stand for hexadecanoate (palmitate) and octadecanoate (stearate) anions, respectively, by complementary X-ray powder diffraction (XRPD) and 13 C and 207 Pb solid state NMR (ssNMR). Mixed lead carboxylates consisting of hexadecanoate and octadecanoate are relevant to the formation of soaps in egg yolk and/or oil-based binders combined with lead-based pigments, which belong to the most common pigments in history. Combining an advanced XRPD analysis with a comparative analysis of ssNMR parameters, we described the structural model of mixed lead carboxylates. We revealed that both hexadecanoate (C16) and octadecanoate (C18) chains are present in one crystal structure, creating the statistical disorder at the ethyl end of the chains. Based on the 207 Pb ssNMR spectra, we revealed two distinct local environments of lead atoms, corresponding to the symmetrically (i.e., (C16)-Pb-(C16) and/or (C18)-Pb-(C18) and asymmetrically (i.e., (C16)-Pb-(C18)) substituted lead carboxylates, and we confirmed the formation of a holo-directed structure for both the structural motifs. The structural models were applied to identify the neo-formed crystalline lead soap in a model experiment simulating the simplified historic paint consisting of the pigment lead tin yellow type I and emulsion binder prepared from egg yolk and linseed oil. We identified the secondary product as a mixed lead carboxylate of the composition Pb(C16)(C18).

Adsorption properties of waste brick dust (WBD) were studied by the removing of Pb II and Cs I from an aqueous system. For adsorption experiments, 0.1 M and 0.5 M aqueous solutions of Cs + and Pb 2+ and two WBD (Libochovice-LB, and Tyn nad Vltavou-TN) in the fraction below 125 µm were used. The structural and surface properties of WBD were characterized by X-ray diffraction (XRD) in combination with solid-state nuclear magnetic resonance (NMR), supplemented by scanning electron microscopy (SEM), specific surface area (S BET ), total pore volume and zero point of charge (pH ZPC ). LB was a more amorphous material showing a better adsorption condition than that of TN. The adsorption process indicated better results for Pb 2+ , due to the inner-sphere surface complexation in all Pb 2+ systems, supported by the formation of insoluble Pb(OH) 2 precipitation on the sorbent surface. A weak adsorption of Cs + on WBD corresponded to the non-Langmuir adsorption run followed by the outer-sphere surface complexation. The leachability of Pb 2+ from saturated WBDs varied from 0.001% to 0.3%, while in the case of Cs + , 4% to 12% of the initial amount was leached. Both LB and TN met the standards for Pb II adsorption, yet completely failed for any Cs I removal from water systems.

Lead, a highly toxic element, is frequently present in various solid wastes as well as in industrial effluents. Sorption with a low cost sorbent is a simple way of Pb removal from liquid streams, but stabilization of spent sorbent has to be ensured in order to prevent Pb leaching out and possible environmental contamination. In previous research, ceramic sorbent, generated as waste product in brick industry, was tested as sorbent and proved high sorption capacity for lead. Lead was sorbed partially as hydrocerussite and partially as adsorbed surface layer. The Pb leaching from sorbent was very high and thus further immobilization of sorbent was necessary. Lead, as well as other heavy metals, is known as retarder of the hydration process of Ordinary Portland Cement (OPC), used for the immobilization. In this paper, influence of sorbed Pb and PbO, as reference compound, on cement hydration was studied by calorimetry, thermogravimetry and Magic Angle Spinning Nuclear Magnetic Resonance Spectroscopy (MAS NMR). The sorbed lead was found to be less detrimental to hydration retardation due to the lower solubility of precipitated hydrocerussite in basic environment compared to PbO, which forms plumbate anion.

Lewis acids and Lewis adducts are widely used in the chemical industry because of their high catalytic activity. Their precise geometrical description and understanding of their electronic structure are a crucial step for targeted synthesis and specific use. Herein, we present an experimental/computational strategy based on a solid-state NMR crystallographic approach allowing for detailed structural characterization of a wide range of organoaluminum compounds considerably differing in their chemical constitution. In particular, we focus on the precise measurement and subsequent quantum-chemical analysis of many different 27 Al NMR resonances in the extremely broad range of quadrupolar coupling constants from 1 to 50 MHz. In this regard, we have optimized an experimental strategy combining a range of static as well as magic angle spinning experiments allowing reliable detection of the entire set of aluminum sites present in trimesitylaluminum (AlMes 3 ) reaction products. In this way, we have spectroscopically resolved six different products in the resulting polycrystalline mixture. All 27 Al NMR resonances are precisely recorded and comprehensively analyzed by a quantum-chemical approach. Interestingly, in some cases the recorded 27 Al solid-state NMR spectra show unexpected quadrupolar coupling constant values reaching up to ca. 30 MHz, which are attributed to tetra-coordinated aluminum species (Lewis adducts with trigonal pyramidal geometry). The cause of this unusual behavior is explored by analyzing the natural bond orbitals and complexation energies. The linear correlation between the quadrupolar coupling constant value and the nature of bonds in the Lewis adducts is revealed. Moreover, the 27 Al NMR data are shown to be sensitive to the geometry of the tetra-coordinated organoaluminum species. Our findings thus provide a viable approach for the direct identification of Lewis acids and Lewis adducts, not only in the investigated multicomponent organoaluminum compounds but also in inorganic zeolites featuring catalytically active trigonal (Al III ) and strongly perturbed Al IV sites.

Framework materials, that is, metal-organic frameworks (MOFs) and inorganic frameworks (zeolites), are porous systems with regular structures that provide valuable properties suitable for sorption, catalysis, molecular sieving, and so on. Herein, an efficient, experimental/computational strategy is presented that allows detailed characterization of a polycrystalline MOF system, namely, zinc boron imidazolate framework ZBIF-1, with two integrated unit cells on the atomic-resolution level. Although high-resolution 1 H, 11 B, 13 C, and 15 N MAS NMR spectra provide valuable structural information on the coexistence of two distinct asymmetric units in the investigated system, an NMR crystallography approach combining X-ray powder diffraction, solid-state NMR spectroscopy, and DFT calculations allowed the exact structure of the secondary crystalline phase to be firmly defined and, furthermore, the mutual interconnectivity of the two crystalline frameworks to be resolved. Thus, this study shows the versatility and efficiency of solid-state NMR crystallography for the investigation of the wide family of MOF materials with their extensive structural complexity., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Carboxylate paddlewheels and their oxo-bridged analogues constitute ideal building blocks for the assembly of two- and three-dimensional framework materials. Here, we present a multinuclear ( 1 H, 13 C, 93 Nb, 95 Mo) magnetic resonance study of solid samples of Nb 2 OCl 6 (O 2 Ph) 2 (1), Mo 2 (O 2 CMe) 4 (2), and Mo 2 (O 2 CCHF 2 ) 4 (3). High-resolution proton and 13 C CP/MAS NMR spectra provide valuable information on structure and crystal symmetry and on cocrystallized solvent. 93 Nb solid-state NMR spectra of 1 provide quadrupolar coupling constants and chemical shift tensors which are characteristic of the axially asymmetric Nb-O-Nb bridging environment. 95 Mo solid-state NMR spectra of 2 and 3 provide quadrupolar coupling constants and chemical shift tensors which are directly characteristic of the molybdenum-molybdenum quadruple bonds in these compounds. The quadruple bonds are characterized by particularly large 95 Mo chemical shift tensor spans on the order of 5500ppm. Density functional theoretical computations provide good agreement with the 93 Nb and 95 Mo experimental data, with some exceptions noted. This work demonstrates possible NMR approaches to characterize more complex framework materials and provides key insight into the Mo-Mo quadruple bond., (Copyright © 2016 Elsevier Inc. All rights reserved.)

A general, easy-to-implement strategy for mapping the structure of organic phases integrated in mesoporous silica drug delivery devices is presented. The approach based on a few straightforward solid-state NMR techniques has no limitations regarding concentrations of the active compounds and enables straightforward discrimination of various organic phases. This way, among a range of typical arrangements of the active compounds and solvent molecules, a unique, previously unknown organogel phase of the self-assembled tapentadol in glucofurol as a solvent was unveiled and clearly identified. Subsequently, with an aid of 2D 1 H- 1 H MAS NMR and high-level quantum-chemical calculations this uncommon low-molecular-weight organogel phase, existing exclusively in the porous system of the silica carrier, was described in detail. The optimized model revealed the tendency of tapentadol molecules to form hydrophobic arrangements through -OH···π interactions combined with π-π stacking occurring in the core of API aggregates, thus precluding the formation of hydrogen bonds with the solvent. Overall, the proposed experimental approach allows for clear discrimination of a variety of local structures of active compounds loaded in mesoporous silica drug delivery devices in reasonably short time being applicable for advancement of novel drug delivery systems in pharmaceutical industry.

The difficulty in the prediction of the complicated solid-state structure of boronic acid derivatives, resulting from the complex pathway of reversible covalent interactions, represents a significant obstacle to the development of a new generation of advanced supramolecular systems such as covalent organic frameworks of efficient anticancer drugs. In this contribution, various 2D 11 B- 11 B solid-state NMR correlation techniques supported by DFT calculations were explored to formulate a reliable tool for monitoring the covalent assembly of boronic acid residues in the solid state. This way, the self-condensation of bortezomib molecules was investigated, different local constitutions of boroxine motifs were unveiled, and the previously unreported boroxine structures of bortezomib polymorphs exhibiting secondary coordination were discovered and described in detail. The recorded 11 B NMR parameters responded sensitively to subtle changes in the local geometries, which were reliably interpreted and directly visualized by the DFT calculations. A uniform 2.6 Å distance in bortezomib 11 B- 11 B spin pairs was conclusively identified by the through-space 11 B- 11 B double-quantum (DQ) coherence build-up curves, whereas distinct 2D 11 B- 11 B DQ correlation patterns revealed unique boroxine structures existing in the crystalline as well as amorphous state. The boroxine rings were found to be internally stabilized through the transformation of the trigonal boron sites toward tetrahedral geometry, as the secondary five-membered rings were formed. This way, the nature of bortezomib polymorphism is disclosed, and an efficient strategy for exploring the assembly of boronic acid derivatives in the solid state, for which no crystallographic data are available, is thus demonstrated.