Chemical Reaction of FA Cations Enables Efficient and Stable Perovskite Solar Cells.

Organometal halide perovskite solar cells (PSCs) have received great attention owing to a rapid increase in power conversion efficiency (PCE) over the last decade. However, the deficit of long-term stability is a major obstacle to the implementation of PSCs in commercialization. The defects in perovskite films are considered as one of the primary causes. To address this issue, isocyanic acid (HNCO) is introduced as an additive into the perovskite film, in which the added molecules form covalent bonds with FA cations via a chemical reaction. This chemical reaction gives rise to an efficient passivation on the perovskite film, resulting in an improved film quality, a suppressed non-radiation recombination, a facilitated carrier transport, and optimization of energy band levels. As a result, the HNCO-based PSCs achieve a high PCE of 24.41% with excellent storage stability both in an inert atmosphere and in air. Different from conventional passivation methods based on coordination effects, this work presents an alternative chemical reaction for defect passivation, which opens an avenue toward defect-mitigated PSCs showing enhanced performance and stability.

Homogeneous and air-water interface properties of nicotine relative to aqueous aerosol: Adsorption, oxidation, and the influence for the HNCO formation.

Nicotine is the most abundant alkaloid compound in cigarette smoke and a known "emerging contaminant" in gas and aqueous environments. The main environmental behavior of nicotine is to be deposited on various surfaces. Aerosol droplets have a rich specific surface area, which has a great influence on air quality and human health. However, the microscopic interaction between aqueous nanoparticles and nicotine has not been revealed. In this work, the theoretical simulation of the adsorption and reaction properties of nicotine onto aerosol droplets is performed. The strong preference for nicotine on aqueous particle surfaces is firstly proven, and its interface retention rate is about 73 %, 4-7 times larger than that in the air/water phase. The k value of the interface reaction (heterogeneous reaction) is 4.34 × 10-9 cm3 molecule-1 s-1, which is about 80 and 571 times higher than that of the gaseous and aqueous reactions (homogeneous reaction). Interface environment can promote the oxidation of nicotine by •OH, and indirectly promote the rapid generation of toxic HNCO. The reaction rate constant of nicotine with •OH decreases with the increase of aerosol acidity, subsequently impeding the formation of HNCO. Considering the larger rate constant at the interface environment, the total effect of aqueous aerosol should be to improve the formation of HNCO. This work provides insight into the adsorption and oxidation of nicotine on the surface of the aerosol and is helpful in accurately evaluating its environmental fate and risk.

Experimental FTIR-MI and Theoretical Studies of Isocyanic Acid Aggregates.

Homoaggregates of isocyanic acid (HNCO) were studied using FTIR spectroscopy combined with a low-temperature matrix isolation technique and quantum chemical calculations. Computationally, the structures of the HNCO dimers and trimers were optimized at the MP2, B3LYPD3 and B2PLYPD3 levels of theory employing the 6-311++G(3df,3pd) basis set. Topological analysis of the electron density (AIM) was used to identify the type of non-covalent interactions in the studied aggregates. Five stable minima were located on the potential energy surface for (HNCO)2, and nine were located on the potential energy surface for (HNCO)3. The most stable dimer (D1) involves a weak, almost linear N-H⋯N hydrogen bond. Other structures are bound by a N-H⋯O hydrogen bond or by O⋯C or N⋯N van der Waals interactions. Similar types of interactions as in (HNCO)2 were found in the case of HNCO trimers. Among nine stable (HNCO)3 structures, five represent cyclic forms. The most stable T1 trimer structure is characterized by a six-membered ring formed by three N-H⋯N hydrogen bonds and representing high symmetry (C3h). The analysis of the HNCO/Ar spectra after deposition indicates that the N-H⋯O hydrogen-bonded dimers are especially prevalent. Upon annealing, HNCO trimers were observed as well. Identification of the experimentally observed species relied on previous experimental data on HNCO complexes as well as computed data on HNCO homoaggregates' vibrational spectra.

Matrix Isolation FTIR and Theoretical Study of Weakly Bound Complexes of Isocyanic Acid with Nitrogen.

Weak complexes of isocyanic acid (HNCO) with nitrogen were studied computationally employing MP2, B2PLYPD3 and B3LYPD3 methods and experimentally by FTIR matrix isolation technique. The results show that HNCO interacts specifically with N2. For the 1:1 stoichiometry, three stable minima were located on the potential energy surface. The most stable of them involves a weak, almost linear hydrogen bond from the NH group of the acid molecule to nitrogen molecule lone pair. Two other structures are bound by van der Waals interactions of N⋯N and C⋯N types. The 1:2 and 2:1 HNCO complexes with nitrogen were computationally tracked as well. Similar types of interactions as in the 1:1 complexes were found in the case of the higher stoichiometry complexes. Analysis of the HNCO/N2/Ar spectra after deposition indicates that the 1:1 hydrogen-bonded complex is prevalent in argon matrices with a small amount of the van der Waals structures also present. Upon annealing, complexes of the 1:2 and 2:1 stoichiometry were detected as well.

Sensitivity-enhanced three-dimensional and carbon-detected two-dimensional NMR of proteins using hyperpolarized water.

Signal enhancements of up to two orders of magnitude in protein NMR can be achieved by employing HDO as a vector to introduce hyperpolarization into folded or intrinsically disordered proteins. In this approach, hyperpolarized HDO produced by dissolution-dynamic nuclear polarization (D-DNP) is mixed with a protein solution waiting in a high-field NMR spectrometer, whereupon amide proton exchange and nuclear Overhauser effects (NOE) transfer hyperpolarization to the protein and enable acquisition of a signal-enhanced high-resolution spectrum. To date, the use of this strategy has been limited to 1D and 1H-15N 2D correlation experiments. Here we introduce 2D 13C-detected D-DNP, to reduce exchange-induced broadening and other relaxation penalties that can adversely affect proton-detected D-DNP experiments. We also introduce hyperpolarized 3D spectroscopy, opening the possibility of D-DNP studies of larger proteins and IDPs, where assignment and residue-specific investigation may be impeded by spectral crowding. The signal enhancements obtained depend in particular on the rates of chemical and magnetic exchange of the observed residues, thus resulting in non-uniform 'hyperpolarization-selective' signal enhancements. The resulting spectral sparsity, however, makes it possible to resolve and monitor individual amino acids in IDPs of over 200 residues at acquisition times of just over a minute. We apply the proposed experiments to two model systems: the compactly folded protein ubiquitin, and the intrinsically disordered protein (IDP) osteopontin (OPN).

An improved protocol for amino acid type-selective isotope labeling in insect cells.

An improved expression protocol is proposed for amino acid type-specific [13C], [15N]-isotope labeling of proteins in baculovirus-infected (BV) insect cell cultures. This new protocol modifies the methods published by Gossert et al. (J Biomol NMR 51(4):449-456, 2011) and provides efficient incorporation of isotopically labeled amino acids, with similar yields per L versus unlabeled expression in rich media. Gossert et al. identified the presence of unlabeled amino acids in the yeastolate of the growth medium as a major limitation in isotope labeling using BV-infected insect cells. By reducing the amount of yeastolate in the growth medium ten-fold, a significant improvement in labeling efficiency was demonstrated, while maintaining good protein expression yield. We report an alternate approach to improve isotope labeling efficiency using BV-infected insect cells namely by replacing the yeast extracts in the medium with dialyzed yeast extracts to reduce the amount of low molecular weight peptides and amino acids. We report the residual levels of amino acids in various media formulations and the amino acid consumption during fermentation, as determined by NMR. While direct replacement of yeastolate with dialyzed yeastolate delivered moderately lower isotope labeling efficiencies compared to the use of ten-fold diluted undialized yeastolate, we show that the use of dialyzed yeastolate combined with a ten-fold dilution delivered enhanced isotope labeling efficiency and at least a comparable level of protein expression yield, all at a scale which economizes use of these costly reagents.

In vivo, large-scale preparation of uniformly (15)N- and site-specifically (13)C-labeled homogeneous, recombinant RNA for NMR studies.

Knowledge of how ribonucleic acid (RNA) structures fold to form intricate, three-dimensional structures has provided fundamental insights into understanding the biological functions of RNA. Nuclear magnetic resonance (NMR) spectroscopy is a particularly useful high-resolution technique to investigate the dynamic structure of RNA. Effective study of RNA by NMR requires enrichment with isotopes of (13)C or (15)N or both. Here, we present a method to produce milligram quantities of uniformly (15)N- and site-specifically (13)C-labeled RNAs using wild-type K12 and mutant tktA Escherichia coli in combination with a tRNA-scaffold approach. The method includes a double selection protocol to obtain an E. coli clone with consistently high expression of the recombinant tRNA-scaffold. We also present protocols for the purification of the tRNA-scaffold from a total cellular RNA extract and the excision of the RNA of interest from the tRNA-scaffold using DNAzymes. Finally, we showcase NMR applications to demonstrate the benefit of using in vivo site-specifically (13)C-labeled RNA.

Crystal structure of 1-ethyl-spiro-[imid-az-olidine-4,1'-indane]-2,5-dione.

In the title compound, C13H14N2O2, the C5 ring has an envelope conformation with the C atom adjacent to the quaternary C being the flap. The five atoms comprising the imidazolidine-2,4-dione ring are almost planar (r.m.s. deviation = 0.004 Å). The dihedral angle between the five-membered rings is 89.66 (10)°. In the crystal, inversion-related mol-ecules are connected via {⋯HNCO}2 synthons. These are linked into a helical supra-molecular chain along [010] by C-H⋯O inter-actions.