Revealing the Dynamics of Hybrid Metal Halide Perovskite Formation via Multimodal In Situ Probes

The exploration of the synthetic space of halide perovskites hinges on an enormous number of parameters requiring time‐consuming experimentation to decouple and optimize. Here, the formation of the prototype material CH₃NH₃PbI₃ (MAPbI₃) is investigated at different time and length scales using multimodal in situ measurements to monitor the evolution of crystalline phases, morphology, and photoluminescence as a function of the lead precursors. Kinetically fast formation of crystalline precursor phases already during the spin‐coat deposition is observed using lead iodide (PbI₂) or lead chloride (PbCl₂) routes. These precursor phases most likely template final MAPbI₃ film morphology. In particular, the emergence of the “needle‐like” structure is shown to appear before film annealing. In situ photoluminescence measurements suggest nanoscale nucleation followed by rapid nuclei densification and growth. Using this multimodal in situ approach, different formation pathways can be identified either via precursor phases in the PbI₂ and PbCl₂ routes or direct perovskite formation from molecular building blocks as observed in the lead acetate (PbAc₂) route. Correlation of in situ results with photovoltaic device performance demonstrates the power of in situ multimodal techniques, paves the way to a fast screening of synthetic parameters, and ultimately leads to controlled synthetic procedures that yield high‐efficiency devices.     

Studies on conformational transition of the maleic acid copolymer with styrene in aqueous salt solution by derivative spectroscopy

The first and second derivative spectra for the optical absorption of maleic acid copolymer with styrene were measured in aqueous 0.09 m NaCl at 25°C within a wavelength range of 240–280 nm, where contributions of groups, other than the phenyl ones, to the second derivatives seem to be negligible. The normal absorption spectra in the range were composed of seven absorption bands and the peak position of each band was determined from the derivative spectra. The peak position of the coiled form copolymer was found to shift to the shorter wavelength range compared with the compact form of the copolymer. From the extent of such blue shifts for each peak, the environment near the phenyl groups in the compact copolymer form was concluded to be similar to aqueous ethanol (40–50 vol%), by comparing with the derivative spectra for $\text{N-}\text{acetyl-}\text{l}\text{-rmphenylalanine}$ in a water-ethanol mixture. However, the first and second derivative spectra and various first derivative spectra were found to have 12 isoderivative points, and all the bands of the different spectra displayed the two-state character of the transition. The degree of transition was determined from the change in the peak height of each band and this coincided well with the pH-titration data.     

Hypomethylation of CLDN4 Gene Promoter Is Associated with Malignant Phenotype in Urinary Bladder Cancer

The tight junction (TJ) protein claudin-4 (CLDN4) is overexpressed in bladder urothelial carcinoma (BUC) and correlates with cancer progression. However, the mechanism of CLDN4 upregulation and promotion of malignant phenotype is not clear. Here, we analyzed 157 cases of BUC and investigated the hypomethylation of CpG island in the CLDN4 promoter DNA and its correlation with cancer progression. In hypomethylated cases, CLDN4 expression, cell proliferation, stemness, and epithelial-mesenchymal transition were increased. Treatment of three human BUC cell lines with the demethylating agent aza-2′-deoxycytidine (AZA) led to excessive CLDN4 expression, and, specifically, to an increase in CLDN4 monomer that is not integrated into the TJ. The TJ-unintegrated CLDN4 was found to bind integrin β1 and increase stemness, drug resistance, and metastatic ability of the cells as well as show an anti-apoptosis effect likely via FAK phosphorylation, which reduces upon knockdown of CLDN4. Thus, CLDN4 is overexpressed in BUC by an epigenetic mechanism and the high expression enhances the malignant phenotype of BUC via increased levels of TJ-unintegrated CLDN4. CLDN4 promoter DNA methylation is expected to be a novel indicator of BUC malignant phenotype and a new therapeutic target.     

Oxidation kinetics of high strength low alloy steels at elevated temperatures

High strength low alloy (HSLA) steels are candidate Rockbolt materials for use as underground roof supports at Yucca Mountain nuclear waste repository. Oxidation kinetics of International Rollforms Split Set Friction Rock Stabilizers (SS46), and Swellex Mn24 steels have been determined by temperature modulated thermogravimetry at temperatures ranging between 600 and 900 °C in pure oxygen atmosphere for 100 hr. The imposed sinusoidal temperature modulations (±5 °C for a period of 1 cycle per 200 s) on the isothermal temperature did not have any noticeable effect on the weight gain characteristics during oxidation. Weight gain data on the steels indicate two distinct regions with different oxidation profiles, where a definite change in rates of oxidation is observed: a first oxidation regime where the steels followed a rate law y = kt^0.40-0.63 (changing index of rate law depending upon steel and temperature) and a second stage oxidation regime that follows the parabolic law. The results of characterization of the oxide films using SEM/EDAX, X-ray diffraction and Synchrotron white beam X-ray microdiffraction are presented. The oxidation data of the steels presented here is expected to be useful for characterizing those steels for use in underground rock bolt system and as roof support for the DOE proposed Yucca Mountain Nuclear Waste Repository. To the best of our knowledge this is the first time thermogravimetric studies of this kind have been done on these steels.     

Determination of Free-Radical Propagation Rate Coefficient of N-Vinylindole by the Pulsed-Laser Polymerization Method

Summary The pulsed-laser polymerization method was applied to determine the propagation rate constant k_p of N-vinylindole (VI), and the Arrhenius parameters were evaluated in the range of 30-70 °C. One of the characteristics of the VI monomer was its low activation energy (17.5 kJ mol^-1) compared with other vinyl monomers, indicating that the propagating radical has a high reactivity. Although the reaction rate constant k_p = 86 L mol^-1 s^-1 at 30 °C was relatively small and similar to that of styrene, the Q-value and the products of photochemical reactions suggested again that it has a higher reactivity than styrene monomer. This property of VI radical probably gives rise to high termination probability and the cyclic structure at the chain end of the linear polymer.     

Biomineral nanoparticles are space-filling

Sea urchin biominerals have been shown to form from aggregating nanoparticles of amorphous calcium carbonate (ACC), which then crystallize into macroscopic single crystals of calcite. Here we measure the surface areas of these biominerals and find them to be comparable to those of space-filling macroscopic geologic calcite crystals. These biominerals differ from synthetic mesocrystals, which are invariably porous. We propose that space-filling ACC is the structural precursor for echinoderm biominerals.     

Hand-scan OCR with a one-dimensional image sensor

We have developed a hand scanning type OCR, an optical character reader, which is applicable to POS terminals, etc. It uses a one-dimensional image sensor for small size and low cost. We developed a new recognition method which can overcome the irregularity of the hand scanning. Our method has two kinds of counters to extract the horizontal line features. One is a black occurrence counter and the other is a front shape counter. Normalizing these data reduces the influence of pattern variation. The method has been tested widely all over the world as a commercial OCR-A font reader.     

Direct measurement of triaxial strain fields around ferroelectric domains using X-ray microdiffraction

Ferroelectric materials, such as BaTiO(3), have piezoelectric properties that make them attractive for microelectronic and sensing applications. It is well known that the application of mechanical stress or electric field can alter the domain structure in ferroelectrics. Indeed, the constitutive behaviour of a ferroelectric is largely governed by the formation, movement and interaction of its domains. Therefore, it is crucial that the micromechanics of domains and their effect on internal stresses in ferroelectrics be understood. Here we show that the emerging technique of scanning X-ray microdiffraction can be used to measure directly, for the first time, the local triaxial strain fields around 90 degrees domains in single-crystal BaTiO(3). Specifically, residual strain maps in a region surrounding an isolated, approximately 40 microm wide, 90 degrees domain were obtained with 3 microm resolution, revealing significant residual strains. This information is critical for accurate micromechanical modelling of domain behaviour in ferroelectrics.     

Behavior of Vaneless Diffuser Stall in a Centrifugal Compressor

The rotating stall in a centrifugal compressor with a vaneless diffuser was investigated both experimentally and numerically with focus on the effect of the internal flow field within the impeller on the diffuser stall.Through numerical analysis,the boundary layer separation at the impeller outlet was found to play an important role in the expansion and rotation processes of the diffuser stall.In particular,the expanded boundary layer separation near the hub side at the outlet of the main blade(M.B.)suction surface passage was considered to be the main cause of the expansion and rotation processes.A longitudinal vortex existed at the throat of the M.B.passage,and the mass flow rate in the M.B.passage was significantly reduced by the blockage effect.In addition,the longitudinal vortex induced the rolling up flow near the hub side at the impeller exit.Thus,the boundary layer separation expanded.     

Cross section adjustment method based on random sampling technique

A cross section adjustment method based on the random sampling technique is proposed. In the proposed method, correlations among cross sections and core parameters are used instead of sensitivity coefficients of cross sections, which are necessary in the conventional method. The correlations are statistically estimated by the random sampling technique. The proposed method is theoretically consistent with the conventional method and provides comparable adjusted cross sections when sufficient number of random sampling is taken into account. The proposed method would be suitable for practical light water reactor (LWR) core analysis since estimation of sensitivity coefficients, which requires considerable computational cost in typical LWR problems, is not necessary. Through a benchmark problem in simple pin-cell geometry, adjusted cross sections by the present and the conventional cross section adjustment method are compared. The adjusted cross sections by the present method well reproduce the conventional ones, thus the feasibility of the present method is confirmed.