Monitoring the Formation of a CH3NH3PbI3–xClx Perovskite during Thermal Annealing Using X‐Ray Scattering

Grazing incidence wide and small angle X‐ray scattering (GIWAXS and GISAXS) measurements have been used to study the crystallization kinetics of the organolead halide perovskite CH₃NH₃PbI_3–xCl_x during thermal annealing. In situ GIWAXS measurements recorded during annealing are used to characterize and quantify the transition from a crystalline precursor to the perovskite structure. In situ GISAXS measurements indicate an evolution of crystallite sizes during annealing, with the number of crystallites having sizes between 30 and 400 nm increasing through the annealing process. Using ex situ scanning electron microscopy, this evolution in length scales is confirmed and a concurrent increase in film surface coverage is observed, a parameter crucial for efficient solar cell performance. A series of photovoltaic devices are then fabricated in which perovskite films have been annealed for different times, and variations in device performance are explained on the basis of X‐ray scattering measurements.     

Phonon Dynamics at Surfaces and Interfaces and Its Implications in Energy Transport in Nanostructured Materials—An opinion Paper

Nanoscale thermal transport has attracted considerable attention because of both fundamental scientific interest and important engineering applications. For semiconductors and insulators, energy transport is dominated by phonons, whose behavior at surfaces and interfaces plays a significant role in energy transport processes. In this article, we present opinions on phonon dynamics at surfaces and interfaces and the implications on nanoscale thermal transport. The effects of roughness, bonding strength, coherence, and nanoscale constrictions are discussed. The existence of two specularity parameters at an interface (separate values for transmitted and reflected phonons) and the implications of phonon reflection at free surfaces to the thermal conductance of nearby interfaces are two concepts that have not been previously discussed in the literature. We provide some outlook and potential topics for future studies.     

Calculation of the electric field enhancement for a degenerate diffusion process

The internal electric field produced by a constant source impurity diffusion is calculated using Fermi-Dirac statistics for the majority carrier. Numerical results indicate that treating the material as if it were nondegenerate always produces an underestimate in the electric field. The field enhancement factor which gives the ratio of the effective diffusion coefficient to the impurity diffusion coefficient valid for a degenerate diffusion process is clarified.     

Construction of validated, non-redundant composite protein sequence databases

A strategy has been developed for the construction of a validated,comprehensive composite protein sequence database. Entries areamalgamated from primary source data bases by a largely automatedset of processes in which redundant and trivially differententries are eliminated. A modular approach has been adoptedto allow scientific judgement to be used at each stage of databaseprocessing and amalgamation. Source databases are assigned apriority depending on the quality of sequence validation andcommenting. Rejection of entries from the lower priority database,in each pairwise comparison of databases, is carried out accordingto optionally defined redundancy criteria based on sequencesegment mismatches. Efficient algorithms for this methodologyare embodied in the COMPO software system. COMPO has been appliedfor over 2 years in construction and regular updating of theOWL composite protein sequence database from the source databasesNBRF-PIR, SWISS-PROT, a GenBank translation retrieved from thefeature tables, NBRF-NEW, NEWAT86, PSD-KYOTO and the sequencescontained in the Brookhaven protein structure databank. OWLis part of the ISIS integrated data resource of protein sequenceand structure [Akrigg et al. (1988) Nature, 335, 745–746].The modular nature of the integration process greatly facilitatesthe frequent updating of OWL following releases of the sourcedatabases. The extent of redundancy in these sources is revealedby the comparison process. The advantages of a robust compositedatabase for sequence similarity searching and information retrievalare discussed.     

Structural Studies of Anomalous Behavior in the Silica-Alumina Gel System

This paper compares the structure ofAl₂O₃-SiO₂ xerogels prepared with Al₂O₃ contents ranging from 21 to 75 wt% (13 to 64 mol%). The 47 wt% Al₂O₃ xerogel (Al/Si ≅ 1) exhibits anomalously low surface area (≅1 m²/g) and skeletal density compared with other Al₂O₃-Si₂ compositions. Based on the results of nitrogen adsorption/condensation, helium displacement, high-resolution transmission electron microscopy (HRTEM), small-angle X-ray scattering (SAXS), and small-angle neutron scattering (SANS), we attribute the low surface area and skeletal density (density of the solid phase which is inaccessable to helium) to the formation of closed micropores, whereas the higher surface area materials exhibit a slightly coarser texture comprising open pores with radii of ≅1 nm. X-ray diffraction (XRD) and ²⁹SI and ²⁷Al magic-angle spinning nuclear magnetic resonance (MASNMR) indicate no anomalous behavior in the 47% sample on molecular length scales. HRTEM indicates the presence of a small fraction of crystallites which is supported by the SAXS results, but it is unknown if this crystallinity is related to low surface area. Low-field ¹H NMR spin-lattice relaxation measurements show that the physical structure of all of the 'wet' gels is similar implying that pore closure occurs during drying. Consistent with this idea, gel surface area and density increased significantly when the pore fluid (water) was replaced with a lower surface tension fluid (formamide, dioxane, ethanol. water/surfactant).     

Thermal denaturation of soy proteins as related to their dye-binding characteristics and functionality

The binding of Cresol Red and of Acid Orange 10 (in the absence and presence of urea) to unheated and progressively heated, defatted soy meal was compared with their NSI values, urease activities,in vitro digestibilities, unreactive lysine contents, and foaming and emulsifying capacities. These results suggested that increased amounts of Cresol Red and of Acid Orange 10 (in the presence of urea) bound to the heated samples were due to the progressive exposure of hydrophobic residues caused thermal denaturation. High statistical correlations were obtained between dye-binding, the duration of heating, and functional properties. Our results indicate that dye-binding has potential for predicting certain functional properties as well as for monitoring thermal denaturation of soy proteins.     

2,2′-OXO-1, 1 ′-azobenzene A microbially transformed allelochemical from 2,3-Benzoxazolinone: I

2,2-Oxo-1,1 -azobenzene (AZOB), a compound with strong herbicidal activity, was isolated and characterized from a soil supplemented with 2,3-benzoxazolinone (BOA). A parallel experiment with 6-methoxy-2,3-benzoxazolinone (MBOA) yielded AZOB as well as its mono-(MAZOB) and dimethoxy-(DIMAZOB) derivatives. These compounds were produced only in the presence of soil microorganisms, via possible intermediates, I and II, which may dimerize or react with the parent molecule to form the final products. In the case of MBOA, it was shown that demethoxylation precedes the oxidation step. Although BOA and 2,4-dihydroxy-1,4(2H)-benzoxazin-3-one (DIBOA) were leached out of rye residues, there were no detectable amounts of the biotransformation products in the soil. When BOA was mixed with soil and rye residue, either under field conditions or in vitro, AZOB was detected. Levels of free BOA in the soil were greatly reduced by incubation with rye residue. AZOB was more toxic to curly cress (Lepidium sativum L.) and barnyardgrass (Echinochloa crusgatti L.) than either DIBOA or BOA.Journal Article No. 12943 of the Michigan Agricultural Experiment Station.     

Passivation of pyrite due to surface treatment

Two samples of naturally occurring pyrite were treated with acetyl acetone, silanes, humic acids, lignin-NaOH mixture, and oxalic acid. The corrosion rate of pyrite was observed to decrease significantly due to the surface treatment by the chemicals used in this study. Surface characterization methods indicate that phenyl triacetoxy silane forms a passive coating a few Angstroms thick on the pyrite, thus preventing its dissolution in 1M H₂SO₄.     

Effects of drought on yield and on grain and malt characters in spring barley

The effects on yield and on grain and malt characters, of drought stress applied at different stages of grain development and ripening were studied in three varieties of spring barley grown in a glasshouse. Differences between variety means were found for most of the characters studied, but only for wort filtration time was there a significant interaction between variety and irrigation treatment. Grain yield was reduced by all the treatments involving drought stress and the reduction was greatest when stress was applied at heading and maintained for at least 14 days. A similar response was found for the number of ears per plant. Number of grains per main-shoot ear was reduced by drought stress applied at heading but not when the stress was applied from 32 days after heading until harvest. Grain size was significantly reduced by all treatments. Raw-grain characters known to be correlated with malt extract were found to be affected by the treatments: grain nitrogen content, barley extract viscosity and the rate of sedimentation of barley flour in ethanol were all increased by drought stress, the degree of response varying with the length and timing of the period of drought. Malt extracts were reduced by drought stress whether this was applied early or late in grain development. Malting loss and germinative energy were reduced, and wort filtration time increased by late stress. α-Amylase activity in the germinating grain was unaffected by any of the treatments.     

A Test of the Equality of Survival Distributions Based on Paired Observations from Conditionally Independent Exponential Distributions

A model describes the joint distribution of paired survival times based on certain reasonable assumptions appropriate for biological data generated in a clinical trial setting or for certain failure data. An exact parametric test for equality of mean survival times for data following this distribution is developed. The power of the exact test is investigated by a computer simulation study for various sample sizes and values of the model parameters and compared to that of alternative tests. Heretofore, researchers desiring to analyze paired survival data have resorted to paired t tests or nonparametric procedures such as the sign test or signed ranks test. The t-test is invalid for non-normally distributed data although the robustness of the test might minimize the difficulty. The nonparametric tests, by their nature, fail to use the data completely. This paper presents an exact parametric test based on a distribution whose justification requires rather modest and reasonable assumptions. Critical values for the test can be obtained from a table of the chi-square distribution. This exact test appears to be a viable alternative to non-parametric approaches to the analysis of paired survival data. It is extremely easy to calculate on a hand calculator. In fact, since no data storage is required (unlike the signed ranks test), the calculations can be readily programmed on a programmable calculator. The modeling of bivariate and multivariate survival data we believe has not been adequately addressed in the statistical and engineering literature. We hope that this paper will spark additional work.