Contacting boron emitters on n‐type silicon solar cells with aluminium‐free silver screen‐printing pastes

In the production of n‐type Si solar cells, B diffusion is commonly applied to form the p⁺ emitter. Up to now, Ag screen‐printing pastes, generally used to contact P emitters, had been incapable of reliably contact B emitters. Therefore, a small amount of Al is generally added to Ag pastes to allow for reasonable contact resistances. The addition of Al, however, results in deep metal spikes growing into the Si surface that can penetrate the emitter. Losses in open‐circuit voltage are attributed to these deep metal spikes. In this investigation we demonstrate, that state‐of‐the‐art Al‐free Ag screen‐printing pastes are capable to contact BBr₃‐based B emitters covered with different dielectric layers and reach specific contact resistances <1 mΩ cm². Bifacial n‐type solar cells with Al‐free Ag pastes on both sides show efficiencies of up to 18.3% and series resistances <0.5 Ω cm². (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Nickel-cysteine binding supported by phosphine chelates

The effect of chelating phosphines was tested on the structure and pH-dependent stability of nickel-cysteine binding. (1,2-Bis(diphenylphosphino)ethane (dppe) and 1,1,1-tris[(diphenylphosphino)methyl]ethane (triphos) were used with three different cysteine derivatives (L-cysteine, Cys; L-cysteine ethyl ester, CysEt; cystamine, CysAm) to prepare complexes of the form (dppe)NiCysR(n+) and (triphos)NiCysR(n+) (n = 0 for Cys; n = 1 for CysEt and CysAm). Similar 31P {1H} NMR spectra for all (dppe)NiCysRn+ confirmed their square-planar P2NiSN coordination spheres. The structure of [(dppe)NiCysAm]PF6 was also confirmed by single-crystal X-ray diffraction methods. The (triphos)NiCysAm+ and (triphos)NiCysEt+ complexes were fluxional at room temperature by 31P NMR. Upon cooling to -80 degrees C, all gave spectra consistent with a P2NiSN coordination sphere with the third phosphorus uncoordinated. Temperature-dependent 31P NMR spectra showed that a trans P-Ni-S pi interaction controlled the scrambling of the coordinated triphos. In aqueous media, (dppe)NiCys was protonated at pH approximately 4-5, leading to possible formation of a nickel-cysteinethiol and eventual cysteine loss at pH < 3. The importance of N-terminus cysteine in such complexes was demonstrated by preparing (dppe)NiCys-bead and trigonal-bipyramidal Tp*NiCys-bead complexes, where Cys-bead represents cysteine anchored to polystyrene synthesis beads and Tp*- = hydrotris(3,5-dimethylpyrazolyl)borate. Importantly, results with these heterogeneous systems demonstrated the selectivity of these nickel centers for cysteine over methionine and serine and most specifically for N-terminus cysteine. The role of Ni-S pi bonding in nickel-cysteine geometries will be discussed, including how these results suggest a mechanism for the movement of electron density from nickel onto the backbone of coordinated cysteine.     

An experimental and theoretical study of the asymmetric lithiation of 1,2,3,5,6,7-hexahydro-3a,4a-diazacyclopenta[def]phenanthren-4-one

The inability of bis-N-Boc-protected octahydrophenanthroline to undergo asymmetric lithiation with (-)-sparteine is circumvented by use of a urea functionality as the directing group. Asymmetric lithiation followed by electrophile quench gives products substituted alpha to nitrogen in better yield (17-30%) but slightly lower enantiomeric ratio (er 84:16) than analogous lithiation of N-Boc-piperidine (er 87:13). Computational studies at the MP2/6-316(d)//B3LYP/6-316(d) level indicate that the prochiral equatorial S-hydrogen is removed preferentially over the pro-R hydrogen, with a difference in transition state activation energies of 1.26 kcal/mol, corresponding to a predicted er of 89:11. The predicted stereochemistry of the reaction was confirmed by single-crystal X-ray analysis of an aryl dibromide prepared from the enantiomerically enriched alpha-methyl-substituted product.     

Coupled Metabolic Cycles Allow Out-of-Equilibrium Autopoietic Vesicle Replication

We report chemically fuelled out-of-equilibrium self-replicating vesicles based on surfactant formation. We studied the vesicles’ autocatalytic formation using UPLC to determine monomer concentration and interferometric scattering microscopy at the nanoparticle level. Unlike related reports of chemically fuelled self-replicating micelles, our vesicular system was too stable to surfactant degradation to be maintained out of equilibrium. The introduction of a catalyst, which introduces a second catalytic cycle into the metabolic network, was used to close the first cycle. This shows how coupled catalytic cycles can create a metabolic network that allows the creation and perseverance of fuel-driven, out-of-equilibrium self-replicating vesicles.     

Liquid chromatography/mass spectrometry compatible approaches for the quantitation of folic acid in fortified juices and cereals using aqueous normal phase conditions

Folic acid was separated under aqueous normal phase (ANP) conditions with Diamond Hydride™ columns and quantitated in fortified cereal and juice matrices using high performance liquid chromatography/ultraviolet absorption (HPLC-UV) and liquid chromatography/mass spectrometry (LC–MS) based methodologies. The folic acid was well-resolved from matrix components under the ANP conditions studied and allowed for the direct analyses of the fortified juices and cereals without the sample cleanup that is often required for other reported LC-based approaches. The calibration curve obtained from the LC–MS analyses demonstrated good linearity (R² = 0.9997) in the studied concentration range of 0.05–0.5 mg/L. The spiked flour percent recovery was 90% with HPLC-UV and 91% with LC–MS. Spiked juice percent recovery was 102% with LC–MS. However, analyses of juices were unsatisfactory either in terms of recovery or sensitivity. Therefore, analyses of juices will either need to be performed by LC–MS or, if by HPLC-UV, will require sample cleanup. Three cereals and one juice were analyzed with the methods.     

Effect of solvent polarity and electrophilicity on quantum yields and solvatochromic shifts of single-walled carbon nanotube photoluminescence

In this work, we investigate the impact of the solvation environment on single-walled carbon nanotube (SWCNT) photoluminescence quantum yield and optical transition energies (E(ii)) using a highly charged aryleneethynylene polymer. This novel surfactant produces dispersions in a variety of polar solvents having a wide range of dielectric constants (methanol, dimethyl sulfoxide, aqueous dimethylformamide, and deuterium oxide). Because a common surfactant can be used while maintaining a constant SWCNT-surfactant morphology, we are able to straightforwardly evaluate the impact of the solvation environment upon SWCNT optical properties. We find that (i) the SWCNT quantum yield is strongly dependent on both the polarity and electrophilicity of the solvent and (ii) solvatochromic shifts correlate with the extent of SWCNT solvation. These findings provide a deeper understanding of the environmental dependence of SWCNT excitonic properties and underscore that the solvent provides a tool with which to modulate SWCNT electronic and optical properties.     

Spatial cues alone produce inaccurate sound segregation: the effect of interaural time differences

To clarify the role of spatial cues in sound segregation, this study explored whether interaural time differences (ITDs) are sufficient to allow listeners to identify a novel sound source from a mixture of sources. Listeners heard mixtures of two synthetic sounds, a target and distractor, each of which possessed naturalistic spectrotemporal correlations but otherwise lacked strong grouping cues, and which contained either the same or different ITDs. When the task was to judge whether a probe sound matched a source in the preceding mixture, performance improved greatly when the same target was presented repeatedly across distinct distractors, consistent with previous results. In contrast, performance improved only slightly with ITD separation of target and distractor, even when spectrotemporal overlap between target and distractor was reduced. However, when subjects localized, rather than identified, the sources in the mixture, sources with different ITDs were reported as two sources at distinct and accurately identified locations. ITDs alone thus enable listeners to perceptually segregate mixtures of sources, but the perceived content of these sources is inaccurate when other segregation cues, such as harmonicity and common onsets and offsets, do not also promote proper source separation.     

Enumerating invariant subspaces of Rn

In this article, we develop an algorithm to calculate the set of all integers m for which there exists a linear operator T on ${\mathbb{R}}^n$ such that ${\mathbb{R}}^n$ has exactly m T-invariant subspaces. Moreover, the algorithm gives a method for the explicit construction of such a linear operator T. A brief discussion is included as how these methods can be extended to vector spaces over arbitrary fields.     

Interconversion of Phosphinyl Radical and Phosphinidene Complexes by Proton Coupled Electron Transfer

The isolable complex [Os(PHMes*)H(PNP)] (Mes*=2,4,6‐^tBu₃C₆H₃; PNP=N{CHCHP^tBu₂}₂) exhibits high phosphinyl radical character. This compound offers access to the phosphinidene complex [Os(PMes*)H(PNP)] by P?H proton coupled electron transfer (PCET). The P?H bond dissociation energy (BDE) was determined by isothermal titration calorimetry and supporting DFT computations. The phosphinidene product exhibits electrophilic reactivity as demonstrated by intramolecular C?H activation.     

Antifreeze Protein‐Induced Selective Crystallization of a New Thermodynamically and Kinetically Less Preferred Molecular Crystal

The formation of a new, dihydrate crystalline form of 5‐methyluridine (m⁵U) was selectively induced by a protein additive, antifreeze protein (AFP) in a highly efficient manner (in 10^?6 molar scale, whereas known kinetic additives need 0.1 molar scale). The hemihydrate form (form I, the only previously known crystalline form of m⁵U) and the dihydrate form of m⁵U (form II) obtained herein were characterized using X‐ray crystallography and differential scanning calorimetry (DSC). Compared to form I, remarkably, form II is thermodynamically and kinetically less preferred. The presence of AFP can selectively inhibit the appearance of form I and hence allows the growth of form II, the pure form of which cannot grow directly from m⁵U supersaturated solutions under the same conditions. An explanation supported by both experimental and theoretical results is provided for the AFP‐induced selection process. Implications on AFP‐induced ice shape changes are also discussed. Control of crystallization from supersaturated solutions is of great interest in both fundamental research and practical applications in fields like chemistry, pharmacology and materials science. These findings suggest that crystallization processes with AFPs could be valuable for selective growth of hydrates and polymorphs of important pharmaceutical compounds.