A deep level transient spectroscopy study on the interface states across grain boundaries in multicrystalline silicon

Degrading the recombination activities of grain boundaries (GBs) is essential to improve the efficiency of multi‐crystalline silicon (mc‐Si) based solar cells. We apply the deep level transient spectroscopy technique to detect interface states at Σ3 and Σ9 GBs in mc‐Si. The density of interface states close to midgap is found comparable for both as‐grown GBs. Gettering or hydrogenation leads to shallower states with a smaller capture cross section and lower density. Recombination activity reduction for Σ3 GBs is stronger than for Σ9 GBs especially after hydrogenation. Both the analysis approach and experimental results could be applied for a specific GB engineering of mc‐Si based solar cells. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Gold-catalysed synthesis of amino acid-derived 2,5-disubstituted oxazoles

Amino acid-derived propargylic amides are cyclised in a one-pot, Au(III)-catalysed operation to yield 5-bromomethyl oxazoles. These compounds are further elaborated to bis-heterocycles, dipeptide mimics and more.     

Triethylamine-Mediated Transformation of Phosphonates into Phosphonamidates

Organophosphorus compounds such as phosphonamidates are gaining attention across different fields of chemistry, with interesting applications as pharmaceuticals, or pesticides. However, practical application of phosphonamidates is complicated by their difficult syntheses which often involve expensive or unstraightforward reagents and harsh conditions. To remedy these issues, we present a flexible, room temperature synthesis for novel P-alkylphosphonamidates without the need for intermediary purification. Commonly available phosphonates are first chlorinated by use of oxalyl chloride and phosphonylaminium salts are used to mediate the harsh reactivity of phosphonochloridates, giving rise to the desired products. We demonstrate the compatibility of our protocol with primary and secondary amines, as well as with different phosphonate esters. The proposed pathway also enables the synthesis of primary phosphonamidates using ammonium acetate as a cheap and safe alternative for ammonia. In future research, this protocol will also enable the synthesis of bioactive targets that are incompatible with current protocols.     

Chiral alignment of OPV chromophores: exploitation of the ureidophthalimide-based foldamer

The ability of foldamers to adopt a secondary structure in solution has been exploited to organize peripheral functionality. Our previously reported poly(ureidophthalimide) foldamer proved to be an excellent scaffold for the chiral organization of peripherally positioned oligo(p-phenylenevinylene) (OPV) chromophores. Facile high-yielding synthesis gave access to the required OPV-decorated building blocks. A condensation polymerization provided polymers of sufficient length to allow construction of a helical architecture comprising several turns. Short and long chains were separated by chromatography. Circular dichroism studies in THF of the longer chains indicate the presence of helically arranged OPVs. However, such an effect is not observed in CHCl3. Remarkable are the measurements of the OPV foldamers in heptane. A bisignate Cotton effect is observed in heptane of a sample with a THF history. No Cotton effect is observed in heptane of a sample with a CHCl3 history. In this example of supramolecular synthesis, the solvent dictates the expression of supramolecular chirality in a secondary structure. The short-chain oligomeric fractions that are unable to create a full turn revealed on scanning tunneling microscopy analysis the presence of circular architectures at the graphite/1-phenyloctane interface. This is in full agreement with the proposed conformation of the decorated foldamers.     

以MH2(M=Ti,Zr)为原料反应烧结制备MB2-SiC复相陶瓷

分别以TiH2,ZrH2为原料,结合原位反应与脉冲电流辅助烧结制备了TiB2-SiC及ZrB2-SiC复相陶瓷.研究发现,所制备的复相陶瓷表现出一定的织构化现象,TiB2及ZrB2晶粒在反应烧结过程中其(001)面沿垂直压力和电流方向生长.金属氢化物粉体的粒径大小对复相陶瓷的致密化及微结构有较大影响:粒径越小越有利于陶瓷的致密化和硼化物晶粒的定向生长.由于金属硼化物的定向,复相陶瓷的机械性能表现出各向异性.TiB2-SiC复相陶瓷具有较高的断裂韧性,最高可达7.3 MPa·m1/2,而ZrB2-SiC复相陶瓷具有更高的抗弯强度(937 MPa).     

(Thio)ureido anion receptors based on a 1,3-alternate oxacalix[2]arene[2]pyrimidine scaffold

In pursuit of highly preorganized macrocyclic host molecules for the complexation of anions, a series of oxacalix[2]arene[2]pyrimidine-based bis(thio)ureido receptors were synthesized and fully characterized. The pincer-like 1,3-alternate conformation of the oxacalix[4]arene scaffold, essential for an efficient host-guest interaction, was visualized by single-crystal X-ray analysis and supported by variable-temperature NMR studies. The anion binding properties of the receptors were evaluated via (1)H NMR titration experiments, showing intermolecular interactions with H(2)PO(4)(-), AcO(-), BzO(-), and Cl(-) ions. The host molecule bearing 4-nitrophenyl substituents on the bisurea binding pocket showed association constants in the range of 200-400 M(-1) in the strongly competitive solvent mixture of DMSO/0.5% H(2)O.     

Assessment of the illumination dependency of Al2O3 and SiO2 rear‐passivated p‐type silicon solar cells

This Letter discusses an important difference between positively charged SiO₂ and negatively charged Al₂O₃ rear‐passivated p‐type Si solar cells: their illumination level dependency. For positively charged SiO₂ rear‐passivated p‐type Si solar cells, a loss in short circuit current (J_SC) and open circuit voltage (V_OC) as a function of illumination level is mainly caused by parasitic shunting and a decrease in surface recombination, respectively. Hence, the relative loss in cell conversion efficiency, J_SC, and V_OC as a function of the illumination level for SiO₂ compared to Al₂O₃ rear‐passivated p‐type Si solar cells has been measured and discussed. Subsequently, an exponential decay fit of the loss in cell efficiency is applied in order to estimate the difference in the energy output for both cell types in three different territories: Belgium (EU), Seattle and Austin (US). The observed trends in the difference in energy output between both cells, as a function of time of the year and region, are as expected and discussed. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Precise Block‐Copolymers by Efficient Coupling of End‐Functionalized Polymers Using Phosgene

Summary: We report the synthesis of well‐defined block copolymers by covalent coupling of hydroxy end‐functionalized polymers. Using the high volatility of the coupling agent phosgene as compared to the solvent, very high conversion (up to 96%) is obtained in a one‐pot reaction with as little as 10⁻⁵ moles of each of the reacting polymers, even without prior purification of the as‐received reagents. This has potential as an alternative to the currently practiced method of sequential living polymerization of constituent monomers, with the added advantage of direct knowledge and control over the length distribution of each block.

Coupling of end‐functionalized polymers using phosgene to form block copolymers of controlled composition.     

Evidence for the isomerization and decarboxylation in the photoconversion of the red fluorescent protein DsRed

Recently, it has been shown that the red fluorescent protein DsRed undergoes photoconversion on intense irradiation, but the mechanism of the conversion has not yet been elucidated. Upon irradiation with a nanosecond-pulsed laser at 532 nm, the chromophore of DsRed absorbing at 559 nm and emitting at 583 nm (R form) converts into a super red (SR) form absorbing at 574 nm and emitting at 595 nm. This conversion leads to a significant change in the fluorescence quantum yield from 0.7 to 0.01. Here we demonstrate that the photoconversion is the result of structural changes of the chromophore and one amino acid. Absorption, fluorescence, and vibrational spectroscopy as well as mass spectrometry suggest that a cis-to-trans isomerization of the chromophore and decarboxylation of a glutamate (E215) take place upon irradiation to form SR. At the same time, another photoproduct (B) with an absorption maximum at 386 nm appears upon irradiation. This species is assigned as a protonated form of the DsRed chromophore. It might be a mixture of several protonated DsRed forms as there is at least two ways of formation. Furthermore, the photoconversion of DsRed is proven to occur through a consecutive two-photon absorption process. Our results demonstrate the importance of the chromophore conformation in the ground state on the brightness of the protein as well as the importance of the photon flux to control/avoid the photoconversion process.     

Total synthesis and initial structure-function analysis of the potent V-ATPase inhibitors salicylihalamide A and related compounds

Salicylihalamide A is the first member of a growing class of macrocyclic salicylate natural products that induce a variety of interesting phenotypes in cultured mammalian cells. Salicylihalamide A was reported to be a unique and highly differential cytotoxin and a potent inhibitor of the mammalian vacuolar (H(+))-ATPase. The total synthesis of both enantiomers of salicylihalamide A, a revision of the absolute configuration assigned to the natural product, and extensive structure-function studies with synthetic salicylihalamide variants are reported. These studies were possible only due to a highly efficient synthetic strategy that features (1) a remarkably E-selective ring-closing olefin metathesis to construct the 12-membered benzolactone skeleton 29, (2) a mild stereocontrolled elaboration to E-alkenyl isocyanate 41, and (3) addition of carbon, oxygen, and sulfur nucleophiles to isocyanate 41 to obtain salicylihalamide A and congeners. We demonstrate for the first time that salicylihalamide A is a potent inhibitor of fully purified reconstituted V-ATPase from bovine brain, and have identified several similarly potent side chain modified derivatives, including salicylihalamide dimers 43-45. In combination, these studies have laid the foundation for ongoing studies aimed at a comprehensive understanding of salicylihalamide's mode-of-action, of potential relevance to the development of lead compounds for the treatment of osteoporosis and cancer.