Laser illumination for manipulation of hydrogen charge states in silicon solar cells

This Letter investigates the important parameters of illumination for control of hydrogen charge states in p‐type silicon solar cells. Through variations in the wavelength and intensity of illumination, evidence is provided for the importance of the neutral charge state of interstitial hydrogen, H⁰, for the passivation of defects in upgraded metallurgical grade (UMG) silicon. It is shown that through this approach minority carrier lifetimes may be achieved in excess of those realised through previous techniques, resulting in open‐circuit voltages (iV_OC) over 710 mV. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Concurrent Block Copolymer Polymersome Stabilization and Bilayer Permeabilization by Stimuli‐Regulated “Traceless” Crosslinking

The fabrication of block copolymer (BCP) vesicles (polymersomes) exhibiting synchronized covalent crosslinking and bilayer permeabilization remains a considerable challenge as crosslinking typically leads to compromised membrane permeability. Herein it is demonstrated how to solve this dilemma by employing a stimuli‐triggered crosslinking strategy with amphiphilic BCPs containing photolabile carbamate‐caged primary amines. Upon self‐assembling into polymersomes, light‐triggered self‐immolative decaging reactions release primary amine moieties and extensive amidation reactions then occur due to suppressed amine pK_a within hydrophobic milieu. This leads to serendipitous vesicle crosslinking and the process is associated with bilayer hydrophobicity‐to‐hydrophilicity transition and membrane permeabilization.     

Titanium-Based Superlattice with Fe(III)-Regulable Bandgap and Performance for Optimal and Synergistic Sonodynamic–Chemotherapy Guided by Magnetic Resonance Imaging

Superlattices have considerable potential as sonosensitizers for cancer therapy because of their flexible and tunable band gaps, although they have not yet been reported. In this study, a Ti-based organic–inorganic superlattice with good electron–hole separation was synthesized, which consisted of orderly layered superlattices of 2,2′-bipyridine-5,5′-dicarboxylic acid (BPDC) and Ti−O layers. In addition, the superlattice was coordinated with Fe(III) and encapsulated doxorubicin (DOX) to prepare Ti-BPDC@Fe@DOX@PEG (TFDP) after biocompatibility modification. TFDP can realize the simultaneous generation of reactive oxygen species and release of DOX under ultrasound irradiation. Moreover, adjusting the Fe(III) content can effectively modulate the band gap of the superlattice and increase the efficiency of sonodynamic therapy (SDT). The mechanisms underlying this modulation were explored. TFDP with Fe(III) can also be used as a contrast agent for magnetic resonance imaging (MRI). Both in vitro and in vivo experiments demonstrated the ability of TFDP to precisely treat cancer using MRI-guided SDT/chemotherapy. This study expands the applications of superlattices as sonosensitizers with flexible and tailored modifications and indicates that superlattices are promising for precise and customized treatments.     

Impact of substrate temperature and film thickness on the interfacial evolution during atomic layer deposition of HfO2 on InP

The effects of both the deposition temperature and the HfO₂ film thickness on the interfacial layer (IL) evolution were studied when tetrakis(ethylmethylamino)hafnium and H₂O based atomic layer deposition (ALD) was performed on InP substrates. While the self‐cleaning effect resulted in an IL‐free structure after formation of ～2 nm thick HfO₂ at 200 °C and 250 °C, substantial IL growth occurred at 300 °C, probably due to simultaneous InP oxidation. Following further growth to ～8 nm at 300 °C, the IL was almost removed and, in particular, a significant In incorporation into the HfO₂ film was observed, which was attributed to IL decomposition and subsequent out‐diffusion of the constituent elements. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Modulated structure and molecular dissociation of solid chlorine at high pressures

Among diatomic molecular halogen solids, high pressure structures of solid chlorine (Cl(2)) remain elusive and least studied. We here report first-principles structural search on solid Cl(2) at high pressures through our developed particle-swarm optimization algorithm. We successfully reproduced the known molecular Cmca phase (phase I) at low pressure and found that it remains stable up to a high pressure 142 GPa. At 150 GPa, our structural searches identified several energetically competitive, structurally similar, and modulated structures. Analysis of the structural results and their similarity with those in solid Br(2) and I(2), it was suggested that solid Cl(2) adopts an incommensurate modulated structure with a modulation wave close to 2∕7 in a narrow pressure range 142-157 GPa. Eventually, our simulations at >157 GPa were able to predict the molecular dissociation of solid Cl(2) into monatomic phases having body centered orthorhombic (bco) and face-centered cubic (fcc) structures, respectively. One unique monatomic structural feature of solid Cl(2) is the absence of intermediate body centered tetragonal (bct) structure during the bco → fcc transition, which however has been observed or theoretically predicted in solid Br(2) and I(2). Electron-phonon coupling calculations revealed that solid Cl(2) becomes superconductors within bco and fcc phases possessing a highest superconducting temperature of 13.03 K at 380 GPa. We further probed the molecular Cmca → incommensurate phase transition mechanism and found that the softening of the A(g) vibrational (rotational) Raman mode in the Cmca phase might be the driving force to initiate the transition.     

Metal-based impurities in graphenes: application for electroanalysis

We show here that metallic impurities presented in graphenes prepared from graphite can be usefully employed for electroanalysis. We demonstrate that cumene hydroperoxide electrochemical reduction on graphene containing iron-based impurities provides significantly larger voltammetric currents than the same experiment using iron oxide nanoparticles. This opens doors for turning metallic impurities into potentially useful components of graphene based electrochemical systems.     

Analytical method for the accurate determination of tricothecenes in grains using LC-MS/MS: a comparison between MRM transition and MS3 quantitation

The current food crisis demands unambiguous determination of mycotoxin contamination in staple foods to achieve safer food for consumption. This paper describes the first accurate LC-MS/MS method developed to analyze tricothecenes in grains by applying multiple reaction monitoring (MRM) transition and MS(3) quantitation strategies in tandem. The tricothecenes are nivalenol, deoxynivalenol, deoxynivalenol-3-glucoside, fusarenon X, 3-acetyl-deoxynivalenol, 15-acetyldeoxynivalenol, diacetoxyscirpenol, and HT-2 and T-2 toxins. Acetic acid and ammonium acetate were used to convert the analytes into their respective acetate adducts and ammonium adducts under negative and positive MS polarity conditions, respectively. The mycotoxins were separated by reversed-phase LC in a 13.5-min run, ionized using electrospray ionization, and detected by tandem mass spectrometry. Analyte-specific mass-to-charge (m/z) ratios were used to perform quantitation under MRM transition and MS(3) (linear ion trap) modes. Three experiments were made for each quantitation mode and matrix in batches over 6 days for recovery studies. The matrix effect was investigated at concentration levels of 20, 40, 80, 120, 160, and 200 μg kg(-1) (n = 3) in 5 g corn flour and rice flour. Extraction with acetonitrile provided a good overall recovery range of 90-108% (n = 3) at three levels of spiking concentration of 40, 80, and 120 μg kg(-1). A quantitation limit of 2-6 μg kg(-1) was achieved by applying an MRM transition quantitation strategy. Under MS(3) mode, a quantitation limit of 4-10 μg kg(-1) was achieved. Relative standard deviations of 2-10% and 2-11% were reported for MRM transition and MS(3) quantitation, respectively. The successful utilization of MS(3) enabled accurate analyte fragmentation pattern matching and its quantitation, leading to the development of analytical methods in fields that demand both analyte specificity and fragmentation fingerprint-matching capabilities that are unavailable under MRM transition.     

Characterization of activation energy distribution for ultraviolet irradiation of T-rich oligonucleotide using high-performance liquid chromatography electrospray ionization mass spectrometry tandem mass spectrometry

Exposure to solar UV radiation gives rise to mutations that may lead to skin cancer of human being. Series of experiments were carried out in order to reveal activation energy distribution of DNA mutation caused by UV radiation. The T-rich oligonucleotides were exposed to UV radiation with increasing intensity for different durations. Photoproducts of T-rich oligonucleotide were investigated using ion-pair reversed-phase high-performance liquid chromatography/tandem electrospray ionization mass spectrometry (IP-RP-HPLC/ESI-MS) at room temperature. Two photoproducts of T-rich oligonucleotide were cis-syn cyclobutane pyrimidine dimmer (T[c,s]T) and the pyrimidine(6,4)pyrimidone product (T[6,4]T). Activation energy distribution of DNA mutation was calculated using a commercial kinetics analysis programs by Robert L. Braun and Alan K. Burnham , Lawrance Livermore International Laboratory (version 2.4.1). To use the software for deriving the kinetics parameters, the factor T (temperature) in the software was substituted with k1R, in which k1 is a factor, R is radiation intensity. The activation energy derived ranges from 55 to 110 kJ mol(-1). By the same software, those kinetics parameters were extrapolated to natural UV radiation process to predict DNA damage degree without the DNA repair process.     

Analysis of single nucleotide polymorphism sites in exon 4 of the p53 gene using high-performance liquid chromatography electrospray ionization mass spectrometry tandem mass spectrometry

Three groups of four oligonucleotides with special single nucleotide polymorphisms (SNP) sites in exon 4 of the p53 gene were analyzed with ion-pair reversed-phase high-performance liquid chromatography electrospray ionization mass spectrometry tandem mass spectrometry. The retention order of four oligonucleotides with SNPs was C < G < A < T, regardless of whether the polymorphisms were at the 3' end, the 5' end, or the middle of the oligonucleotides. The charge state of the molecular ion affects the MS/MS spectra of the oligonucleotides. SNPs at the 3' end can be easily identified from the fragmentation pattern of the 2- charge state, but not from the 3- charge state, especially from the w1 fragment. The single base may be taken as the symbol of the 5' end SNP site derived from [M3H]2, but not from the [M3H]2 charge state. The oligonucleotides with SNPs in the middle were also determined from the [M2H]2 precursor ion.     

Improvement of 2,4-dinitrophenylhydrazine derivatization method for carbon isotope analysis of atmospheric acetone

Through simulation experiments of atmospheric sampling, a method via 2,4-dinitrophenylhydrazine (DNPH) derivatization was developed to measure the carbon isotopic composition of atmospheric acetone. Using acetone and a DNPH reagent of known carbon isotopic compositions, the simulation experiments were performed to show that no carbon isotope fractionation occurred during the processes: the differences between the predicted and measured data of acetone-DNPH derivatives were all less than 0.5 per thousand. The results permitted the calculation of the carbon isotopic compositions of atmospheric acetone using a mass balance equation. In this method, the atmospheric acetone was collected by a DNPH-coated silica cartridge, washed out as acetone-DNPH derivatives, and then analyzed by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). Using this method, the first available delta13C data of atmospheric acetone are presented.