Advances in theory and algorithms for electronic structure calculations must be incorporated into program packages to enable them to become routinely used by the broader chemical community. This work reviews advances made over the past five years or so that constitute the major improvements contained in a new release of the Q-Chem quantum chemistry package, together with illustrative timings and applications. Specific developments discussed include fast methods for density functional theory calculations, linear scaling evaluation of energies, NMR chemical shifts and electric properties, fast auxiliary basis function methods for correlated energies and gradients, equation-of-motion coupled cluster methods for ground and excited states, geminal wavefunctions, embedding methods and techniques for exploring potential energy surfaces.

Organic semiconductors that can be fabricated by simple processing techniques and possess excellent electrical performance, are key requirements in the progress of organic electronics. Both high semiconductor charge-carrier mobility, optimized through understanding and control of the semiconductor microstructure, and stability of the semiconductor to ambient electrochemical oxidative processes are required. We report on new semiconducting liquid-crystalline thieno[3,2-b ]thiophene polymers, the enhancement in charge-carrier mobility achieved through highly organized morphology from processing in the mesophase, and the effects of exposure to both ambient and low-humidity air on the performance of transistor devices. Relatively large crystalline domain sizes on the length scale of lithographically accessible channel lengths ( approximately 200 nm) were exhibited in thin films, thus offering the potential for fabrication of single-crystal polymer transistors. Good transistor stability under static storage and operation in a low-humidity air environment was demonstrated, with charge-carrier field-effect mobilities of 0.2-0.6 cm(2) V(-1) s(-1) achieved under nitrogen.

Oesophageal cancer is one of the most aggressive cancers and is the sixth leading cause of cancer death worldwide. Approximately 70% of global oesophageal cancer cases occur in China, with oesophageal squamous cell carcinoma (ESCC) being the histopathological form in the vast majority of cases (>90%). Currently, there are limited clinical approaches for the early diagnosis and treatment of ESCC, resulting in a 10% five-year survival rate for patients. However, the full repertoire of genomic events leading to the pathogenesis of ESCC remains unclear. Here we describe a comprehensive genomic analysis of 158 ESCC cases, as part of the International Cancer Genome Consortium research project. We conducted whole-genome sequencing in 17 ESCC cases and whole-exome sequencing in 71 cases, of which 53 cases, plus an additional 70 ESCC cases not used in the whole-genome and whole-exome sequencing, were subjected to array comparative genomic hybridization analysis. We identified eight significantly mutated genes, of which six are well known tumour-associated genes (TP53, RB1, CDKN2A, PIK3CA, NOTCH1, NFE2L2), and two have not previously been described in ESCC (ADAM29 and FAM135B). Notably, FAM135B is identified as a novel cancer-implicated gene as assayed for its ability to promote malignancy of ESCC cells. Additionally, MIR548K, a microRNA encoded in the amplified 11q13.3-13.4 region, is characterized as a novel oncogene, and functional assays demonstrate that MIR548K enhances malignant phenotypes of ESCC cells. Moreover, we have found that several important histone regulator genes (MLL2 (also called KMT2D), ASH1L, MLL3 (KMT2C), SETD1B, CREBBP and EP300) are frequently altered in ESCC. Pathway assessment reveals that somatic aberrations are mainly involved in the Wnt, cell cycle and Notch pathways. Genomic analyses suggest that ESCC and head and neck squamous cell carcinoma share some common pathogenic mechanisms, and ESCC development is associated with alcohol drinking. This study has explored novel biological markers and tumorigenic pathways that would greatly improve therapeutic strategies for ESCC.

Abstract:We report herein a comparison of the photophysics of a series of polythiophenes with ionization potentials ranging from 4.8 to 5.6 eV as pristine films and when blended with 5 wt% 1-(3-methoxycarbonyl)propyl-1-phenyl-[6,6]C 61 (PCBM). Three polymers are observed to give amorphous films, attributed to a non-planar geometry of their backbone whilst the other five polymers, including poly(3-hexylthiophene), give more crystalline films. Optical excitation of the pristine films of the amorphous polymers is observed by transient absorption spectroscopy to give rise to polymer triplet formation. For the more crystalline pristine polymers, no triplet formation is observed, but rather a short-lived (~ 100 ns), broad photoinduced absorption feature assigned to polymer polarons. For all polymers, the addition of 5 wt% PCBM resulted in 70 -90% quenching of polymer photoluminescence (PL), indicative of efficient quenching of polythiophene excitons. Remarkably, despite this efficient exciton quenching, the yield of dissociated polymer + and PCBM − polarons, assayed by the appearance of a long-lived, powerlaw decay phase assigned to bimolecular recombination of these polarons, was observed to vary by over two orders of magnitude depending upon the polymer employed. In addition to this power-law decay phase, the blend films exhibited short-lived decays assigned, for the amorphous polymers, to neutral triplet states generated by geminate recombination of bound radical pairs and, for the more crystalline polymers, to the direct observation of the geminate recombination of these bound radical pairs to ground. These observations are discussed in terms of a two-step kinetic model for charge generation in polythiophene/PCBM blend films analogous to that reported to explain the observation of exciplex-like emission in poly(p-phenylenevinylene)-based blend films. Remarkably, we find a excellent correlation between the free energy difference for charge separation (ΔG CS rel ) and yield of the long-lived charge generation yield, with efficient charge generation requiring a much larger ΔG CS rel than that required to achieve efficient PL 3 quenching. We suggest this observation is consistent with a model where the excess thermal energy of the initially formed polarons pairs is necessary to overcome their coulomb binding energy. This observation has important implications for synthetic strategies to optimize organic solar cell performance, as it implies that, at least devices based on polythiophene/PCBM blend films, a large ΔG CS rel (or LUMO level offset) is required to achieve efficient charge dissociation.4

No abstract

Many software tools have been developed for the automated identification of peptides from tandem mass spectra. The accuracy and sensitivity of the identification software via database search are critical for successful proteomics experiments. A new database search tool, PEAKS DB, has been developed by incorporating the de novo sequencing results into the database search. PEAKS DB achieves significantly improved accuracy and sensitivity over two other commonly used software packages. Additionally, a new result validation method, decoy fusion, has been introduced to solve the issue of overconfidence that exists in the conventional target decoy method for certain types of peptide identification software.

Based on theoretical prediction, a g-C(3)N(4)@carbon metal-free oxygen reduction reaction (ORR) electrocatalyst was designed and synthesized by uniform incorporation of g-C(3)N(4) into a mesoporous carbon to enhance the electron transfer efficiency of g-C(3)N(4). The resulting g-C(3)N(4)@carbon composite exhibited competitive catalytic activity (11.3 mA cm(-2) kinetic-limiting current density at -0.6 V) and superior methanol tolerance compared to a commercial Pt/C catalyst. Furthermore, it demonstrated significantly higher catalytic efficiency (nearly 100% of four-electron ORR process selectivity) than a Pt/C catalyst. The proposed synthesis route is facile and low-cost, providing a feasible method for the development of highly efficient electrocatalysts.

ABSTRACT:We report the synthesis and polymerization of a novel thieno[3,2-b]thiophene-diketopyrrolopyrrolebased monomer. Copolymerization with thiophene afforded a polymer with a maximum hole mobility of 1.95 cm 2 V -1 s -1 , which is the highest mobility from a polymer-based OFET reported to date. Bulk-heterojunction solar cells comprising this polymer and PC 71 BM gave a power conversion efficiency of 5.4%. T here is considerable interest in the synthesis of narrow-bandgap conjugated polymers for use in organic photovoltaic (OPV) and organic field-effect transistor (OFET) devices. Their solution processability and mechanical properties allow access to a new generation of cheap and flexible transistors and solar devices. Current state of the art polymeric materials have allowed for the fabrication of OFETs with mobilities of ∼1 cm 2 V -1 s -1 1 and OPV devices with power conversion efficiencies (PCEs) of over 7%.2 Diketopyrrolopyrrole (DPP)-based copolymers have emerged as extremely attractive materials for both thin-film transistors and solar cell devices in recent years. The DPP core's electrondeficient nature has been exploited for the synthesis of extremely narrow band gap donor-acceptor-type materials that are wellsuited for use in OPVs with high PCEs reported from both small molecules and polymers.3-6 Furthermore, the planarity of the DPP skeleton and its ability to accept hydrogen bonds (and other types of electrostatic interactions) result in copolymers that encourage π-π stacking. Typically, these DPP-based copolymers are prepared via either Suzuki or Stille coupling of the 3,6-bis(5-bromothiophen-2-yl)-2,5-dialkylpyrrolo[3,4-c]pyrrole-1,4-(2H,5H)-dione core with the desired comonomer, which as a result means that the electron-deficient DPP unit is always flanked by two thiophenes. Variation of the comonomer has yielded polymers with extremely attractive properties for both OPV and OFET devices. For instance, copolymerization with thiophene derivatives or benzothiadiazole resulted in polymers with impressive ambipolar charge-carrier mobilities. 7,8 Recently, a copolymer of 3,6-bis(5-bromothiophen-2-yl)-N,N 0 -bis(2-octyl-1-dodecyl)-1,4-dioxopyrrolo[3,4-c]pyrrole and 2,5-bis(trimethylstannyl)thieno[3,2-b]thiophene showed an impressive hole mobility of ∼0.9 cm 2 V -1 s -1 . 9 In terms of materials for OPVs, copolymerization of the same DPP monomer (albeit having a slightly different solubilizing alkyl chain) with phenylene-1,4-diboronic acid bispinacol ester afforded a polymer that was used to fabricate OPV devices with efficiencies of ∼5.5%. 10Despite the significant number of reports on DPP-based copolymers, there have been very few studies on the effect of modifying the 3,6-bis(5-bromothiophen-2-yl)-2,5-dialkylpyrrolo-[3,4-c]pyrrole-1,4-(2H,5H)-dione monomer. One very recent example was the replacement of the flanking thiophenes by furans, which resulted in polymers with high PCEs in solar cell devices. 11 We were interested in increasing the intermolecular association of DPP-based copolymers by repla...