Boron difluorides with formazanate ligands:redox-switchable fluorescent dyes with large stokes shifts

The synthesis of a series of (formazanate)boron difluorides and their 1-electron reduction products is described. The neutral compounds are fluorescent with large Stokes shifts. DFT calculations suggest that a large structural reorganization accompanies photoexictation and accounts for the large Stokes shift. Reduction of the neutral boron difluorides occurs at the ligand and generates the corresponding radical anions. These complexes are non-fluorescent, allowing switching of the emission by changing the ligand oxidation state

Kallikrein-related peptidase 4 (KLK4) mRNA predicts short-term relapse in colorectal adenocarcinoma patients

The members of the kallikrein-related peptidase (KLK) family are aberrantly expressed in cancer, including colorectal adenocarcinoma. KLK4 is an endogenous activator of protease-activated receptor 1 (PAR1) in HT-29 colorectal adenocarcinoma cells, inducing PAR1 signaling and subsequent ERK1/2 activation. The aim of this study was to analyze . KLK4 mRNA expression in colorectal adenocarcinoma and to examine its prognostic value as a novel molecular tissue biomarker in this malignancy. Therefore, total RNA was isolated from primary tumors of 81 colorectal adenocarcinoma patients, cDNA was prepared, and . KLK4 mRNA expression analysis was performed using quantitative real-time PCR. . KLK4 mRNA was significantly associated with the Dukes stage, tumor invasion, size, and histological grade. Survival analysis demonstrated that . KLK4 mRNA expression constitutes an unfavorable prognostic biomarker in colorectal adenocarcinoma, predicting poor disease-free survival (DFS), independently of the nodal status and tumor size. Furthermore, . KLK4 mRNA predicts short-term relapse of lymph node-negative patients or those with tumors of early Dukes stage. In conclusion, . KLK4 mRNA expression can be regarded as a novel potential tissue biomarker in colorectal adenocarcinoma. © 2012 Elsevier Ireland Ltd

Ab Initio Wave Function-Based Determination of Element Specific Shifts for the Efficient Calculation of X-ray Absorption Spectra of Main Group Elements and First Row Transition Metals

In this study, a detailed calibration of the performance of modern ab initio wave function methods in the domain of X-ray absorption spectroscopy (XAS) is presented. It has been known for some time that for a given level of approximation, for example, using time-dependent density functional theory (TD-DFT) in conjunction with a given basis set, there are systematic deviations of the calculated transition energies from their experimental values that depend on the functional, the basis set, and the chosen treatment of scalar relativistic effects. This necessitates a linear correlation for a given element/functional/basis set combination to be established before chemical applications can be performed. This is a laborious undertaking since it involves sourcing trustworthy experimental data, lengthy geometry optimizations, and detailed comparisons between theory and experiment. In this work, reference values for the element-specific shifts of all the first-row transition metal atoms and the main group elements C, N, O, F, Si, P, S, and Cl have been computed by using a protocol that is based on the complete active space configuration interaction in conjunction with second-order N-electron valence state perturbation theory (CASCI/NEVPT2). It is shown that by extrapolating the results to the basis set limit of the method and taking into account scalar relativistic effects via the second-order Douglas–Kroll–Hess (DKH2) corrections, the predicted element shifts are on average less than 0.75 eV across all the absorption edges and a very good agreement between theory and experiment in all the studied XAS cases is observed. The transferability of these errors to molecular systems is thoroughly investigated. The constructed CASCI/NEVPT2 database of element shifts is used to evaluate the performance and to automatically calibrate prior to comparison with the experiment two commonly used methods in X-ray spectroscopy, namely, DFT/Restricted open shell configuration interaction singles (DFT/ROCIS) and TD-DFT methods

CCDC 1471288: Experimental Crystal Structure Determination

Related Article: M.-C. Chang, A. Chantzis, D. Jacquemin, E. Otten|2016|Dalton Trans.|45|9477|doi:10.1039/C6DT01226D,An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

CCDC 1471289: Experimental Crystal Structure Determination

Related Article: M.-C. Chang, A. Chantzis, D. Jacquemin, E. Otten|2016|Dalton Trans.|45|9477|doi:10.1039/C6DT01226D,An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

CCDC 1471287: Experimental Crystal Structure Determination

Related Article: M.-C. Chang, A. Chantzis, D. Jacquemin, E. Otten|2016|Dalton Trans.|45|9477|doi:10.1039/C6DT01226D,An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.