On the ambiguity of 1,3,2-benzodiazaboroles as donor/acceptor functionalities in luminescent molecules

A series of 1,3-bis(perfluoroaryl)-2-(hetero)aryl-1,3,2-benzodiazaboroles, 1,3-FAr2-2-Ar-1,3,2-N2BC6H4 (Ar = Ph, FAr = C6F5 5; Ar = Ph, FAr = 4-C5F4N 6; Ar = Ph, FAr = 4-NCC6F4 7; Ar = 2-C4H3S, FAr = C6F5 8; Ar = 2-C4H3S, FAr = 4-C5F4N 9; Ar = 2-C4H3S, FAr = 4-NCC6F4 10), were synthesised by cyclocondensation of the adducts PhBBr2·PPh3 or 2-thienylBBr2·PPh3 with N,N′-bis(perfluoroaryl)-o-phenylenediamines in the presence of 2,2,6,6-tetramethylpiperidine. Similar treatments of the PPh3 adducts of 4-(1′,3′-diethyl-1′,3′,2′-benzodiazaborolyl)-phenyldibromoborane with the corresponding diamines gave rise to the push–pull compounds, C6H4(NEt)2B-1,4-C6H4-B(NFAr)2C6H4 (FAr = C6F5 11; 4-C5F4N 12) and C6H4(NEt)2B-2,5-C4H2S-B(NFAr)2C6H4 (FAr = C6F5 13; 4-C5F4N 14). The X-ray structures of 8, 11, 12 and 13 were determined. Electronic structure calculations reveal that the LUMOs are located at the perfluoroaryl groups in 5–14; thus the fluorinated benzodiazaborolyl groups are considered as electron-withdrawing moieties. These moieties differ from alkylated benzodiazaborolyl groups which are regarded as donors. The emission spectra for 5–14 show charge transfer bands with significant solvatochromism and large Stokes shifts (6100–12500 cm−1 in cyclohexane and 8900–15900 cm−1 in CH2Cl2). The emissions of the benzodiazaboroles, 5–10, arise from a different charge transfer (CT) process to the local charge transfer (LCT) process typically found in many fluorescent benzodiazaboroles. This novel remote charge transfer (RCT) process involving the perfluoroaryl groups is supported by CAM-B3LYP computations. The push–pull systems 11–14 here give fluorescent emissions with moderate to high fluorescence quantum yields (65–97%) that arise from the usual LCT process only

A high proliferation rate measured by cyclin A predicts a favourable chemotherapy response in soft tissue sarcoma patients

A small but not insignificant number of patients experience a prolonged survival after treatment of metastatic soft tissue sarcoma. This must be weighed against the majority of the patients who benefit little from the therapy, but nevertheless experience its side-effects. It would therefore be of utmost importance to be able to screen for those patients who respond to the treatment. Since proliferating cells are more sensitive to chemotherapy than non-proliferative cells, we measured the proliferation rate of the primary tumour of 55 soft tissue sarcoma patients with locally advanced or metastatic disease by determining the flow cytometric S phase fraction and immunohistochemical Ki-67 and cyclin A scores. S phase fraction or Ki-67 score did not predict chemotherapy response or progression-free survival. A high cyclin A score, however, correlated with a better chemotherapy response (P = 0.02) and longer progression-free survival time (P = 0.04). Our results suggest that a high cyclin A score predicts chemotherapy sensitivity. © 1999 Cancer Research Campaig

Comparison of the Ki-67 score and S-phase fraction as prognostic variables in soft-tissue sarcoma

Immunohistochemically determined Ki-67 scores and flow cytometrically determined S-phase fractions were successfully evaluated from the primary tumours of 123 patients with soft-tissue sarcoma. All patients had either limb or superficial trunk tumours. Ki-67 score correlated strongly with ploidy, S-phase fraction and grade. Ki-67 did not correlate with the size of the primary tumour. When analysed as a continuous variable, Ki-67 was a stronger predictor of both metastasis-free survival and disease-specific overall survival (P= 0.003 and 0.04 respectively) than was the S-phase fraction (P= 0.06 and 0.07 respectively). We tested the relevance of different cut-point values by dividing the whole material into two parts at every 10% (e.g. 10% of patients vs. the remaining 90%, 20% vs. 80%, etc.). We counted the relative risk and confidence interval at all these cut-off points. Ki-67 had good prognostic discriminating power irrespective of the cut-point value, but S-phase fraction lost its prognostic power at higher cut-point values. In conclusion, we found that Ki-67 is a useful prognostic tool in the treatment of soft-tissue sarcoma patients irrespective of the cut-point value. S-phase fraction can be used at lower cut-point values. © 1999 Cancer Research Campaig

A test on Ellenberg indicator values in the Mediterranean evergreen woods (Quercetea ilicis)

The consistency and reliability of Ellenberg’s indicator values (Eiv) as ecological descriptors of the Mediterranean evergreen vegetation ascribed to the phytosociological class Quercetea ilicis have been checked on a set of 859 phytosociological relevés × 699 species. Diagnostic species were identified through a Twinspan analysis and their Eiv analyzed and related to the following independent variables: (1) annual mean temperatures, (2) annual rainfall. The results provided interesting insights to disentangle the current syntaxonomical framework at the alliance level demonstrating the usefulness of ecological indicator values to test the efficiency and predictivity of the phytosociological classification

Understanding Communication of Sustainability Reporting: Application of Symbolic Convergence Theory (SCT)

The purpose of this paper is to investigate the nature of rhetoric and rhetorical strategies that are implicit in the standalone sustainability reporting of the top 24 companies of the Fortune 500 Global. We adopt Bormann’s (Q J Speech 58(4):396–407, 1972) SCT framework to study the rhetorical situation and how corporate sustainability reporting (CSR) messages can be communicated to the audience (public). The SCT concepts in the sustainability reporting’s communication are subject to different types of legitimacy strategies that are used by corporations as a validity and legitimacy claim in the reports. A content analysis has been conducted and structural coding schemes have been developed based on the literature. The schemes are applied to the SCT model which recognizes the symbolic convergent processes of fantasy among communicators in a Society. The study reveals that most of the sample companies communicate fantasy type and rhetorical vision in their corporate sustainability reporting. However, the disclosure or messages are different across locations and other taxonomies of the SCT framework. This study contributes to the current CSR literature about how symbolic or fantasy understandings can be interpreted by the users. It also discusses the persuasion styles that are adopted by the companies for communication purposes. This study is the theoretical extension of the SCT. Researchers may be interested in further investigating other online communication paths, such as human rights reports and director’s reports

Syntheses and Reductions of C-Dimesitylboryl-1,2-dicarba-closo-dodecaboranes

Two C-dimesitylboryl-1,2-dicarba-closo-dodecaboranes, 1-(BMes2)-2-R-1,2-C2B10H10 (1, R = H, 2, R = Ph), were synthesised by lithiation of 1,2-dicarba-closo-dodecaborane and 1-phenyl-1,2-dicarba-closo-dodecaborane, respectively, with n-butyllithium and subsequent reaction with fluorodimesitylborane. These novel compounds were structurally characterised by X-ray crystallography. Compounds 1 and 2 are hydrolysed on prolonged exposure to air to give mesitylene and boronic acids 1-(B(OH)2)-2-R-1,2-C2B10H10 (3, R = H, 4, R = Ph respectively). Addition of fluoride anions to 1 and 2 resulted in boryl-carborane bond cleavage to give dimesitylborinic acid HOBMes2. UV absorption bands at 318–333 nm were observed for 1 and 2 corresponding to local π–π*-transitions within the dimesitylboryl groups while visible emissions at 541–664 nm with Stokes shifts of 11920–16170 cm−1 were attributed to intramolecular charge transfer transitions between the mesityl and cluster groups. Compound 2 was shown by cyclic voltammetry to form a stable dianion on reduction. NMR spectra for the dianion [2]2− were recorded from solutions generated by reductions of 2 with alkali metals and compared with NMR spectra from reductions of 1,2-diphenyl-ortho-carborane 5. On the basis of observed and computed 11B NMR shifts, these nido-dianions contain bowl-shaped cluster geometries. The carborane is viewed as the electron-acceptor and the mesityl group is the electron-donor in C-dimesitylboryl-1,2-dicarba-closo-dodecaboranes