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Liu, R.; Azenkeng, A.; Zhouc, D.; Li, Y.; Glusac, K.D.; Sun, W. |
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Tuning Photophysical Properties and Improving Nonlinear Absorption of Pt(II) Diimine Complexes with Extended π-Conjugation in the Acetylide Ligands |
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2013 |
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The Journal of Physical Chemistry A |
Abbreviated Journal |
J. Phys. Chem. A |
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130227065352006 |
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NMR FID Relaxation |
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Tuning Photophysical Properties and Improving Nonlinear Absorption of Pt(II) Diimine Complexes with Extended π-Conjugation in the Acetylide Ligands
Abstract
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Rui Liu , Alexander Azenkeng , Dapeng Zhouc §, Yuhao Li , Ksenija D. Glusac §, and Wenfang Sun *
Department of Chemistry and Biochemistry, North Dakota State University, Fargo, North Dakota 58108-6050, United States
Energy and Environmental Research Center, University of North Dakota, Grand Forks, North Dakota 58202-9018, United States
§ Department of Chemistry, Bowling Green State University, Bowling Green, Ohio 43403-0001, United States
J. Phys. Chem. A, Article ASAP
DOI: 10.1021/jp309841x
Publication Date (Web): February 11, 2013
Copyright © 2013 American Chemical Society
*E-mail: Wenfang.Sun@ndsu.edu. Phone: 701-231-6254. Fax: 701-231-8831.
Abstract
Abstract Image
Two new Pt(II) 4,4′-di(5,9-diethyltridecan-7-yl)-2,2′-bipyridine complexes (1 and 2) bearing 9,9-diethyl-2-ethynyl-7-(2-(4-nitrophenyl)ethynyl)-9H-fluorene ligand and N-(4-(2-(9,9-diethyl-7-ethynyl-9H-fluoren-2-yl)ethynyl)phenyl)-N-phenylbenzeneamine ligand, respectively, were synthesized and characterized. Their photophysical properties were investigated systematically by UVvis absorption, emission, and transient absorption (TA) spectroscopy, and the nonlinear absorption was studied by nonlinear transmission technique. Theoretical TD-DFT calculations using the CAM-B3LYP functional were carried out to determine the nature of the singlet excited electronic states and to assist in the assignment of significant transitions observed in experiments. Complex 1 exhibits an intense, structureless absorption band at ca. 397 nm in CH2Cl2 solution, which is attributed to mixed metal-to-ligand charge transfer (1MLCT)/ligand-to-ligand charge transfer (1LLCT)/intraligand charge transfer (1ILCT)/1π,π* transitions, and two 1MLCT/1LLCT transitions in the 300350 nm spectral region. Complex 2 possesses an intense acetylide ligand localized 1π,π* absorption band at ca. 373 nm and a moderately intense 1MLCT/1LLCT tail above 425 nm in CH2Cl2. Both complexes are emissive in solution at room temperature, with the emitting state being tentatively assigned to the predominant 3π,π* state for 1, whereas the emitting state of 2 exhibits a switch from 3π,π* state in high-polarity solvents to 3MLCT/3LLCT state in low-polarity solvents. Both 1 and 2 exhibit strong singlet excited-state TA in the visible to NIR region, where reverse saturable absorption (RSA) is feasible. The spectroscopic studies and theoretical calculations indicate that the photophysical properties of these Pt complexes can be tuned drastically by extending the π-conjugation of the acetylide ligands. In addition, strong RSA was observed at 532 nm for nanosecond (ns) laser pulses from 1 and 2, demonstrating that the RSA of the Pt(II) diimine complexes can be improved by extending the π-conjugation of the acetylide ligands. |
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13970 |
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Antonelli, A.; Bocci, G.; Fallahi, P.; La Motta, C.; Martina Ferrari, S.; Mancusi, C.; Fioravanti, A.; Di Desidero, T.; Sartini, S.; Corti, A.; Piaggi, S.; Materazzi, G.; Spinelli, C.; Fontanini, G.; Danesi, R.; Da Settimo, F.; Miccoli, P. |
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CLM3, a multitarget tyrosine kinase inhibitor with antiangiogenic properties, is active against primary anaplastic thyroid cancer in vitro and in vivo |
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Journal Article |
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2014 |
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The Journal of Clinical Endocrinology and Metabolism |
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J Clin Endocrinol Metab |
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jc20132321 |
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Context and Objective. We have studied the antitumor activity of a “pyrazolo[3,4-d]pyrimidine” compound (CLM3) proposed for a multiple signal transduction inhibition [including the RET tyrosine kinase, epidermal growth factor receptor, vascular endothelial growth factor (VEGF) receptor (VEGFR) and with antiangiogenic activity], in primary anaplastic thyroid cancer (ATC) cells, in the human cell line 8305C (undifferentiated thyroid cancer) and in an ATC-cell line (AF). Design and Main Outcome Measures. CLM3 was tested: in primary ATC cells at the concentrations of 5, 10, 30, 50 muM; in 8305C cells, and in AF cells, at 1, 5, 10, 30, 50 or 100 muM; in AF cells in CD nu/nu mice. Results. CLM3 significantly inhibited proliferation of 8305C and AF cells, inducing also apoptosis. A significant reduction of proliferation with CLM3 in ATC cells (P < 0.01, ANOVA) was shown. CLM3 increased the percentage of apoptotic ATC cells dose-dependently (P < 0.001, ANOVA) and inhibited migration (P < 0.01) and invasion (P < 0.001). AF-cell line was injected sc in CD nu/nu mice and tumor masses became detectable 15 days after. CLM3 (50 mg/kg/die) inhibited significantly tumor growth (starting 16 days after the beginning of treatment). CLM3 significantly decreased the VEGF-A expression and microvessel density in AF tumor tissues. Furthermore, CLM3 inhibited EGFR, AKT and ERK1/2 phosphorylation and down-regulated cyclin D1 in 8305C and AF cells. Conclusions. The antitumor and antiangiogenic activity of a “pyrazolo[3,4-d]pyrimidine” compound (CLM3) is very promising in anaplastic thyroid cancer, opening the way to a future clinical evaluation. |
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Department of Clinical and Experimental Medicine, University of Pisa, Via Savi 10, 56126, Pisa, Italy |
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0021-972X |
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PMID:24423321 |
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35477 |
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Antonelli, A.; Bocci, G.; Fallahi, P.; La Motta, C.; Martina Ferrari, S.; Mancusi, C.; Fioravanti, A.; Di Desidero, T.; Sartini, S.; Corti, A.; Piaggi, S.; Materazzi, G.; Spinelli, C.; Fontanini, G.; Danesi, R.; Da Settimo, F.; Miccoli, P. |
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Title |
CLM3, a multitarget tyrosine kinase inhibitor with antiangiogenic properties, is active against primary anaplastic thyroid cancer in vitro and in vivo |
Type |
Journal Article |
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Year |
2014 |
Publication |
The Journal of Clinical Endocrinology and Metabolism |
Abbreviated Journal |
J Clin Endocrinol Metab |
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jc20132321 |
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Context and Objective. We have studied the antitumor activity of a “pyrazolo[3,4-d]pyrimidine” compound (CLM3) proposed for a multiple signal transduction inhibition [including the RET tyrosine kinase, epidermal growth factor receptor, vascular endothelial growth factor (VEGF) receptor (VEGFR) and with antiangiogenic activity], in primary anaplastic thyroid cancer (ATC) cells, in the human cell line 8305C (undifferentiated thyroid cancer) and in an ATC-cell line (AF). Design and Main Outcome Measures. CLM3 was tested: in primary ATC cells at the concentrations of 5, 10, 30, 50 muM; in 8305C cells, and in AF cells, at 1, 5, 10, 30, 50 or 100 muM; in AF cells in CD nu/nu mice. Results. CLM3 significantly inhibited proliferation of 8305C and AF cells, inducing also apoptosis. A significant reduction of proliferation with CLM3 in ATC cells (P < 0.01, ANOVA) was shown. CLM3 increased the percentage of apoptotic ATC cells dose-dependently (P < 0.001, ANOVA) and inhibited migration (P < 0.01) and invasion (P < 0.001). AF-cell line was injected sc in CD nu/nu mice and tumor masses became detectable 15 days after. CLM3 (50 mg/kg/die) inhibited significantly tumor growth (starting 16 days after the beginning of treatment). CLM3 significantly decreased the VEGF-A expression and microvessel density in AF tumor tissues. Furthermore, CLM3 inhibited EGFR, AKT and ERK1/2 phosphorylation and down-regulated cyclin D1 in 8305C and AF cells. Conclusions. The antitumor and antiangiogenic activity of a “pyrazolo[3,4-d]pyrimidine” compound (CLM3) is very promising in anaplastic thyroid cancer, opening the way to a future clinical evaluation. |
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Department of Clinical and Experimental Medicine, University of Pisa, Via Savi 10, 56126, Pisa, Italy |
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PMID:24423321 |
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35581 |
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Ragauskas, A.; Bartusis, L.; Piper, I.; Zakelis, R.; Matijosaitis, V.; Petrikonis, K.; Rastenyte, D. |
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Improved diagnostic value of a TCD-based non-invasive ICP measurement method compared with the sonographic ONSD method for detecting elevated intracranial pressure |
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2014 |
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Neurological Research |
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Neurol Res |
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Absolute intracranial pressure,; Diagnostic reliability,; Doppler technology,; Non-invasive measurement,; Optic nerve sheath diameter |
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Objectives: To compare the diagnostic reliability of optic nerve sheath diameter (ONSD) ultrasonography with a transcranial Doppler (TCD)-based absolute intracranial pressure (ICP) value measurement method for detection of elevated ICP in neurological patients. The ONSD method has been only tested previously on neurosurgical patients. Methods: A prospective clinical study of a non-invasive ICP estimation method based on ONSD correlation with ICP and an absolute ICP value measurement method based on a two-depth TCD technology has recruited 108 neurological patients. Ninety-two of these patients have been enrolled in the final analysis of the diagnostic reliability of ONSD ultrasonography and 85 patients using the absolute ICP value measurement method. All non-invasive ICP measurements were compared with 'Gold Standard' invasive cerebrospinal fluid (CSF) pressure measurements obtained by lumbar puncture. Receiver-operating characteristic (ROC) analysis has been used to investigate the diagnostic value of these two methods. Results: The diagnostic sensitivity, specificity, and the area under the ROC curve (AUC) of the ONSD method for detecting elevated intracranial pressure (ICP >14.7 mmHg) were calculated using a cutoff point of ONSD at 5.0 mm and found to be 37.0%, 58.5%, and 0.57, respectively. The diagnostic sensitivity, specificity, and AUC for the non-invasive absolute ICP measurement method were calculated at the same ICP cutoff point of 14.7 mmHg and were determined to be 68.0%, 84.3%, and 0.87, respectively. Conclusions: The non-invasive ICP measurement method based on two-depth TCD technology has a better diagnostic reliability on neurological patients than the ONSD method when expressed by the sensitivity and specificity for detecting elevated ICP >14.7 mmHg. |
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47375 |
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Rana, F.; Shaikh, M.M.; Bowles, J. |
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Listeria meningitis and resultant symptomatic hydrocephalus complicating infliximab treatment for ulcerative colitis |
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2014 |
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JRSM Open |
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JRSM Open |
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5 |
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3 |
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2054270414522223 |
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Listeria monocytogenes, an uncommon pathogen, should be considered by clinicians as a source of sepsis and meningitis in the immunocompromised individuals, including those on anti-TNF alpha agents. Immunosuppressant agents including biologic therapies have transformed the management of various rheumatological and dermatological conditions.(1) We report a case of life-threatening L. monocytogenes sepsis and meningitis in a 75-year-old man receiving infliximab for severe ulcerative colitis (UC). |
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Great Western Hospital, Swindon, SN3 6BB, UK |
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