Bu araştırma, Avrupa Birliği'nin ufuk 2020 araştırma ve İnovasyon programından Marie Skłodowska-Curie hibe sözleşmesi kapsamında H2020-MSCA-ITN-2015/674990 "EXCILIGHT" parasal aldı. Pijama Royal Society Wolfson araştırma Merit Ödülü için teşekkürler.

dikkat: tüm ilgili malzeme güvenlik veri sayfaları (MSDS) kullanılmadan önce gözden geçirin. Birkaç sentezinde kullanılan kimyasalların son derece toksik ve kanserojen vardır. Silika jel ile çalışırken, parçacık inhalasyon önlemek için koruyucu bir solunum maskesi takılmalıdır. Lütfen tüm uygun güvenlik kuralları mühendislik kontrolleri (duman dolap) ve kişisel koruyucu ekipman (koruyucu gözlük, eldiven, önlük, tam uzunlukta pantolon, kapalı-toe ayakkabı) kullanımı gibi bir kimyasal reaksiyon gerçekleştirirken gözlemlemek.
 tüm reaktifler ve çözücüler ticari olarak satın alınan ve daha fazla herhangi bir arıtma kullanılmıştır. 1 H ve 13 C NMR spectra CDCl 3 solvent kullanarak bir 400 MHz NMR spektrometresi tarihinde kaydedildi. Proton NMR kimyasal vardiya δ değerler ppm deuterated çözücüler göreli olarak rapor edilmektedir: CDCl 3 (7.26). Verileri aşağıdaki gibi sunulmaktadır: kimyasal değişme, çeşitlilik ve constant(s) (J) kaplin vardır Hz. Multiplets bildirilen aralığında (ppm) üzerinde onlar ortaya çıktı. Karbon NMR veri karşılık gelen solvent sinyalleri CDCl 3 göre (77.16) toplanmıştır. Erime noktaları bir erime noktası cihazları kullanılarak ölçüldü. Matris yardımlı lazer desorption iyonize-zaman--kütle spektrometresi Shimadzu AXIMA-CFR Spektrometre üzerinde çalıştırmak uçuş (MALDI-TOF) (1-150 000 Da kütle aralığı).
 1. bildirilen bileşiklerin sentezi <ol><li>500 mL üç-boyun kullanarak Bileşik 1 (3,6-di-tert-butyl-9H-carbazole) sentezi 19 <ol><li>yuvarlak-alt flask, 9 - dağıtılması H-Karbazol (10.0 g, 60 mmol) nitromethane (300 mL) altında bir azot atmosferi içinde. O zaman, çinko (II) klorür (24.3 g, 180 mmol) bu çözüm.</li>
		<li>2-kloro-2-methylpropane (19,5 mL, 180 mmol) 100 mL ek huni dökün ve dropwise altında dinç karıştırmaya eklenir.</li>
		<li>6 h. için oda sıcaklığında elde edilen karışımı ilave edin</li>
		<li>İzlemek diklorometan kullanarak ince tabaka Kromatografi (TLC), ile tepki tamamlanması: hekzan 1:1 v/v bir eluent karışımı gibi. 9-H-Karbazol tüketimi sonra 100 mL çözüm nötralize etmek için su ekle.</li>
		<li>Üç kez ile diklorometan 150 mL ürün her zaman ayıklayın. Organik katman sulu katmandan ayrı ve ayrıca iki kez 150 mL su yıkayın.
		<ol><li>15 g Magnezyum sülfat ile elde edilen organik katman kuru ve solvent gri toz almak için düşük basınç altında buharlaşır.</li>
		</ol></li> <li>Kalıntı diklorometan kullanarak sütun Kromatografi tarafından arındırmak: hekzan 1:1 v/v solvent karışımı bir eluent olarak sağlanan 13.1 g (% 79) bir beyaz toz olarak bileşik 1. 
		1 karakterizasyonu bileşik: 1 H NMR (400 MHz, CDCl 3, 25 ° C, ppm): 8.12 (d, J 1,9 Hz, 2 H =), 7.78 (s b, 1 H), 7.5 (dd, J 8.5, 1.9 Hz, 2 H =), 7.33 (dd, J 5.6, 0.5 Hz, 2 H =), 1.49 (s, 18 H). 
		13 C NMR (400 MHz, CDCl 3, 25 ° C, ppm): 142.4, 138.2, 123.7, 123,4, 116.3, 110.2, 34,9, 32.2. 
		MS: m/z 279,4 (M +). 
		Erime noktası: 233-235 ° C.</li>
	</ol></li> <li>Bileşik 2 (2,8-dibromodibenzothiophene) sentezi 20 <ol><li>500 mL üç-boyun yuvarlak alt kabı kullanarak kloroform (100 mL) altında azot içinde dibenzothiophene (15,0 g, 81.3 mmol) dağıtılması atmosfer. Sonra dinç karıştırma altında 0 ° C'de dropwise Brom (9,3 mL, 180 mmol) ekleyin.</li>
		<li>Brom, tam eklenmesi sonra sıcaklığı oda sıcaklığına artırmak ve 18 h. tepki karışımı ilave edin</li>
		<li>Filtre kapalı elde edilen beyaz çökelti ve art arda ile 15 mL metanol 2,8-dibromodibenzothiophene bir verim 23 g (% 83) beyaz bir toz olarak izole etmek ve daha sonra 50 mL su ile yıka. 
		Bileşik 2 karakterizasyonu: 1 H NMR (400 MHz, CDCl 3, 25 ° C, ppm): 8.24 (d, J 2.0 Hz, 2 H =), 7,71 (d, J 8.0 Hz, 2 H =), 7.58 (d, J 2.0 Hz, 2 H =). 
		13 C NMR (400 MHz, CDCl 3, 25 ° C, ppm): 138.8, 136.3, 130.5, 124,9, 124.3, 118.8. 
		MS: m/z 342.1 (M +). 
		Erime noktası: 227-229 ° C.</li>
	</ol></li> <li>Bileşik 3 (2,8-dibromodibenzothiophene-5-dioksit) sentezi 21 <ol><li>500 mL one-boyun yuvarlak alt şişesi 2,8-dibromodibenzothiophene (21,3 g, 60 mmol) süspansiyon ile yük ve buzul Asetik asit (250 mL) ve reflü azot atmosferi altında 2 h için hidrojen peroksit çözüm (30 mL %30 (w/w) H 2 O).</li>
		<li>Oda sıcaklığında elde edilen karışıma serin ve filtre bir beyaz çökelti.</li>
		15 mL su ve 10 mL metanol 19.3 g (% 85) elde etmek için ile <li>yıkama üç kez beyaz toz. 
		Bileşik 3 karakterizasyonu: 1 H NMR (400 MHz, CDCl 3, 25 ° C, ppm): 8.22 (d, J 1,6 Hz, 2 H =), 7.70 (d, J 8.0 Hz, 2 H =), 7.57 (d, J 2 Hz, 2 H =). 
		13 C NMR (400 MHz, CDCl 3, 25 ° C, ppm): 133.3, 130.4, 129.1, 125.6, 124.8, 124.3. 
		MS: m/z 374.1 (M +). 
		Erime noktası: 360-362 ° C.</li>
	</ol></li> <li>Sentezi bileşik 4 (2,8-bis(3,6-di-tert-butyl-9H-carbazol-9-yl)dibenzothiophene-S,S-dioxide) 22 <ol><li>500 mL üç-boyun yuvarlak alt flask, kullanarak dağıtılması 2,8 - dibromodibenzothiophene-S, S-dioksit (0,45 g, 1.2 mmol) ve 3,6-di-tert-butyl-9H-carbazole (0,80 g, 2,86 mmol) susuz toluen (250 mL) ve azot güçlü karıştırma altında 15 dakika boyunca köpüren degas.</li>
		<li>Bundan sonra tris(dibenzylideneacetone)dipalladium(0) (0.025 g, 0,03 mmol) ve 2-dicyclohexylphosphino-2 eklemek &#8242;, 4 &#8242;, 6 &#8242;-triisopropylbiphenyl (XPhos, 0,06 g, 0,12 mmol) tepki karışıma ve başka bir 15 dakika çözüm degas. </li> <li>Sodyum tert-butoxide (0,32 g, 0.834 mmol) ve tert-butanol (6 mL) ekleyin ve 15 dakika süreyle elde edilen karışımı degas</li>
		<li>Isı 18 h. için azot atmosferi altında 110 ° C'de tepki çözüm</li>
		<li>Sıcaklığı Oda, (150 mL) su ekleyin ve organik ürünler diklorometan (250 mL) hulâsa ve organik katman iki kez 150 mL su ile yıkamak için soğumasını.</li>
		<li>15 g Magnezyum sülfat ile elde edilen organik katman kuru ve solvent ham ürün elde etmek için düşük basınç altında kaldırmak.</li>
		<li>Arındırmak ham malzeme tarafından sütun Kromatografi (solvent karışımı bir eluent kullanarak: diklorometan: Petrol eter 1:1 v/v) bileşik 4 beyaz katı (0,58 g, % 63'ü) verim için. 
		Bileşik 4 karakterizasyonu: 1 H NMR (400 MHz, CDCl 3, 25 ° C, ppm): 8.13 (d, J 1,6 Hz, 4 H =), 8,11 (d, J 8.2 Hz, 2 H =), 7.99 (d, J 1.7 Hz, 2 H =), 7.82 (dd, J 8.2, 1,8 Hz, 2 H =), 7.48 (dd, J = 8,7, 1.9 Hz, 4 H), 7,40 (d, J = 8.6 Hz, 4 H), (s, 36 H) 1,45. 
		13 C NMR (400 MHz, CDCl 3, 25 ° C, ppm): 144.4 144.2 138.5, 135.8, 133.4, 128,4, 124.4, 124.3, 119.5, 116.8, 109.2, 35,0, 32.2. 
		MS: m/z 769.97 (M +). 
		Erime noktası: 351-353 ° C.</li>
	</ol></li> <li>Sentezini 5 bileşik (2,8-bis(10H-phenothiazin-10-yl)dibenzothiophene-S,S-dioxide) 23 <ol><li>USING 250 mL üç-boyun yuvarlak alt flask, 2,8-dibromodibenzothiophene-S, S-dioksit (0.67 g, 1.8 mmol) ve phenothiazine (0.75 g, 3,77 mmol) susuz toluen (60 mL) dağıtılması ve azot güçlü karıştırma altında 15 dakika boyunca köpüren degas.</li>
		<li>Bundan sonra tris(dibenzylideneacetone)dipalladium(0) (0,11 g, 0,12 mmol) ve 2-dicyclohexylphosphino-2 eklemek &#8242;, 4 &#8242;, 6 &#8242;-triisopropylbiphenyl (XPhos, 0,12 g, 0,23 mmol) tepki karışıma ve başka bir 15 dakika çözüm degas. </li> <li>Sodyum tert-butoxide (0.38 g, 3,94 mmol) ekleyin ve ek 15 dakika süreyle elde edilen karışımı degas</li>
		<li>Isı tepki çözüm 18 h. için azot atmosferi altında 110 ° c</li>
		<li>Reaksiyon karışımı Oda sıcaklık, su (150 mL) ekleyin ve organik ürünler diklorometan (250 mL) hulâsa ve ayrıca iki kez 150 mL su yıkama soğumasını.</li>
		<li>Elde edilen organik katman yapıldı 15 g Magnezyum sülfat, Kaldır ham ürün vermek için düşük basınç altında solvent ile kuru.</li>
		<li>Arındırmak ham ürün sütun Kromatografi tarafından (solvent karışımı bir eluent kullanarak: diklorometan: hekzan 2:1 v/v) bileşik 5 beyaz katı (0.9 g, % 55) elde etmek için. 
		Bileşik 5 karakterizasyonu: 1 H NMR (400 MHz, CDCl 3, 25 ° C, ppm): 7,71 (d, J 8.2 Hz, 2 H =), 7,36 (dd, J 7,7, 1,5 Hz, 4 H =), 7,28-(m, 8 H), 7.19 7,16 (dd, J 7,7, 1.3 Hz, 4 H =), 7,02 (dd, J = 8.1, 1.3 Hz 4 H). 
		13 C NMR (400 MHz, CDCl 3, 25 ° C, ppm): 148.8, 141.1, 133.2, 131.8, 129.7, 128.1, 126.9, 125.1, 125.3, 123.1, 121.2, 111,7. 
		MS: m/z 610.08 (M +). 
		Erime noktası: 353-355 ° C.</li>
	</ol>
	</li>
</ol>

<ol>
	<li>Tang, C. W., VanSlyke, S. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Organic+electroluminescent+diodes.">Organic electroluminescent diodes.</a> Appl.Phys. Lett. 51, 913-915 (1987).</li><li>Pope, M., Kallmann, H. P., Magnante, P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Electroluminescence+in+Organic+Crystals.">Electroluminescence in Organic Crystals.</a> J. Chem. Phys. 38, 2042-2043 (1963).</li><li>Friend, R. H., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Electroluminescence+in+conjugated+polymers.">Electroluminescence in conjugated polymers.</a> Nature. 397, 121-128 (1999).</li><li>Rothberg, L. J., Lovinger, A. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Status+of+and+prospects+for+organic+electroluminescence.">Status of and prospects for organic electroluminescence.</a> J. Mater. Res. 11, 3174-3187 (1996).</li><li>Brown, A. R., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Poly(p-phenylenevinylene)+light-emitting+diodes:+Enhanced+electroluminescent+efficiency+through+charge+carrier+confinement.">Poly(p-phenylenevinylene) light-emitting diodes: Enhanced electroluminescent efficiency through charge carrier confinement.</a> Appl. Phys. Lett. 61, 2793-2795 (1992).</li><li>Wang, Q., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+Non-Doped+Phosphorescent+Organic+Light-Emitting+Device+with+Above+31%+External+Quantum+Efficiency.">A Non-Doped Phosphorescent Organic Light-Emitting Device with Above 31% External Quantum Efficiency.</a> Adv. Mater. 26, 8107-8113 (2014).</li><li>Wang, X., Gong, S. L., Song, D., Lu, Z. H., Wang, S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Highly+Efficient+and+Robust+Blue+Phosphorescent+Pt(II)+Compounds+with+a+Phenyl-1,2,3-triazolyl+and+a+Pyridyl-1,2,4-triazolyl+Chelate+Core.">Highly Efficient and Robust Blue Phosphorescent Pt(II) Compounds with a Phenyl-1,2,3-triazolyl and a Pyridyl-1,2,4-triazolyl Chelate Core.</a> Adv. Funct. Mater. 24, 7257-7271 (2014).</li><li>Ulbricht, C., Beyer, B., Friebe, C., Winter, A., Schubert, U. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Recent+Developments+in+the+Application+of+Phosphorescent+Iridium+(III)+Complex+Systems.">Recent Developments in the Application of Phosphorescent Iridium (III) Complex Systems.</a> Adv. Mater. 21, 4418-4441 (2009).</li><li>Adachi, C., Baldo, M. A., Thompson, M. E., Forrest, S. R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Nearly+100%+internal+phosphorescence+efficiency+in+an+organic+light-emitting+device.">Nearly 100% internal phosphorescence efficiency in an organic light-emitting device.</a> J. Appl. Phys. 90, 5048-5051 (2001).</li><li>Park, Y. S., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Exciplex-Forming+Co-host+for+Organic+Light-Emitting+Diodes+with+Ultimate+Efficiency.">Exciplex-Forming Co-host for Organic Light-Emitting Diodes with Ultimate Efficiency.</a> Adv. Funct. Mater. 23, 4914-4920 (2013).</li><li>Xu, H., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Recent+progress+in+metal-organic+complexes+for+optoelectronic+applications.">Recent progress in metal-organic complexes for optoelectronic applications.</a> Chem. Soc. Rev. 43, 3259-3302 (2014).</li><li>Uoyama, H., Goushi, K., Shizu, K., Nomura, H., Adachi, C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Highly+efficient+organic+light-emitting+diodes+from+delayed+fluorescence.">Highly efficient organic light-emitting diodes from delayed fluorescence.</a> Nature. 492, 234-238 (2012).</li><li>Zhang, Q., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Efficient+Blue+Organic+Light-Emitting+Diodes+Employing+Thermally+Activated+Delayed+Fluorescence.">Efficient Blue Organic Light-Emitting Diodes Employing Thermally Activated Delayed Fluorescence.</a> Nat. Photonics. 8, 326-332 (2014).</li><li>Hirata, S., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Highly+Efficient+Blue+Electroluminescence+based+on+Thermally+Activated+Delayed+Fluorescence.">Highly Efficient Blue Electroluminescence based on Thermally Activated Delayed Fluorescence.</a> Nat. Mater. 14, 330-335 (2015).</li><li>Yang, Z., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Recent+Advances+in+Organic+Thermally+Activated+Delayed+Fluorescence+Materials.">Recent Advances in Organic Thermally Activated Delayed Fluorescence Materials.</a> Chem. Soc. Rev. 46, 915-1016 (2017).</li><li>Im, Y., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Molecular+Design+Strategy+of+Organic+Thermally+Activated+Delayed+Fluorescence+Emitters.">Molecular Design Strategy of Organic Thermally Activated Delayed Fluorescence Emitters.</a> Chem. Mater. 29, 1946-1963 (2017).</li><li>Wong, M. Y., Zysman-Colman, E. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Purely+Organic+Thermally+Activated+Delayed+Fluorescence+Materials+for+Organic+Light-Emitting+Diodes.">Purely Organic Thermally Activated Delayed Fluorescence Materials for Organic Light-Emitting Diodes.</a> Adv. Mater. 1605444, (2017).</li><li>Dias, F. B., Penfold, T. J., Monkman, A. P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Photophysics+of+thermally+activated+delayed+fluorescence+molecules.">Photophysics of thermally activated delayed fluorescence molecules.</a> Methods Appl. Fluoresc. 5, 012001 (2017).</li><li>Liu, Y., Nishiura, M., Wang, Y., Hou, Z. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=&#960;-Conjugated+Aromatic+Enynes+as+a+Single-Emitting+Component+for+White+Electroluminescence.">&#960;-Conjugated Aromatic Enynes as a Single-Emitting Component for White Electroluminescence.</a> J. Am. Chem. Soc. 128, 5592-5593 (2006).</li><li>Neumoyer, C. R., Amstutz, E. D. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Studies+in+the+Sulfone+Series.+I.+The+Preparation+of+2,8-Diaminodibenzothiophene-5-dioxide.">Studies in the Sulfone Series. I. The Preparation of 2,8-Diaminodibenzothiophene-5-dioxide.</a> J. Am. Chem. Soc. 69, 1920-1921 (1947).</li><li>Gilman, H., Nobis, J. F. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Rearrangement+with+4-Iododibenzothiophene+in+Amination+by+Sodamide.">Rearrangement with 4-Iododibenzothiophene in Amination by Sodamide.</a> J. Am. Chem. Soc. 67, 1479-1480 (1945).</li><li>Dias, F. B., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Triplet+Harvesting+with+100%+Efficiency+by+Way+of+Thermally+Activated+Delayed+Fluorescence+in+Charge+Transfer+OLED+Emitters.">Triplet Harvesting with 100% Efficiency by Way of Thermally Activated Delayed Fluorescence in Charge Transfer OLED Emitters.</a> Adv. Mater. 25, 3707-3714 (2013).</li><li>Dias, F. B., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+role+of+local+triplet+excited+states+and+D-A+relative+orientation+in+thermally+activated+delayed+fluorescence:+photophysics+and+devices.">The role of local triplet excited states and D-A relative orientation in thermally activated delayed fluorescence: photophysics and devices.</a> Adv. Sci. 3, 1600080 (2016).</li><li>Moss, K. C., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Tuning+the+Intramolecular+Charge+Transfer+Emission+from+Deep+Blue+to+Green+in+Ambipolar+Systems+Based+on+Dibenzothiophene+S,S-Dioxide+by+Manipulation+of+Conjugation+and+Strength+of+the+Electron+Donor+Units.">Tuning the Intramolecular Charge Transfer Emission from Deep Blue to Green in Ambipolar Systems Based on Dibenzothiophene S,S-Dioxide by Manipulation of Conjugation and Strength of the Electron Donor Units.</a> J. Org. Chem. 75, 6771-6781 (2010).</li></ol>

İfşa etmek yok.

Piyasada bulunan başlangıç malzemelerden OLED uygulamalar için yüksek verimli organik maddeler (Şekil 1) büyük ölçekli sentezi göstermek için bu kağıt amacı budur. Önceki raporları yalnızca son çapraz-bağlantı tepki adım tarif ve modası geçmiş yayınları başvurmak nedeniyle gerçeğini, biz onların tam NMR ve kütle spektrometresi ile birlikte tüm malzemelerin ayrıntılı adım adım sentez raporu deneyler için geliştirilmiş tekrarlanabilirlik karakterizasyonu.
Her iki yayıcılar aynı dibenzothiophene-5-dioksit elektron alıcısı çekirdek ayı. Piyasada bulunan dibenzothiophene molekülünün bromination bileşik 3 (Şekil 2) hazırlanmasında ilk adımdır. 20 büyük ölçekli tepki gecede bir verim % 83 ile oluşur. Elde edilen dibrominated bileşik 2 daha fazla hidrojen peroksit buzul Asetik asit, filtrasyon ve yıkama sonra beyaz bir toz 19.3 g verimli bir çözüm ile okside. 21 3 bileşik olmadan herhangi bir daha fazla arıtma çapraz-bağlantı tepki olarak kullanılmıştır.
Photophysical özellikleri bileşik 4 ve 5 arasındaki farkı Amin birimleri elektron özelliklerinde yatıyor. Diğer phenothiazine grupları sahipken bir bileşiklerin periferik alkylated Karbazol birimler bulunmaktadır. Phenothiazine molekül kimyasal satıcılardan satın alınabilir ve herhangi bir değişiklik kullanılır. Ancak, bileşik 4 tert-butil grubu söz konusu olduğunda Karbazol birim aromatik halkanın organik çözücüler çözünürlük artırmak amacıyla sunulması gerekir. Bu uygun alkil grupları olmaması durumunda, ürünün çözünürlük düştüğünü, hangi sonuçları önemli ölçüde daha düşük bir tepki verim bildirildi. 24 alkil grupları Friedel-el sanatları tepki tert-butil klorür ve 9-H-Karbazol çinko (II) klorür huzurunda arasında nitromethane electrophilic aromatik değiştirme mekanizması üzerinde dayalı kullanarak her fenil halka içine tanıttı olabilir. 19 bu çarpım saflığı yeterince yüksek değil ve birkaç yan ürünleri karışımı mevcuttur bulundu; Bu nedenle ham gri toz Ayrıca sütun Kromatografi yalıtım 13.1 g bileşik 1 beyaz bir toz olarak kurtarılan sonuçlanan tarafından saf olmalı.
İstenen TADF yayıcılar 4 ve 5 yukarıda açıklanan edebiyat yordamları kullanarak Paladyum katalize karbon-azot çapraz-bağlantı reaksiyonlar ile sentezlenmiş. 22 , Başlangıç malzemeleri miktarda artan değil olumsuz mu bulduk 23 tepki ölçeği için daha fazla artar mümkün olduğunu düşündüren istenen Ürün verimini etkiler. Bileşikler 4 ve 5 olabilir % 63 ve % 55 verim, sırasıyla elde.
Sonuç olarak, ışık yayan olasılığı kadar tüm sentetik prosedürü ölçeklemek için hazır malzemelerden başlangıç uygulamaları için yüksek verimli organik moleküllerin hazırlamak nasıl ayrıntılı bir kılavuz kanıtlanmıştır. Bu çalışma sayesinde, büyük ölçekli birçok diğer TADF yayıcılar sentezi laboratuvar tezgah teknoloji endüstriyel uygulamalar için hızlı bir geçiş sağlayacak niyeti olduğunu.

Son birkaç on yıl boyunca, araştırmacılar onların ilk giriş 1987 yılında beri organik moleküller ve onların türevleri organik ışık - yayan diyot (OLED) içinde kullanımı araştırdı. 1 organik malzemeler geniş bir uygulama yelpazesi görüntüler ve aydınlatma bulma elektriksel (EL) keşif açmıştır. 2 yeni organik bileşikler üreten ve photophysical özelliklerini eğitim çok büyük ilgi OLED'lerin avantajları mevcut teknolojileri tarafından tahrik edilmektedir; En önemlisi onlar daha enerji-verimli ve üstün aygıtı performansı yüksek düzeyde esneklik, küçük kalınlık ve düşük ağırlığı muhafaza ederken sunabilir. Yine de, inorganik ışık - yayan diyotlar ile karşılaştırıldığında (LED), OLED'lerin hala bu teknoloji daha kısa yaşam süreleri ve düşük verimleri de dahil olmak üzere büyük ölçekli ticari üretimden önlemek dezavantajları zarar. Yakın zamana kadar çoğu araştırma ilk nesil OLED'lerin dayanıyordu ve emisyon organik maddeler Floresans dayanıyordu. Floresans sadece singlet durumundan oluşabilir nedeniyle aslında bu, cihazın en fazla teorik iç kuantum verimliliği (IQE) sadece % 25 olduğunu. 3 , 4 , 5 ağır metal içeren organik kompleksleri (Örneğin IR, Pt) kullanarak, araştırmacılar % 25 verimliliği bariyer singlet ve üçlü Birleşik Elektron ışınımsal geçiş işlemi tarafından hasat tarafından üstesinden gelebilir. 6 , 7 , 8 böylece, ikinci nesil en fazla teorik verimliliğini fosforlu OLED'lerin (PHOLEDs) % 100 olarak yüksek olabilir. 9 , 10 günümüzde, yeşil ve kırmızı Organometalik kompleksleri iridyum üzerinde dayalı yayan fosforlu birçok ticari OLED Aygıt kullanmaktadır. 11 bu malzemelerin yaygın kullanımı mobil görüntüler ve diğer elektronik uygulamalarda kazanmış olsa da, ağır metal habercisi maliyetini tuzlar ve onların kısa ömürleri araştırmacılar için alternatifler aramaya itti.
OLED teknolojisi, yüksek kararlılık, etkili bir enerji tüketimi ve düşük üretim maliyeti cihazın gibi yaygın ticari kullanım için Ulaşılması gereken çeşitli amaçları vardır. Son yıllarda, termal aktif gecikmeli floresan (TADF) yayıcılar şimdi üçüncü nesil OLED malzemesi olarak kabul bu malzeme ile aynı IQE değer ulaşmak için etkili bir yerine PHOLED malzemeler için olabilir gösterilmiştir. 12 , 13 , 14 tamamen organik TADF yayıcılar hazır başlangıç malzemelerden genel aygıt uydurma ticari olarak piyasada cazip hale birkaç adımda hazırlanabilir. Orada bugüne kadar birkaç kapsamlı edebiyatı değerlendirmeleri malzeme sentezi-cihaz imalat her yönüyle kapsayan vardır. 15,16,17,18 TADF malzeme hazırlama ile ana konu çapraz-bağlantı reaksiyonlar için Katalizörler Pd içeren kullanmaktır. TADF malzeme hazırlama için potansiyel artan bir ölçekte gösterebilmek için. Biz ölçekli-malzemeler 4 ve 5 (şekil 1) istenen ürünlere başlatılmasını TADF yayıcılar sentezi up. 22 , 23 bu ayrıntılı iletişim kuralı alanında yeni uygulayıcıları TADF malzeme sentezi ile ilişkili bilgileri anlamaya yardımcı olmak içindir.

<table><tbody><tr><td>2-Chloro-2-methylpropane, 99+%</td><td>Sigma Aldrich</td><td>19780</td><td></td></tr><tr><td>2-Dicyclohexylphosphino-2&amp;prime;,4&amp;prime;,6&amp;prime;-triisopropylbiphenyl (XPhos), 97%</td><td>Sigma Aldrich</td><td>638064</td><td>Air sensitive</td></tr><tr><td>9-H-carbazole, 95%</td><td>Alfa Aesar</td><td>A11448</td><td>Air sensitive</td></tr><tr><td>Bromine, 99.5%</td><td>Fisher</td><td>10452553</td><td>Highly toxic</td></tr><tr><td>Chloroform, anhydrous, 99%</td><td>Sigma Aldrich</td><td>288306</td><td></td></tr><tr><td>Dibenzothiophene, 98%</td><td>Sigma Aldrich</td><td>D32202</td><td></td></tr><tr><td>Dichloromethane, anhydrous, 99.8%</td><td>Sigma Aldrich</td><td>270997</td><td></td></tr><tr><td>Glacial acetic acid, 99.7+%</td><td>Alfa Aesar</td><td>36289</td><td>Corrosive to skin</td></tr><tr><td>Hexane, anhydrous, 95%</td><td>Sigma Aldrich</td><td>296090</td><td></td></tr><tr><td>Hydrogen peroxide solution (30 % (w/w) in H&lt;sub&gt;2&lt;/sub&gt;O)</td><td>Sigma Aldrich</td><td>H1009</td><td>Corrosive to skin</td></tr><tr><td>Magnesium sulfate, 99.5%</td><td>Alfa Aesar</td><td>33337</td><td></td></tr><tr><td>Nitromethane, 98+%</td><td>Alfa Aesar</td><td>A11806</td><td>Highly explosive</td></tr><tr><td>Phenothiazine, 98+%</td><td>Alfa Aesar</td><td>A12517</td><td>Air sensitive</td></tr><tr><td>Sodium tert-butoxide, 97%</td><td>Sigma Aldrich</td><td>359270</td><td></td></tr><tr><td>Tert-butanol, anhydrous, 99.5%</td><td>Sigma Aldrich</td><td>471712</td><td></td></tr><tr><td>Toluene, anhydrous, 99.8%</td><td>Sigma Aldrich</td><td>244511</td><td></td></tr><tr><td>Tris(dibenzylideneacetone) dipalladium(0), Pd 21.5% min</td><td>Alfa Aesar</td><td>12760-03</td><td>Air sensitive</td></tr><tr><td>Zinc (II) chloride, anhydrous, 98+%</td><td>Alfa Aesar</td><td>A16281</td><td></td></tr></tbody></table>

scale-up chemical synthesis of thermally-activated delayed fluorescence emitters based on the dibenzothiophene-s,s-dioxide core

Biz doğrusal ölçek-up 2,8-bis (3,6-di-tert-butyl-9H-carbazol-9-yl) dibenzothiophene-S, S-dioksit (bileşik 4) ve 2,8-bis(10H-phenothiazin-10-yl) dibenzothiophene-S, sentezi için bir yordam raporu S-dioksit (bileşik 5) kullanarak Buchwald Hartwig çapraz-bağlantı reaksiyon koşulları. Buna ek olarak, biz amination çapraz-bağlantı reaksiyon için gerekli olan tüm ticari olmayan başlangıç malzemeler ölçekli-up sentezi göstermek. Bugünkü yazıda, tüm açıklanan bileşiklerin onların spektral karakterizasyonu birlikte ayrıntılı sentetik yordamlar sağlar. Bu eser uygulanışını gerçek dünya cihazların içine kolaylaştırır bir büyük ölçekte opto-elektronik uygulamalar için organik moleküller üretmeye olasılığını gösterir.

Son TADF emitters (şekil 1) kimyasal yapıları için elektron grupları ve elektron çekilmesi çekirdek için kırmızı mavi işaretlenir. Bir alkylated Karbazol türev ve bir dibrominated dibenzothiopene-S, S-dioksit alıcısı molekül ucuz başlangıç malzemelerden (Şekil 2) hazırlanabilir. Son ürünler Pd katalize amination çapraz-bağlantı reaksiyonu (şekil 3), büyük ölçekli bir sürümü ile hazır olun.
<img alt="Figure 1" class="xfigimg" src="/files/ftp_upload/56501/56501fig1.jpg"> 
Resim 1 . Kimyasal yapıları, 3,6-di-tert-butyl-9H-carbazol-9-yl ve 10 H-phenothiazin-10-yl donör moieties taşıyan 2,8-dibenzothiophene-5-dioksit elektron alıcısı çekirdek üzerinde (gösterilen kırmızı) dayalı termik harekete geçirmek gecikmeli Floresans yayıcılar Bileşik 4 ve 5 sırasıyla bileşik. Elektron grupları mavi renkle gösterilir. <a href="//ecsource.jove.com/files/ftp_upload/56501/56501fig1large.jpg" target="_blank">Bu rakam daha büyük bir versiyonunu görüntülemek için buraya tıklayınız.</a>
<img alt="Figure 2" class="xfigimg" src="/files/ftp_upload/56501/56501fig2.jpg"> 
Resim 2 . 9-H-Karbazol ve 2,8-dibromodibenzothiophene-5-dioksit (bileşik 3) ticari olarak mevcut dibenzothiophene başlayan iki adımda alkillenme tarafından 3,6-Di-tert-butyl-9H-carbazole (bileşik 1) hazırlamak için kimyasal reaksiyon yollar. <a href="//ecsource.jove.com/files/ftp_upload/56501/56501fig2large.jpg" target="_blank">Bu rakam daha büyük bir versiyonunu görüntülemek için buraya tıklayınız.</a>
<img alt="Figure 3" class="xfigimg" src="/files/ftp_upload/56501/56501fig3.jpg"> 
Şekil 3 . Buchwald-2,8-dibromodibenzothiophene-5-dioksit (bileşik 3) ve karşılık gelen bir ikincil Amin arasında reaksiyonlar kaplin çapraz bileşikleri 4 ve 5 üretmek için Hartwig. <a href="//ecsource.jove.com/files/ftp_upload/56501/56501fig3large.jpg" target="_blank">Bu rakam daha büyük bir versiyonunu görüntülemek için buraya tıklayınız.</a>

Watch this Scientific Journal Video about Scale-up Chemical Synthesis of Thermally-activated Delayed Fluorescence Emitters Based on the Dibenzothiophene-S,S-Dioxide Core at JoVE.com

Scale-up Chemical Synthesis of Thermally-activated Delayed Fluorescence Emitters Based on the Dibenzothiophene-S,S-Dioxide Core

Yüksek verimli termal aktif gecikmeli Floresans yayıcılar sentezi ölçek-up sunulan makalede anlatılan.

Dibenzothiophene-S, S-dioksit göbek üzerinde esaslı gecikmeli Floresans termal aktif Emitters ölçek-up kimyasal sentez

We report a procedure to linearly scale-up the synthesis of 2,8-bis(3,6-di-tert-butyl-9H-carbazol-9-yl)dibenzothiophene-S,S-dioxide (compound 4) and ...

scale-up-chemical-synthesis-thermally-activated-delayed-fluorescence

Universidad de Cartagena UDEC

Research

JoVE Journal

Chemistry

9.5K Görüntüleme.  University of Strathclyde. Yüksek verimli termal aktif gecikmeli Floresans yayıcılar sentezi ölçek-up sunulan makalede anlatılan.

Video: Scale-up Chemical Synthesis of Thermally-activated Delayed Fluorescence Emitters Based on the Dibenzothiophene-S,S-Dioxide Core

Microwave-assisted Intramolecular Dehydrogenative Diels-Alder Reactions for the Synthesis of Functionalized Naphthalenes/Solvatochromic Dyes

Functionalized naphthalenes have applications in a variety of research fields ranging from the synthesis of natural or biologically active molecules to the preparation of new organic dyes. Although numerous strategies have been reported to access naphthalene scaffolds, many procedures still present limitations in terms of incorporating functionality, which in turn narrows the range of available substrates. The development of versatile methods for direct access to substituted naphthalenes is therefore highly desirable.
The Diels-Alder (DA) cycloaddition reaction is a powerful and attractive method for the formation of saturated and unsaturated ring systems from readily available starting materials. A new microwave-assisted intramolecular dehydrogenative DA reaction of styrenyl derivatives described herein generates a variety of functionalized cyclopenta[b]naphthalenes that could not be prepared using existing synthetic methods. When compared to conventional heating, microwave irradiation accelerates reaction rates, enhances yields, and limits the formation of undesired byproducts.
The utility of this protocol is further demonstrated by the conversion of a DA cycloadduct into a novel solvatochromic fluorescent dye via a Buchwald-Hartwig palladium-catalyzed cross-coupling reaction. Fluorescence spectroscopy, as an informative and sensitive analytical technique, plays a key role in research fields including environmental science, medicine, pharmacology, and cellular biology. Access to a variety of new organic fluorophores provided by the microwave-assisted dehydrogenative DA reaction allows for further advancement in these fields.

Microwave-assisted intramolecular dehydrogenative Diels-Alder (DA) reactions provide concise access to functionalized cyclopenta[b]naphthalene building blocks. The utility of this methodology is demonstrated by one-step conversion of the dehydrogenative DA cycloadducts into novel solvatochromic fluorescent dyes via Buchwald-Hartwig palladium-catalyzed cross-coupling reactions.

Fonksiyonlu naftalenlerin / Solvatochromic Boyaların Sentez için Mikrodalga-destekli Moleküliçi Dehydrogenative Diels-Alder Reaksiyonları

Functionalized naphthalenes have applications in a variety of research fields ranging from the synthesis of natural or biologically active molecules to ...

Kimya

Electroactive Polymer Nanoparticles Exhibiting Photothermal Properties

A method for the synthesis of electroactive polymers is demonstrated, starting with the synthesis of extended conjugation monomers using a three-step process that finishes with Negishi coupling. Negishi coupling is a cross-coupling process in which a chemical precursor is first lithiated, followed by transmetallation with ZnCl2. The resultant organozinc compound can be coupled to a dibrominated aromatic precursor to give the conjugated monomer. Polymer films can be prepared via electropolymerization of the monomer and characterized using cyclic voltammetry and ultraviolet-visible-near infrared (UV-Vis-NIR) spectroscopy. Nanoparticles (NPs) are prepared via emulsion polymerization of the monomer using a two-surfactant system to yield an aqueous dispersion of the polymer NPs. The NPs are characterized using dynamic light scattering, electron microscopy, and UV-Vis-NIR-spectroscopy. Cytocompatibility of NPs is investigated using the cell viability assay. Finally, the NP suspensions are irradiated with a NIR laser to determine their effectiveness as potential materials for photothermal therapy (PTT).

A protocol is presented for the synthesis and preparation of nanoparticles consisting of electroactive polymers.

Elektroaktif Polimer nanopartiküller Sergileme Fototermal Özellikleri

A method for the synthesis of electroactive polymers is demonstrated, starting with the synthesis of extended conjugation monomers using a three-step ...

Mühendislik

Synthesis of Cyclic Polymers and Characterization of Their Diffusive Motion in the Melt State at the Single Molecule Level

We demonstrate a method for the synthesis of cyclic polymers and a protocol for characterizing their diffusive motion in a melt state at the single molecule level. An electrostatic self-assembly and covalent fixation (ESA-CF) process is used for the synthesis of the cyclic poly(tetrahydrofuran) (poly(THF)). The diffusive motion of individual cyclic polymer chains in a melt state is visualized using single molecule fluorescence imaging by incorporating a fluorophore unit in the cyclic chains. The diffusive motion of the chains is quantitatively characterized by means of a combination of mean-squared displacement (MSD) analysis and a cumulative distribution function (CDF) analysis. The cyclic polymer exhibits multiple-mode diffusion which is distinct from its linear counterpart. The results demonstrate that the diffusional heterogeneity of polymers that is often hidden behind ensemble averaging can be revealed by the efficient synthesis of the cyclic polymers using the ESA-CF process and the quantitative analysis of the diffusive motion at the single molecule level using the MSD and CDF analyses.

A protocol for the synthesis and characterization of diffusive motion of cyclic polymers at the single molecule level is presented.

Tek Molekül Düzeyde Halkalı Polimerlerin Sentezi ve eritin Devlet Onların Pasif Hareket Karakterizasyonu

We demonstrate a method for the synthesis of cyclic polymers and a protocol for characterizing their diffusive motion in a melt state at the single ...

Self-assembling Morphologies Obtained from Helical Polycarbodiimide Copolymers and Their Triazole Derivatives

A facile method for the preparation of polycarbodiimide-based secondary structures (e.g., nano-rings, &#34;craters,&#34; fibers, looped fibers, fibrous networks, ribbons, worm-like aggregates, toroidal structures, and spherical particles) is described. These aggregates are morphologically influenced by extensive hydrophobic side chain-side chain interactions of the singular polycarbodiimide strands, as inferred by atomic force microscopy (AFM) and scanning electron microscopy (SEM) techniques. Polycarbodiimide-g-polystyrene copolymers (PS-PCDs) were prepared by a combination of synthetic methods, including coordination-insertion polymerization, copper(I)-catalyzed azide alkyne cycloaddition (CuAAC) &#34;click&#34; chemistry, and atom transfer radical polymerization (ATRP). PS-PCDs were found to form specific toroidal architectures at low concentrations in CHCl3. To determine the influence of a more polar solvent medium (i.e., THF and THF/EtOH) on polymer aggregation behavior, a number of representative PS-PCD composites have been tested to show discrete concentration-dependent spherical particles. These fundamental studies are of practical interest to the development of experimental procedures for desirable architectures by directed self-assembly in thin film. These architectures may be exploited as drug carriers, whereas other morphological findings represent certain interest in the area of novel functional materials.

Here, we present a protocol to prepare and visualize secondary structures (e.g., fibers, toroidal architectures, and nano-spheres) derived from helical polycarbodiimides. The morphology characterized by both atomic force microscopy (AFM) and scanning electron microscopy (SEM) was shown to depend on molecular structure, concentration, and the solvent of choice.

Sarmal polikarbodiimidden Kopolimer ve Bunların Triazole Türevleri elde edilen kendinden montaj morfolojileri

A facile method for the preparation of polycarbodiimide-based secondary structures (e.g., nano-rings, &#34;craters,&#34; fibers, looped fibers, fibrous ...

Time-resolved Photophysical Characterization of Triplet-harvesting Organic Compounds at an Oxygen-free Environment Using an iCCD Camera

Here, we present a sensible method of the acquisition and analysis of time-resolved photoluminescence using an ultrafast iCCD camera. This system enables the acquisition of photoluminescence spectra covering the time regime from nanoseconds up to 0.1 s. This enables us to follow the changes in the intensity (decay) and emission of the spectra over time. Using this method, it is possible to study diverse photophysical phenomena, such as the emission of phosphorescence, and the contributions of prompt and delayed fluorescence in molecules showing thermally activated delayed fluorescence (TADF). Remarkably, all spectra and decays are obtained in a single experiment. This can be done for solids (thin film, powder, crystal) and liquid samples, where the only limitations are the spectral sensitivity of the camera and the excitation wavelength (532 nm, 355 nm, 337 nm, and 266 nm). This technique is, thus, very important when investigating the excited state dynamics in organic emitters for their application in organic light-emitting diodes and other areas where triplet harvesting is of paramount importance. Since triplet states are strongly quenched by oxygen, emitters with efficient TADF luminescence, or those showing room temperature phosphorescence (RTP), must be correctly prepared in order to remove any dissolved oxygen from solutions and films. Otherwise, no long-lived emission will be observed. The method of degassing solid samples as presented in this work is basic and simple, but the degassing of liquid samples creates additional difficulties and is particularly interesting. A method of minimizing solvent loss and changing the sample concentration, while still enabling to remove oxygen in a very efficient and a repeatable manner, is presented in this work.

Here, we present a method of the spectroscopic characterization of organic molecules by means of time-resolved photoluminescence spectroscopy on the nanosecond-to-millisecond timescale in oxygen-free conditions. Methods to efficiently remove oxygen from the samples and, thus, limit luminescence quenching are also described.

Zaman karar vermek Photophysical karakterizasyonu üçlüsü-hasat organik bileşikler bir oksijensiz ortamı kullanarak bir ICCD kamera

Here, we present a sensible method of the acquisition and analysis of time-resolved photoluminescence using an ultrafast iCCD camera. This system enables ...

Constructing Thioether/Vinyl Sulfide-tethered Helical Peptides Via Photo-induced Thiol-ene/yne Hydrothiolation

Here, we describe a detailed protocol for the preparation of thioether-tethered peptides using on-resin intramolecular/intermolecular thiol-ene hydrothiolation. In addition, this protocol describes the preparation of vinyl-sulfide-tethered peptides using in-solution intramolecular thiol-yne hydrothiolation between amino acids that possess alkene/alkyne side chains and cysteine residues at i, i+4 positions. Linear peptides were synthesized using a standard Fmoc-based solid-phase peptide synthesis (SPPS). Thiol-ene hydrothiolation is carried out using either an intramolecular thio-ene reaction or an intermolecular thio-ene reaction, depending on the peptide length. In this research, an intramolecular thio-ene reaction is carried out in the case of shorter peptides using on-resin deprotection of the trityl groups of cysteine residues following the complete synthesis of the linear peptide. The resin is then set to UV irradiation using photoinitiator 4-methoxyacetophenone (MAP) and 2-hydroxy-1-[4-(2-hydroxyethoxy)-phenyl]-2-methyl-1-propanone (MMP). The intermolecular thiol-ene reaction is carried out by dissolving Fmoc-Cys-OH in an N,N-dimethylformamide (DMF) solvent. This is then reacted with the peptide using the alkene-bearing residue on resin. After that, the macrolactamization is carried out using benzotriazole-1-yl-oxytripyrrolidinophosphonium hexafluorophosphate (PyBop), 1-hydroxybenzotriazole (HoBt), and 4-Methylmorpholine (NMM) as activation reagents on the resin. Following the macrolactamization, the peptide synthesis is continued using standard SPPS. In the case of the thio-yne hydrothiolation, the linear peptide is cleaved from the resin, dried, and subsequently dissolved in degassed DMF. This is then irradiated using UV light with photoinitiator 2,2-dimethoxy-2-phenylacetophenone (DMPA). Following the reaction, DMF is evaporated and the crude residue is precipitated and purified using high-performance liquid chromatography (HPLC). These methods could function to simplify the generation of thioether-tethered cyclic peptides due to the use of the thio-ene/yne click chemistry that possesses superior functional group tolerance and good yield. The introduction of thioether bonds into peptides takes advantage of the nucleophilic nature of cysteine residues and is redox-inert relative to disulfide bonds.

We present a protocol for the construction of thioether/vinyl sulfide-tethered helical peptides using photo-induced thiol-ene/thiol-yne hydrothiolation.

Thioether/vinil sülfür-gergin helisel peptidler fotoğraf yolu ile indüklenen Thiol-KD/yne Hydrothiolation oluşturmak

Here, we describe a detailed protocol for the preparation of thioether-tethered peptides using on-resin intramolecular/intermolecular thiol-ene ...

Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework

We present a method for preparing thioester molecules as the masked form of the thiol linkers and their utilization for accessing a semiconducting and porous metal-dithiolene network in the highly ordered single crystalline state. Unlike the highly reactive free-standing thiols, which tend to decompose and complicate the crystallization of metal-thiolate open frameworks, the thioester reacts in situ to provide the thiol species, serving to mitigate the reaction between the mercaptan units and the metal centers, and to improve crystallization consequently. Specifically, the thioester was synthesized in a one-pot procedure: an aromatic bromide (hexabromotriphenylene) reacted with excess sodium thiomethoxide under vigorous conditions to first form the thioether intermediate product. The thioether was then demethylated by the excess thiomethoxide to provide the thiolate anion that was acylated to form the thioester product. The thioester was conveniently purified by standard column chromatography, and then used directly in the framework synthesis, wherein NaOH and ethylenediamine serve to revert in situ the thioester to the thiol linker for assembling the single-crystalline Pb(II)-dithiolene network. Compared with other methods for thiol synthesis (e.g., by cleaving alkyl thioether using sodium metal and liquid ammonia), the thioester synthesis here uses simple conditions and economical reagents. Moreover, the thioester product is stable and can be conveniently handled and stored. More importantly, in contrast to the generic difficulty in accessing crystalline metal-thiolate open frameworks, we demonstrate that using the thioester for in situ formation of the thiol linker greatly improves the crystallinity of the solid-state product. We intend to encourage broader research efforts on the technologically important metal-sulfur frameworks by disclosing the synthetic protocol for the thioester as well as the crystalline framework solid.

Here, we present a one-pot, transition-metal-free synthesis of thiols and thioesters from aromatic halides and sodium thiomethoxide, followed by the preparation of single crystals of a metal-dithiolene network using thiol species generated in situ from the more stable and tractable thioester.

Bir yarıiletken Gyroidal Metal-kükürt çerçeve kristalleşme için Thiol yapı taşı sentezi

We present a method for preparing thioester molecules as the masked form of the thiol linkers and their utilization for accessing a semiconducting and ...

Synthesis and Bioconjugation of Thiol-Reactive Reagents for the Creation of Site-Selectively Modified Immunoconjugates

Maleimide-bearing bifunctional probes have been employed for decades for the site-selective modification of thiols in biomolecules, especially antibodies. Yet maleimide-based conjugates display limited stability in vivo because the succinimidyl thioether linkage can undergo a retro-Michael reaction. This, of course, can lead to the release of the radioactive payload or its exchange with thiol-bearing biomolecules in circulation. Both of these processes can produce elevated activity concentrations in healthy organs as well as decreased activity concentrations in target tissues, resulting in reduced imaging contrast and lower therapeutic ratios. In 2018, we reported the creation of a modular, stable, and easily accessible phenyloxadiazolyl methyl sulfone reagent &#8212; dubbed &#8216;PODS&#8217; &#8212; as a platform for thiol-based bioconjugations. We have clearly demonstrated that PODS-based site-selective bioconjugations reproducibly and robustly create homogenous, well-defined, highly immunoreactive, and highly stable radioimmunoconjugates. Furthermore, preclinical experiments in murine models of colorectal cancer have shown that these site-selectively labeled radioimmunoconjugates exhibit far superior in vivo performance compared to radiolabeled antibodies synthesized via maleimide-based conjugations. In this protocol, we will describe the four-step synthesis of PODS, the creation of a bifunctional PODS-bearing variant of the ubiquitous chelator DOTA (PODS-DOTA), and the conjugation of PODS-DOTA to the HER2-targeting antibody trastuzumab.

In this protocol, we will describe the synthesis of PODS, a phenyoxadiazolyl methyl sulfone-based reagent for the site-selective attachment of cargos to the thiols of biomolecules, particularly antibodies. In addition, we will describe the synthesis and characterization of a PODS-bearing bifunctional chelator and its conjugation to a model antibody.

Sentez ve Site seçici olarak oluşturulması için Thiol reaktif reaktif Bioconjugation Immunoconjugates modifiye

Maleimide-bearing bifunctional probes have been employed for decades for the site-selective modification of thiols in biomolecules, especially antibodies. ...

Synthesis and Calibration of Phosphorescent Nanoprobes for Oxygen Imaging in Biological Systems

Oxygen measurement by phosphorescence quenching [1, 2] consists of the following steps: 1) the probe is delivered into the medium of interest (e.g. blood or interstitial fluid); 2) the object is illuminated with light of appropriate wavelength in order to excite the probe into its triplet state; 3) the emitted phosphorescence is collected, and its time course is analyzed to yield the phosphorescence lifetime, which is converted into the oxygen concentration (or partial pressure, pO2). The probe must not interact with the biological environment and in some cases to be 4) excreted from the medium upon the measurement completion. Each of these steps imposes requirements on the molecular design of the phosphorescent probes, which constitute the only invasive component of the measurement protocol. Here we review the design of dendritic phosphorescent nanosensors for oxygen measurements in biological systems. The probes consist of Pt or Pd porphyrin-based polyarylglycine (AG) dendrimers, modified peripherally with polyethylene glycol (PEG's) residues. For effective two-photon excitation, termini of the dendrimers may be modified with two-photon antenna chromophores, which capture the excitation energy and channel it to the triplet cores of the probes via intramolecular FRET (F&ouml;rster Resonance Energy Transfer). We describe the key photophysical properties of the probes and present detailed calibration protocols.

We present principles of oxygen measurements by phosphorescence quenching and review design of porphyrin-based dendritic nanosensors for oxygen imaging in biological systems.

Biyolojik Sistemleri Oksijen Görüntüleme Fosforlu Nanoprobes sentezi ve Kalibrasyon

Oxygen measurement by phosphorescence quenching [1, 2] consists of the following steps: 1) the probe is delivered into the medium of interest (e.g. blood ...

Biyoloji

Synthesis of pH Dependent Pyrazole, Imidazole, and Isoindolone Dipyrrinone Fluorophores using a Claisen-Schmidt Condensation Approach

Methine-bridged conjugated bicyclic aromatic compounds are common constituents of a range of biologically relevant molecules such as porphyrins, dipyrrinones, and pharmaceuticals. Additionally, restricted rotation of these systems often results in highly to moderately fluorescent systems as observed in 3H,5H-dipyrrolo[1,2-c:2',1'-f]pyrimidin-3-ones, xanthoglows, pyrroloindolizinedione analogs, BODIPY analogs, and the phenolic and imidazolinone ring systems of Green Fluorescent Protein (GFP). This manuscript describes an inexpensive and operationally simple method of performing a Claisen-Schmidt condensation to generate a series of fluorescent pH dependent pyrazole/imidazole/isoindolone dipyrrinone analogs. While the methodology illustrates the synthesis of dipyrrinone analogs, it can be translated to produce a wide range of conjugated bicyclic aromatic compounds. The Claisen-Schmidt condensation reaction utilized in this method is limited in scope to nucleophiles and electrophiles that are enolizable under basic conditions (nucleophile component) and non-enolizable aldehydes (electrophile component). Additionally, both the nucleophilic and electrophilic reactants must contain functional groups that will not inadvertently react with hydroxide. Despite these limitations, this methodology offers access to completely novel systems that can be employed as biological or molecular probes.

The Claisen-Schmidt condensation reaction is an important methodology for the generation of methine-bridged conjugated bicyclic aromatic compounds. Through utilizing a base-mediated variant of the aldol reaction, a range of fluorescent and/or biologically relevant molecules can be accessed through a generally inexpensive and operationally simple synthetic approach.