Pochodne tetraaryloporfiryny o potencjalnym zastosowaniu w terapii fotodynamicznej : synteza i wybrane właściwości fizykochemiczne

Związki organiczne, zawierające cztery pierścienie pirolowe połączone ze sobą w aromatyczny układ cykliczny są substancjami chemicznymi o bardzo ważnym znaczeniu biologicznym. Biorą one udział w najważniejszych procesach biochemicznych zachodzących w organizmach żywych, takich jak fotosynteza (chlorofil) czy transport tlenu (hem). Ze względu na rolę jaką spełniają, na przełomie XIX i XX wieku naturalne porfuyny stały się obiektami systematycznych badań mających na celu określenie ich struktur i podstawowych właściwości. Spośród różnych układów tetrapirolowych porfiryny zarówno naturalne jak i syntetyczne do dzisiaj cieszą się zainteresowaniem wielu ośrodków naukowych na świecie. Zainteresowanie tymi związkami naukowców z dziedzin takich jak fizyka, chemia, biologia, medycyna czy nauk badających właściwości oraz potencjalne zastosowanie nowych materiałów w różnych gałęziach przemysłu spowodowane jest możliwością pozyskiwania ich z natury oraz, co wydaje się nawet ważniejsze, na drodze syntezy chemicznej. Wiele syntetycznych porfiryn, ze względu na podobieństwo do naturalnych układów, może służyć do modelowania procesów biochemicznych takich jak fotosynteza czy procesów związanych z transportem tlenu w organizmach. Szczególnie interesująca wydaje się możliwość zastosowania tego typu związków w katalizie chemicznej lub chemii materiałów, gdzie bada się ich potencjalne zastosowanie jako ciekłych kryształów, czujników chemicznych, polimerów przewodzących czy materiałów używanych w optoelektronice. Porfiryny i ich pochodne są również wykorzystywane w medycynie. Stosuje się je w diagnostyce medycznej na przykład jako kontrasty w rezonansie magnetycznym, jednak największe zainteresowanie budzi możliwość ich zastosowania jako fotouczulaczy w terapii fotodynamicznej. W ramach niniejszej pracy otrzymano szereg nowych pochodnych tetraaryloporfiryny o potencjalnym zastosowaniu w terapii fotodynamicznej. Różna budowa otrzymanych związków, a co za tym idzie różne właściwości hydrofobowo-hydrofilowe przy podobnych wydajnościach tlenu singletowego pozwalają zastosować je w różnego rodzaju próbach biologicznych, z różnymi typami nośników leków, jak również bez użycia takowych. W pracy zostały przedstawione metody syntezy badanych fotosensybilizatorów oraz pełna ich charakterystyka fizykochemiczna istotna z punktu widzenia potencjalnego użycia otrzymanych związków jako fotouczulaczy w terapii fotodynamicznej

Spectroscopic and crystallographic characterization of two cathinone derivatives : 1-(4-fluorophenyl)-2-(methylamino)pentan-1-one (4-FPD) hydrochloride and 1-(4-methylphenyl)-2-(ethylamino)pentan-1-one (4-MEAP) hydrochloride

Purpose In this study, we performed identification and physicochemical characterization of two cathinone derivatives, 4-FPD and 4-MEAP, found in market-available materials. Methods The compounds were characterized by electrospray ionization ion trap mass spectrometry (MS) in MS2 and MS3 modes, gas chromatography–MS, infrared, Raman and ultraviolet-visible spectroscopies, X-ray crystallography, differential scanning calorimetry and nuclear magnetic resonance spectroscopy. Results We could obtain detailed and comprehensive physicochemical characterization of 4-FPD and 4-MEAP—new cathinone derivatives available on the designer drugs market. Conclusions Dynamic growth in the number of psychoactive substances available on the designer drug markets makes it compulsory to obtain analytical data allowing unequivocal identification of these drugs in the fastest possible way. In this study we presented analytical data useful in quick identification of the investigated compounds

2,3-O-Isopropylidene-1-O-p-tolylsulfonylglycerol

In the title compound, C13H18O5S, the five-membered ring has an envelope conformation. The packing involves four C— H O interactions, three of which combine to form layers of molecules parallel to the bc plane

Spectroscopic characterization and crystal structures of two cathinone derivatives : 1-(4-chlorophenyl)-2-(1-pyrrolidinyl)-pentan-1-one (4-chloro-α-PVP) sulfate and 1-(4-methylphenyl)-2-(dimethylamino)-propan-1-one (4-MDMC) hydrochloride salts, seized on illicit drug market

Purpose: Two compounds newly found in the seizures by drug enforcement agencies were identified and characterized by various instrumental analytical methods. Methods: The obtained powder samples were analyzed by gas chromatography–mass spectrometry (GC–MS), liquid chromatography–mass spectrometryn (LC–MSn), nuclear magnetic resonance (NMR) spectroscopy, infrared and Raman spectroscopy and X-ray crystallography. Results: The two compounds were tentatively identified as 4-chloro-α-PVP and 4-MDMC by GC–MS, and LC–MS/MS. The confirmation of the results was made by NMR spectroscopy. The X-ray crystallography gave information that 4-chloro-α-PVP and 4-MDMC were in salted forms with sulfate and hydrochloride, respectively; in addition, both compounds existed as racemic mixtures. Conclusions: We could identify 4-chloro-α-PVP and 4-MDMC in the seizure powder samples by various analytical methods. X-ray crystallography was especially useful for identifying the salted forms and enantiomeric forms

Spectroscopic and crystallographic characterization of a new cathinone derivative: 1‑phenyl‑2‑(butylamino)hexan‑1‑one hydrochloride (N‑butylhexedrone)

Purpose In this study, a new cathinone derivative, N-butylhexedrone, emerged on new psychoactive substances (NPS) market in Poland was described and characterized. Methods The compound was analyzed by gas chromatography—mass spectrometry, X-ray crystallography and infrared, Raman, ultraviolet-visible and nuclear magnetic resonance spectroscopic approaches. Results We confirmed the presence of the compound in the seized material and obtained detailed and comprehensive physicochemical characterization of N-butylhexedrone—new cathinone derivative available on the NPS market. Conclusions In this study, we presented chromatographic, spectroscopic and crystallographic characterization of a new cathinone derivative that emerged on the NPS market in 2019. The obtained analytical data should be useful for forensic and toxicological purposes in quick and reliable compound identification

Identification and characterization of new designer drug 4-fluoro-PV9 and [alfa]-PHP in the seized materials

In this study, we present identification and physicochemical characterization of new cathinone derivatives, 4-fluoro-PV9 and already known a-PHP in seized materials. Although the disclosure of a-PHP from an illegal product had been reported and characterized to some extent, the data on a-PHP are also presented together with those of 4-fluoro-PV9. The data of characterization for the two compounds were obtained by high-performance liquid chromatography (HPLC)–mass spectrometry and HPLC– diode array detection, electrospray ionization/ion trap mass spectrometry in MS2 and MS3 modes, gas chromatography– mass spectrometry, thermogravimetric analysis, differential scanning calorimetry, Fourier transform infrared spectroscopy, ultraviolet-visible spectroscopy, and nuclear magnetic resonance spectroscopy. To our knowledge, this is the first report for identification and detailed characterization of 4-fluoro-PV9 circulated on the illegal drug market

Spectroscopic characterization and crystal structures of two cathinone derivatives : N-ethyl-2-amino-1-phenylpropan-1-one (ethcathinone) hydrochloride and N-ethyl-2-amino-1-(4-chlorophenyl)propan-1-one (4-CEC) hydrochloride

Comprehensive chemical characterization for two cathinone derivatives, N-ethyl-2-amino-1-phenylpropan-1-one (ethcathinone) hydrochloride and N-ethyl-2-amino-1-(4-chlorophenyl)-propan-1-one (4-chloroethcathinone, 4-CEC) hydrochloride, in material seized by drug enforcement agencies was performed by nuclear magnetic resonance (NMR) spectroscopy, infrared spectroscopy, gas chromatography–mass spectrometry in positive electron ionization mode, liquid chromatography–mass spectrometry in positive electrospray ionization mode and X-ray crystallography. The examined samples of these two compounds proved to be very pure for ethcathinone and mixed with very small quantities of other substances for 4-CEC by NMR spectroscopy and mass spectrometry. X-ray crystallographic studies confirmed the occurrence of both compounds as racemic mixtures. These spectroscopic and crystallographic data seem very useful for their identification. Especially for 4-CEC, this is the first description on its spectroscopic characterization in a scientific context to our knowledge

Crystal structures and other properties of ephedrone (methcathinone) hydrochloride, N‑acetylephedrine and N‑acetylephedrone

Purpose Three compounds obtained from ephedrine were identified and characterized by various instrumental analytical methods. Ephedrone (methcathinone) hydrochloride and its fundamental derivatives N-acetylephedrine and N-acetylephedrone were analyzed as precursors of a cathinone derivative. Methods The obtained samples were analyzed by gas chromatography coupled with mass spectrometry, nuclear magnetic resonance spectroscopy, infrared and Raman spectroscopy, and X-ray crystallography. Results The three compounds were confirmed as: N-methyl-2-amino-1-phenylpropan-1-one (methcathinone) hydrochloride, N-acetyl-N-methyl-2-amino-1-phenylpropan-1-one (cathinone derivative), and N-acetyl-N-methyl-2-amino-1-phenylpropan- 1-ol (acetyl derivative of ephedrine). Conclusions X-ray crystallography is especially useful for identifying the new designer drugs and their different precursor forms

The synthesis of new potential photosensitizers.[Pt].1 Mono-carboxylic acid derivatives of tetraphenylporphyrin

A series of mono-alkylcarboxylic acid derivatives of tetraphenylporphyrin have been prepared. All the porphyrins were completely characterized by use of mass, 1H NMR, UV–visible, and fluorescence spectroscopy. Experimental log P were determined by use of reversedphase thin-layer chromatography with use of log PRekker. These porphyrins are potential photosensitizers in photodynamic therapy

Spectroscopic characterization and crystal structures of four hydrochloride cathinones : N-ethyl-2-amino-1-phenylhexan-1-one (hexen, NEH), N-methyl-2-amino-1-(4-methylphenyl)-3-methoxypropan-1-one (mexedrone), N-ethyl-2-amino-1-(3,4-methylenedioxyphenyl)pentan-1-one (ephylone) and N-butyl-2-amino-1-(4-chlorophenyl) propan-1-one (4-chlorobutylcathinone)

Purpose Four compounds found during seizure by drug enforcement agencies were identified and characterized by various instrumental analytical methods. Methods The samples were analyzed by nuclear magnetic resonance (NMR), infrared and Raman spectroscopies and X-ray crystallography. Results The four compounds were confirmed as: N-ethyl-2-amino-1-phenylhexan-1-one hydrochloride, N-methyl-2-amino-1-(4-methylphenyl)-3-methoxypropan-1-one hydrochloride, N-ethyl-2-amino-1-(3,4-methylenedioxyphenyl)pentan-1-one hydrochloride and N-butyl-2-amino-1-(4-chlorophenyl)propan-1-one hydrochloride; all four were cathinone derivatives available on the designer drug market. Conclusions X-ray crystallography is especially useful for identifying the new and unknown designer drugs and their enantiomeric forms