Publications by authors named "Mahmut Durmuş"

98 Publications

BSA/DNA binding behavior and the photophysicochemical properties of novel water soluble zinc(II)phthalocyanines directly substituted with piperazine groups.

J Biol Inorg Chem 2021 May 4. Epub 2021 May 4.

Department of Chemistry, Gebze Technical University, 41400, Gebze, Kocaeli, Turkey.

In the current research, two novel zinc(II) phthalocyanines (ZnPcs) (1 and 2) directly connecting with 4-(4-methylpiperazin-1-yl)phenyl groups have been synthesized through the Suzuki-Miyaura coupling reaction. These ZnPcs 1 and 2 were converted to their water-soluble derivatives (1Q and 2Q) by quaternization. The photochemical and photophysical properties were determined in DMSO for the non-ionic zinc(II) phthalocyanines (1 and 2) and in both DMSO and aqueous solutions for the quaternized cationic derivatives (1Q and 2Q) to establish their photosensitizer capabilities in photodynamic therapy (PDT). The spectrofluorometric and spectrophotometric techniques were employed for the determination of interaction between water-soluble ZnPcs (1Q and 2Q) and BSA or ct-DNA. The binding constants of these compounds to BSA were found in the order of 10 M. The binding constant of the ct-DNA interaction with 2Q (1.09 × 10 M) was found higher than 1Q (6.87 × 10 M). The thermodynamic constants were determined for both 1Q and 2Q. The endothermic and spontaneous nature of interaction was observed with ct-DNA. Besides, the thermal denaturation and viscosity studies proved the non-intercalative mode of binding for both compounds to ct-DNA.
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http://dx.doi.org/10.1007/s00775-021-01868-6DOI Listing
May 2021

A highly sensitive "ON-OFF-ON" dual optical sensor for the detection of Cu(II) ion and triazole pesticides based on novel BODIPY-substituted cavitand.

Dalton Trans 2021 May;50(19):6437-6443

Department of Chemistry, Faculty of Basic Sciences, Gebze Technical University, Kocaeli, Turkey.

The synthesis with full structural characterization including elemental analysis and 1H, 13C, 11B and 19F NMR, FT-IR and MALDI-TOF spectral data, along with the florescence sensing behavior of a new resorcin[4]arene cavitand 3 bearing multiple BODIPY sites achieved by the Cu-catalyzed azide-alkyne cycloaddition (CuAAC) is being reported. The spatial orientation of multiple BODIPY-1,2,3-triazole arms based on the macrocyclic rigid core is of great interest since the resulting structure has been utilized as a fluorescent chemosensor for numerous metal cations. In particular, a remarkable decrease in the fluorescence emission towards Cu(ii) ions, i.e., "turn-off" response, has been obtained giving rise to an optical sensor for the detection of triazole fungicides, namely tebuconazole, triadimenol, triadimefon, i.e. "turn-on" response. Such a molecular system, hence, can be feasibly applied as a dual optical sensor, i.e. "a turn-on-off-on" system, for dangerous contaminants such as heavy metals and pesticides.
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http://dx.doi.org/10.1039/d1dt00792kDOI Listing
May 2021

Novel nonperipheral octa-3-hydroxypropylthio substituted metallo-phthalocyanines: synthesis, characterization, and investigation of their electrochemical, photochemical and computational properties.

Turk J Chem 2021 17;45(1):143-156. Epub 2021 Feb 17.

Department of Chemical Engineering, Uşak University, Uşak Turkey.

The current study describes the synthesis, electrochemical, computational, and photochemical properties of octa (3-hydroxypropylthio) substituted cobalt (II) ( ), copper (II) ( ), nickel (II) ( ) and zinc(II) ( ) phthalocyanine derivatives. These novel compounds were characterized by elemental analysis,H,C NMR, FT-IR, UV-Vis, and MS. The redox behaviors of these metallo-phthalocyanines were investigated by the cyclic voltammetric method. The optimized molecular structure and gauge-including atomic orbital (GIAO)H andC NMR chemical shift values of these phthalocyanines in the ground state had been calculated by using B3LYP/6-31G(d,p) basis set. The outcomes of the optimized molecular structure were given and compared with the experimental NMR values. The photochemical properties including photodegradation and singlet oxygen generation of zinc(II) phthalocyanine were studied in DMSO solution for the determination of its photosensitizer behaviors.
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http://dx.doi.org/10.3906/kim-2008-48DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7925307PMC
February 2021

Experimental and theoretical investigation of water-soluble silicon(IV) phthalocyanine and its interaction with bovine serum albumin.

J Biol Inorg Chem 2021 May 8;26(2-3):235-247. Epub 2021 Feb 8.

Department of Chemistry, Gebze Technical University, 41400, Gebze, Kocaeli, Turkey.

Photodynamic therapy (PDT) has drawn a great scientific attention to cancer treatment over the last decades. However, the bottleneck for the PDT is to find good photosensitizers (PSs) with greater water solubility, no aggregation, and fast discharge from the body. Therefore, there are still a big scientific desire for the synthesizing new rational PSs for treatment of cancer by PDT technique. In favor of improving the competence of PDT, an axially bis[4-(diphenylamino-1,1'-biphenyl-4-ol)] substituted silicon(IV) phthalocyanine (3) was converted to its water-soluble quaternized derivative (3Q). Their structures were fully characterized by single-crystal X-ray diffraction, elemental analysis, and different spectroscopic methods such as FT-IR, UV-Vis, MALDI-TOF, and H-NMR. The photophysical properties such as fluorescence quantum yields and lifetimes, and the photochemical properties such as singlet oxygen generation of both phthalocyanines were investigated. Ground and excited-state calculations were performed to explain the observed electronic absorption spectra. The addition of the 4-diphenylamino-1,1'-biphenyl-4-ol groups on the axially positions of the silicon(IV) phthalocyanine increased the singlet oxygen quantum yield from 0.15 to around 0.20. Especially quaternized compound 3Q showed high singlet oxygen quantum yield of 0.26 in water solution. In addition, a spectroscopic investigation of the binding behavior of the quaternized silicon (IV) phthalocyanine complex to bovine serum albumin (BSA) is also studied in this work, confirming the possible interaction. Further theoretical calculations were carried out to find out the plausible-binding regions of the BSA protein. Axially bis[4-(diphenylamino-1,1'-biphenyl-4-ol)] substituted silicon(IV) phthalocyanine (3) was converted to its quaternized water soluble derivative (3Q). The photophysical properties such as fluorescence quantum yields and lifetimes, and the photochemical properties such as singlet oxygen generation of both phthalocyanines were investigated. In addition, a spectroscopic investigation of the binding behavior of the quaternized silicon (IV) phthalocyanine complex to bovine serum albumin (BSA) is also studied in this work, confirming the possible interaction. Further theoretical calculations were carried out to find out the plausible binding regions of the BSA protein.
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http://dx.doi.org/10.1007/s00775-021-01848-wDOI Listing
May 2021

Synthesis and photodynamic activities of novel silicon(iv) phthalocyanines axially substituted with water soluble groups against HeLa cancer cell line.

Dalton Trans 2021 Feb 1;50(7):2570-2584. Epub 2021 Feb 1.

Kocaeli University, Department of Chemistry, Umuttepe, 41380, Kocaeli, Turkey.

In this study, compounds 1 and 2, and their silicon(iv) phthalocyanine (SiPc) derivatives 3 and 4, which bear these ligands as substituents on the axial positions were synthesized. These SiPcs (3 and 4) were also converted to their water soluble derivatives (3a and 4a). All these novel compounds were fully characterized by a combination of spectroscopic data such as FT-IR, H-NMR, C-NMR and UV-vis as well as mass spectroscopy. The photophysicochemical properties (fluorescence quantum yields and lifetimes, singlet oxygen, and photodegradation quantum yields) were investigated in DMSO for all the studied SiPcs (3 and 4) and in both DMSO and aqueous solutions for the water soluble SiPcs (3a and 4a). Effects of quaternization of these phthalocyanines on photophysicochemical properties were also determined. The photodynamic therapy activities of the water soluble SiPcs (3a and 4a) were tested against to the HeLa cancer cell lines and these phthalocyanines exhibited cytotoxicity against these cell lines.
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http://dx.doi.org/10.1039/d0dt03858jDOI Listing
February 2021

Synthesis of peripheral and non-peripheral substituted metallophthalocyanines containing (E)-3-(5-bromo-2-hydroxphenyl)-1-o-tolyprop-2-en-1-one: Investigation of the photophysical and photochemical properties.

Spectrochim Acta A Mol Biomol Spectrosc 2021 May 15;252:119474. Epub 2021 Jan 15.

Gebze Technical University, Department of Chemistry, Gebze 41400, Kocaeli, Turkey.

In this study, the novel peripherally (5-7) and non-peripherally (9-11) metallo (zinc, magnesium and lead) phthalocyanine derivatives were synthesized from their (E)-4-(4-bromo-2-(3-oxo-3-o-tolyprop-1-enyl)phenoxy) substituted phthalonitrile precursors (4 and 8). These novel phthalocyanine derivatives including chalcone groups were characterized by spectroscopic techniques such as FT-IR, UV-vis, H NMR, C NMR and MALDI-TOF mass spectra. In the next stage, the photophysical and photochemical properties of synthesized compounds were searched in DMSO which is not cause toxic effects at a certain concentration in biological applications. As a result of investigations, it was determined that phthalocyanine complexes did not demonstrate aggregation in DMSO solutions.
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http://dx.doi.org/10.1016/j.saa.2021.119474DOI Listing
May 2021

A novel selective fluorescent chemosensor for Fe ions based on phthalonitrile dimer: synthesis, analysis, and theoretical studies.

Turk J Chem 2020 26;44(5):1254-1264. Epub 2020 Oct 26.

Department of Chemistry, Faculty of Basic Sciences, Gebze Technical University, Kocaeli Turkey.

Phenyl-4,4-di(3,6-dibutoxyphthalonitrile) ( ) was synthesized by the reaction of 1,4-phenylenebisboronic acid ( ) and 4-bromo-3,6-dibutoxyphthalonitrile ( ), using Suzuki cross-coupling reaction. The newly synthesized compound ( ) was characterized by FT-IR, MALDI-MS, ESI-MS, H-NMR, C-NMR, and C-DEPT-135-NMR. The fluorescence property of phenyl-4,4-di(3,6-dibutoxyphthalonitrile) ( ) towards various metal ions was investigated by fluorescence spectroscopy, and it was observed thatthe compound ( ) displayed a significantly 'turn-off' response to Fe , which was referred to 1:2 complex formation between ligand ( ) and Fe . The compound was also studied via density functional theory calculations revealing the interaction mechanism of the molecule with Fe ions.
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http://dx.doi.org/10.3906/kim-2004-68DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7751899PMC
October 2020

Chemosensor properties of 7-hydroxycoumarin substituted cyclotriphosphazenes.

Turk J Chem 2020 11;44(1):64-73. Epub 2020 Feb 11.

Department of Chemistry, Faculty of Art and Science, Marmara University, Kadıköy, İstanbul Turkey.

The newly synthesized cyclotriphosphazene cored coumarin chemosensors 5, 6, and 7 were successfully characterized by H NMR, P NMR, and MALDI-TOF mass spectrometry. Additionally, the photophysical and metal sensing properties of the targeted compounds were determined by fluorescence spectroscopy in the presence of various metals (Li , Na , K , Cs , Mg , Ca , Ba , Cr , Mn , Fe , Co , Al , Hg , Cu , Zn , Ag , and Cd ) . The fluorescence titration results showed that compounds 5, 6, and 7 could be employed as fluorescent chemosensors for Fe ions with high sensitivity. The complex stoichiometry between final cyclotriphosphazene chemosensors and Fe ions was also determined by Job's plots.
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http://dx.doi.org/10.3906/kim-1908-51DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7751823PMC
February 2020

Sensitive, simple and fast voltammetric determination of pesticides in juice samples by novel BODIPY-phthalocyanine-SWCNT hybrid platform.

Food Chem Toxicol 2021 Jan 25;147:111886. Epub 2020 Nov 25.

Gebze Technical University, Department of Chemistry, 41400, Gebze, Kocaeli, Turkey. Electronic address:

The present work describes the first synthesis of novel asymmetric zinc (II) phthalocyanine (ZnPc) including three boron dipyrromethene (BODIPY) and one ethyloxy azido moieties. Moreover, single walled carbon nanotube (SWCNT) surface was functionalized by this ZnPc containing BODIPY; using the azide-alkyne Huisgen cycloaddition (Click) reaction to obtain SWCNT-ZnPc hybrid material. Structural, thermal and morphological characterizations of both ZnPc and SWCNT-ZnPc hybrid were carried out in-depth by spectroscopic, thermal and microscopic techniques. In this study, the synthesized SWCNT-ZnPc material was decorated on composite glassy carbon electrode (GCE) by means of an easy and a practical drop cast method. The modified electrode was tested as a non-enzymatic electrochemical sensor in various common pesticides such as methyl parathion, deltamethrin, chlorpyrifos and spinosad. Electrochemical behavior of non-enzymatic electrode (GCE/SWCNT-ZnPc) was determined via cyclic voltammetry and differential pulse voltammetry. The non-enzymatic sensor demonstrated high selectivity for methyl parathion in a wide linear range (2.45 nM-4.0 × 10 M), low limit of detection value (1.49 nM) and high sensitivity (0.1847 μA nM). Also, the developing non-enzymatic sensor exhibited good repeatability (RSD = 2.3% for 10 electrodes) and stability (85.30% for 30 days). Validation guidelines by HPLC and statistical analysis showed that the proposed voltammetric method were precise, accurate, sensitive, and can be used for the routine quality control of methyl parathion determination in juice samples.
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http://dx.doi.org/10.1016/j.fct.2020.111886DOI Listing
January 2021

A synergetic and sensitive physostigmine pesticide sensor using copper complex of 3D zinc (II) phthalocyanine-SWCNT hybrid material.

Biosens Bioelectron 2021 Feb 19;174:112819. Epub 2020 Nov 19.

Gebze Technical University, Department of Chemistry, Gebze, Kocaeli, 41400, Turkey. Electronic address:

2,3,9,10,16,17,23,24-Octakis (4-methyl-2,6-bis((prop-2-yn-1-yloxy)methyl)phenoxy) phthalocyaninato zinc(II) (Pc) bearing sixteen terminal ethynyl groups was synthesized and attached to SWCNT (Single-walled carbon nanotube) covalently to obtain three dimensional porous hybrid material (SWCNT-Pc 3D) and its copper complex (Cu-SWCNT-Pc 3D). The structural characterization and electrochemical sensor features of the Cu-SWCNT-Pc hybrid towards to physostigmine pesticide were performed. A fast, direct and suitable determination method for physostigmine detection was offered. The designed sensor, Cu-SWCNT-Pc 3D/GCE (glassy carbon electrode) shows sensitivity ca 1.8, 4.3 and 2.8 times more than that of SWCNT/GCE, SWCNT-Pc-noncovalent/GCE and SWCNT-Pc 3D/GCE in terms of peak heights while bare and Pc/GCE had almost no voltammetric response to 2 μM physostigmine in PBS at a pH of 7.0. The limit of detection and quantification of physostigmine determination with Cu-SWCNT-Pc 3D/GCE were found to be 53 and 177 nM in the range of 0.1-4.8 μM, respectively. This study demonstrated that the modification of the GCE with Cu-SWCNT-Pc 3D as an electrochemical sensor was acted as catalytic role toward physostigmine presence of other interfering pesticides as high sensitivity and selectivity. The electrochemical determination of physostigmine in real samples was performed under the optimized conditions, also accuracy of the electrochemical determination method was evaluated with HPLC as a standard determination method.
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http://dx.doi.org/10.1016/j.bios.2020.112819DOI Listing
February 2021

Efficacy of antimicrobial photodynamic therapy administered using methylene blue, toluidine blue and tetra 2-mercaptopyridine substituted zinc phthalocyanine in root canals contaminated with Enterococcusaecalis.

Photodiagnosis Photodyn Ther 2020 Dec 1;32:102038. Epub 2020 Oct 1.

Gebze Technical University, Department of Chemistry, Kocaeli, Turkey.

Background: Traditional chemomechanical treatment procedures are an indispensable part of endodontic treatment, however, additional treatment approaches such as antimicrobial photodynamic therapy (aPDT) may also be recommended for the elimination of residual microorganisms. In this study, the disinfection efficiency of aPDT performed using methylene blue (MB), toluidine blue (TB), and tetra 2-mercaptopyridine substituted zinc phthalocyanine (TM-ZnPc) was compared in the roots contaminated with Enterococcus faecalis (E. faecalis).

Materials And Methods: Forty-nine teeth with a single root and canal were included in this study. The roots were sterilized, and inoculated with E. faecalis. The roots were kept in an incubator for 30 days to form the biofilm. Forty-five teeth were prepared up to the F3 file of the ProTaperNext system under 2.5 % NaOCL irrigation. The samples were divided into three groups according to the type of used photosensitizer (PS) (n = 15); MB (313 μM), TB (327 μM), and TM-ZnPc (6μM). All PSs were irradiation with a light-emitting diode (LED) lamp (630 nm, 2-4 mW/cm²) for the 60 s. Two microbiological samples of the intracanal content were taken (one before and one immediately after additional aPDT in all groups) using sterile paper points. The colony-forming units per milliliter (CFU/mL) were calculated after 24 h of incubation at 37 °C.

Results: After all aPDT protocols, intracanal bacterial load decreased significantly compared to the amount after chemomechanical preparation (P < 0.05). No significant difference in the reduction in intracanal bacterial load was found between the PSs (P < 0.05).

Conclusions: In the current study, the aPDT protocol performed with TM-ZnPc provided similar antimicrobial efficacy, although it was used at a lower concentration compared to MB and TB. Therefore, the use of TM-ZnPc in intra-canal disinfection in endodontics seems promising.
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http://dx.doi.org/10.1016/j.pdpdt.2020.102038DOI Listing
December 2020

Effects of different epidural initiation volumes on postoperative analgesia in cesarean section

Turk J Med Sci 2020 12 17;50(8):1955-1962. Epub 2020 Dec 17.

Department of Anesthesiology and Reanimation, Faculty of Medicine, İnönü University, Malatya, Turkey

Background/aim: The aim of this study was to compare the effects of different epidural initiation volumes on postoperative pain scores, analgesic requirements, and side effects in pregnant women administered patient-controlled epidural analgesia (PCEA) for postoperative pain after cesarean sections.

Materials And Methods: Eighty-one pregnant women, aged 18–45 years, were included in this randomized, double-blind study. Combined spinal epidural anesthesia was administered for each cesarean section. The patients were divided into 3 groups and different volumes (20 mL, 10 mL, and 5 mL) of the study drug (0.0625% bupivacaine plus 2 μg/mL of fentanyl) were administered 90 min after the spinal block via epidural catheter. The visual analogue scale (VAS) scores at rest and during movement, first PCEA dose time, number of PCEA doses required per hour, total analgesic consumed, and side effects were recorded postoperatively.

Results: There were no statistically significant differences among the groups in terms of the VAS rest and VAS movement scores. The times to the first analgesic dose requirement were longer in Group 10 and Group 20 than in Group 5. The analgesic requirement during the first 2 h was lower in Group 20 than in the other groups.

Conclusions: The PCEA initiations with different volumes provided similar pain scores. However, the 20 mL volume resulted in a lower analgesic dose requirement during the early postoperative period, and it also delayed the requirement for analgesia.
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http://dx.doi.org/10.3906/sag-1905-44DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7775685PMC
December 2020

A Hybrid Nanomaterial Based on Single Walled Carbon Nanotubes Cross-Linked via Axially Substituted Silicon (IV) Phthalocyanine for Chemiresistive Sensors.

Molecules 2020 Apr 29;25(9). Epub 2020 Apr 29.

Nikolaev Institute of Inorganic Chemistry SB RAS, Ak. Lavrentiev Avenue, 3, 630090 Novosibirsk, Russia.

In this work, the novel hybrid nanomaterial SWCNT/SiPc made of single walled carbon nanotubes (SWCNT) cross-linked via axially substituted silicon (IV) phthalocyanine (SiPc) was studied as the active layer of chemiresistive layers for the detection of ammonia and hydrogen. SWCNT/SiPc is the first example of a carbon-based nanomaterial in which an axially substituted phthalocyanine derivative is used as a linker. The prepared hybrid material was characterized by spectroscopic methods, thermogravimetry, scanning and transmission electron microscopies. The layers of the prepared hybrid were tested as sensors toward ammonia and hydrogen by a chemiresistive method at different temperatures and relative humidity as well as in the presence of interfering gases like carbon dioxide, hydrogen sulfide and volatile organic vapors. The hybrid layers exhibited the completely reversible sensor response to both gases at room temperature; the recovery time was 100-200 s for NH and 50-120 s in the case of H depending on the gas concentrations. At the relative humidity (RH) of 20%, the sensor response was almost the same as that measured at RH 5%, whereas the further increase of RH led to its 2-3 fold decrease. It was demonstrated that the SWCNT/SiPc layers can be successfully used for the detection of both NH and H in the presence of CO. On the contrary, HS was found to be an interfering gas for the NH detection.
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http://dx.doi.org/10.3390/molecules25092073DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7273219PMC
April 2020

Comparison of videolaryngoscope-guided versus standard digital insertion techniques of the ProSeal™ laryngeal mask airway: a prospective randomized study.

BMC Anesthesiol 2019 12 30;19(1):244. Epub 2019 Dec 30.

School of Medicine, Department of Anesthesiology and Reanimation, Inonu University, Malatya, Turkey.

Background: This study were designed to investigate the usefulness of the videolaryngoscope-guided insertion technique compared with the standard digital technique for the insertion success rate and insertion conditions of the Proseal™ laryngeal mask airway (PLMA).

Methods: Prospective, one hundred and nineteen patients (ASA I-II, aged 18-65 yr) were randomly divided for PLMA insertion using the videolaryngoscope-guided technique or the standard digital technique. The PLMA was inserted according to the manufacturer's instructions in the standard digital technique group. The videolaryngoscope-guided technique was performed a C-MAC® videolaryngoscope with D-Blade, under gentle videolaryngoscope guidance, the epiglottis was lifted, and the PLMA was advanced until the tip of the distal cuff reached the oesophagus inlet. The number of insertion attempts, insertion time, oropharyngeal leak pressure, leak volume, fiberoptic bronchoscopic view, peak inspiratory pressure, ease of gastric tube placement, hemodynamic changes, visible blood on PLMA and postoperative airway morbidity were recorded.

Results: The first-attempt success rate (the primary outcome) was higher in the videolaryngoscope-guided technique than in the standard digital technique (p = 0.029). The effect size values with 95% confidence interval were 0.19 (0.01-0.36) for the first and second attempts, 0.09 (- 0.08-0.27) for the first and third attempts, and not computed for the second and third attempts by the groups, respectively.

Conclusion: Videolaryngoscope-guided insertion technique can be a help in case of difficult positioning of a PLMA and can improve the PLMA performance in some conditions. We suggest that the videolaryngoscope-guided technique may be a useful technique if the digital technique fails.

Trial Registration: ClinicalTrials.gov NCT03852589 date of registration: February 22th 2019.
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http://dx.doi.org/10.1186/s12871-019-0915-3DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC6936072PMC
December 2019

Synthesis and characterization of novel 7-oxy-3-ethyl-6-hexyl-4-methylcoumarin substituted metallo phthalocyanines and investigation of their photophysical and photochemical properties.

Dalton Trans 2019 Sep 13;48(34):13046-13056. Epub 2019 Aug 13.

Marmara University, Department of Chemistry, 34722 Kadikoy, Istanbul, Turkey.

In this study, the synthesis of novel 7-hydroxy-3-ethyl-6-hexyl-4-methylcoumarin (1), four respective phthalonitriles; 4-(7-oxy-3-ethyl-6-hexyl-4-methylcoumarin)phthalonitrile (2), 3-(7-oxy-3-ethyl-6-hexyl-4-methylcoumarin)phthalonitrile (3), 4-chloro-5-(7-oxy-3-ethyl-6-hexyl-4-methylcoumarin)phthalonitrile (4), and 4,5-bis(7-oxy-3-ethyl-6-hexyl-4-methylcoumarin)phthalonitrile (5) and their corresponding alpha tetra, beta tetra and beta octa 7-oxy-3-ethyl-6-hexyl-4-methylcoumarin and beta octa 4-chloro-5-(7-oxy-3-ethyl-6-hexyl-4-methylcoumarin) substituted Zn(ii) (6a-9a) and In(iii) Cl (6b-9b) phthalocyanines has been performed. The novel purified compounds were characterized by standard characterization techniques such as elemental analysis, thermal analysis, FT-IR, UV-vis, H-NMR and MALDI-TOF mass spectrometry. All of the obtained phthalocyanines showed lipophilic behaviour with excellent solubility in organic solvents such as acetone, dichloromethane, chloroform, pyridine and ethyl acetate. The fluorescence quenching behaviour was investigated using 1,4-benzoquinone and potassium iodide as quenchers. The photophysical (fluorescence quantum yields and lifetimes) and photochemical (singlet oxygen and photodegradation quantum yields) properties of these novel phthalocyanines (6a-9a and 6b-9b) were studied in DMF. They produced high singlet oxygen (for example Φ = 0.99 for 7b) and showed appropriate photodegradation (in the order of 10) which is very important for photodynamic therapy (PDT), and thus these phthalocyanines can be used as Type II photosensitizers in PDT applications.
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http://dx.doi.org/10.1039/c9dt02687hDOI Listing
September 2019

Impact of water-soluble zwitterionic Zn(II) phthalocyanines against pathogenic bacteria.

Z Naturforsch C J Biosci 2019 Jul;74(7-8):183-191

Institute of Organic Chemistry with Centre of Phytochemistry, Bulgarian Academy of Sciences, Acad. G. Bonchev str., Bld. 9, 1113 Sofia, Bulgaria.

The photodynamic impact of water-soluble zwitterionic zinc phthalocyanines (ZnPc1-4) was studied on pathogenic bacterial strains after specific light exposure (LED 665 nm). The structural differences between the studied ZnPc1-4 are in the positions and the numbers of substitution groups as well as in the bridging atoms (sulfur or oxygen) between substituents and macrocycle. The three peripherally substituted compounds (ZnPc1-3) are tetra-2-(N-propanesulfonic acid)oxypyridine (ZnPc1), tetra-2-(N-propanesulfonic acid)mercaptopyridine (ZnPc2), and octa-substituted 2-(N-propanesulfonic acid)mercaptopyridine (ZnPc3). The nonperipherally substituted compound is tetra-2-(N-propanesulfonic acid)mercaptopyridine (ZnPc4). The uptake and localization capability are studied on Gram (+) Enterococcus faecalis and Gram (-) Pseudomonas aeruginosa as suspensions and as 48 h biofilms. Relatively high accumulations of ZnPc1-4 show bacteria in suspensions with different cell density. The compounds have complete penetration in E. faecalis biofilms but with nonhomogenous distribution in P. aeruginosa biomass. The cytotoxicity test (Balb/c 3T3 Neutral Red Uptake) with ZnPc1-4 suggests the lack of dark toxicity on normal cells. However, only ZnPc3 has a minimal photocytotoxic effect toward Balb/c 3T3 cells and a comparable high potential in the photoinactivation of pathogenic bacterial species.
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http://dx.doi.org/10.1515/znc-2018-0203DOI Listing
July 2019

The peripheral and non-peripheral 2H-benzotriazole substituted phthalocyanines: Synthesis, characterization, photophysical and photochemical studies of zinc derivatives.

Spectrochim Acta A Mol Biomol Spectrosc 2019 Jun 22;217:128-140. Epub 2019 Mar 22.

Gebze Technical University, Department of Chemistry, Gebze 41400, Kocaeli, Turkey.

In this study, the novel 3-(1H-benzo[d][1,2,3]triazol-1-yl)methoxy substituted novel phthalonitrile compounds (2 and 6) were synthesized. Their non-peripheral and peripheral zinc (II) (3 and 7), manganese (III) (4 and 8) and copper (II) (5 and 9) phthalocyanine complexes were synthesized for the first time. These novel compounds were characterized by elemental analysis and different spectroscopic techniques such as FT-IR, UV-Vis, H NMR, C NMR and MALDI-TOF mass. Also, photochemical and photophysical properties of non-peripheral and peripheral substituted zinc (II) phthalocyanines (3 and 7) were investigated for determination of photodynamic therapy applications of these phthalocyanines.
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http://dx.doi.org/10.1016/j.saa.2019.01.095DOI Listing
June 2019

Comparison of hemodynamic responses and QTc intervals to tracheal intubation with the McGRATH MAC videolaryngoscope and the Macintosh direct laryngoscope in elderly patients.

Kaohsiung J Med Sci 2019 Feb;35(2):116-122

Department of Anaesthesiology and Reanimation, Inonu University, School of Medicine, Malatya, Turkey.

Our hypothesis was that intubations with the McGRATH MAC videolaryngoscope in elderly patients would produce less hemodynamic responses and ECG changes than the Macintosh direct laryngoscope. The patients were divided into two groups: patients who were intubated using the McGRATH MAC (Group V, n = 45) and patients who were intubated using the Macintosh direct laryngoscope (Group L, n = 45). Systolic blood pressure (SBP), diastolic blood pressure (DBP), mean arterial blood pressure (MAP), heart rate (HR) were recorded before induction with anesthesia (baseline), immediately after induction and at 1 min, 3 min, and 5 min after intubation, with simultaneous ECG. When Group L was compared to Group V, there was an increase in the first, third and fitth minutes after intubation in terms of HR. SBP, MAP increased only at 1 min after intubation and DBP increased in the first and third minutes after intubation in Group L. In Group L, there was a significant difference in the HR values immediately after induction and the first minute after intubation compared with the baseline values. There was a difference in the SBP values immediately after induction and at 3 min and 5 min after intubation compared with the baseline values. There was a difference in DBP and MAP values immediately after induction and at 5 min after intubation. When the McGRATH MAC videolaryngoscope was compared with the Macintosh direct laryngoscope in elderly patients, the McGRATH MAC videolaryngoscope decreased the hemodynamic fluctuations due to tracheal intubation.
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http://dx.doi.org/10.1002/kjm2.12017DOI Listing
February 2019

North Polar Tube Reduces the Risk of Epistaxis during Nasotracheal Intubation: A prospective, Randomized Clinical Trial.

Curr Ther Res Clin Exp 2019 9;90:21-26. Epub 2018 Oct 9.

Department of Anesthesia and Reanimation, Faculty of Medicine, Inonu University, Malatya, Turkey.

Objective: In this study, a north polar tube (Portex North Polar tube [Ivory PVC Portex tube; Smiths Medical International, Hythe, United Kingdom]) (NPT) and spiral tube (ST) were compared for their ability to provide a nasal airway in patients during maxillofacial surgery.

Methods: Patients who were aged 18 to 65 years with American Society of Anaesthesiologists score 1 to 2 and Mallampati score 1 to 2 were included in the study. The anesthesia technique was standardized in all patients. Patients were divided into 2 groups randomly: the NPT (n = 35) and ST groups (n = 35). Anesthesia was administered with 1% to 2% sevoflurane and a mixture of 50% oxygen + 50% air in both groups. The mean arterial pressure and heart rate values of preinduction; preintubation; and the first, second, third, and fifth minutes of intubation were recorded. Epistaxis, intraoral bleeding, cuff burst, use of Magill pens, duration of intubation, intubation difficulty, laryngeal compression, head position change, and glottic grade were evaluated.

Results: There were no significant differences between groups in terms of demographic data (gender, age, height, weight, body mass index, American Society of Anaesthesiologists score, and Mallampati score). Macintosh laryngoscopes were used during intubation in all patients. There was no significant difference between groups in terms of intubation difficulty, duration of intubation, use of Magill pens, and determination of the glottic grade ( > 0.05). Epistaxis was significantly lower in the NPT group than in the ST group ( = 0.012). Intraoral bleeding was significantly higher in the ST group than in the NPT group ( = 0.001). During intubation, laryngeal compression (Sellick maneuver) and head position changes were significantly lower in the NPT group than in the ST group ( = 0.003 and < 0.001, respectively). There were no significant differences in mean arterial pressure and heart rate between the 2 groups.

Conclusions: We conclude that the NPT was associated with less epistaxis and manipulations such as laryngeal compression and head position changes when compared with the ST during nasotracheal intubation. The velvet-soft polyvinyl chloride material of the NPT appears to be responsible for this advantage.
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http://dx.doi.org/10.1016/j.curtheres.2018.09.002DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC6369142PMC
October 2018

The synthesis and investigation of photochemical, photophysical and biological properties of new lutetium, indium, and zinc phthalocyanines substituted with PEGME-2000 blocks.

J Biol Inorg Chem 2019 03 23;24(2):191-210. Epub 2019 Jan 23.

Department of Chemistry, Faculty of Science and Letters, Istanbul Technical University, Maslak, 34469, Istanbul, Turkey.

Zinc(II) (5), indium(III) (6), and lutetium(III) (7) phthalocyanines (Pcs) peripherally substituted with poly (ethylene glycol) (PEG) monomethyl ether 2000 (PEGME-2000) blocks were synthesized via Sonogashira coupling reaction with high yields and their photophysical, photochemical and photobiological properties were investigated. We elucidated the interactions of these compounds with calf thymus DNA and bovine serum albumin (BSA), and determined K and K binding constants at degrees of 10 and 10, respectively. Singlet oxygen quantum yields were found (Ф = 0.44, 0.54, and 0.68 for 5, 6, and 7, respectively). Thermodynamic parameters, as well as thermal denaturation profile of double-stranded CT-DNA were examined to determine the type of binding mode. According to our experimental data, we report that PEGME-2000 favors the formation of binary complex between DNA, and phthalocyanine complexes. Therein, thermodynamic data suggest that this binding mode is indeed spontaneous under reported conditions, and rather non-specific. Additionally, Pcs 5, 6, and 7 substituted with PEGME-2000 blocks showed antimicrobial activity against Gram-positive and Gram-negative bacteria, as well as fungi (yeast), and Pc 5 had the highest antimicrobial activity among them, as revealed by disc diffusion assay results. In short, our results suggest that these compounds could be used for photodynamic therapy, they have both antibacterial and antifungal activity, and the binding ability of new phthalocyanines 5, 6, and 7 with BSA paves the way for their utilization as drug vehicle in blood plasma.
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http://dx.doi.org/10.1007/s00775-019-01638-5DOI Listing
March 2019

Highly selective and ultra-sensitive electrochemical sensor behavior of 3D SWCNT-BODIPY hybrid material for eserine detection.

Biosens Bioelectron 2019 Mar 9;128:144-150. Epub 2019 Jan 9.

Department of Chemistry, Gebze Technical University, 41400 Gebze, Kocaeli, Turkey. Electronic address:

In this work, 4,4-difluoro-8-(4-hydroxyphenyl)- 2,6-diethynly-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene (BODIPY) having double terminal ethynyl groups was synthesized. Three dimensional single walled carbon nanotube (SWCNT)-BODIPY hybrid material (3D SWCNT-BODIPY) was synthesized by the reaction of BODIPY bearing double terminal ethynyl groups with azido containing SWCNTs via "Click" reaction. The structural properties and electrochemical detection of eserine (a pesticide) on BODIPY functionalized SWCNTs as a three dimensional (3D) material were investigated. A glassy carbon electrode (GCE) was modified by 3D SWCNT-BODIPY hybrid material for the determination of eserine in the range of 0.25-2.25 μM. In the study by the square wave voltammetry (SWV), the bare GCE showed no response, while the new peak at - 0.6 V appeared in the case of the modified electrode. The detection limit and quantification were determined as 160 nM and 528 nM for eserine on the 3D SWCNT-BODIPY modified electrode, respectively. Eserine was also determined with a standard addition method in different brands of orange juices, and the recovery of eserine was obtained to be in the range of 102.09% and 103.22%. This study clearly indicates that the 3D SWCNT-BODIPY modified electrode tested as an electrochemical sensor was found to be highly selective and sensitive to eserine.
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http://dx.doi.org/10.1016/j.bios.2018.12.052DOI Listing
March 2019

Novel Hexadeca-Substituted Metal Free and Zinc(II) Phthalocyanines; Design, Synthesis and Photophysicochemical Properties.

Molecules 2018 Dec 26;24(1). Epub 2018 Dec 26.

Department of Chemistry, Taibah University, Al-Madinah Al Munawrah, P.O. Box 344, Saudi Arabia.

The syntheses of a novel 1,4,8,11,15,18,22,25-octahexyloxy-2,3,9,10,16,17,23,24-octa-(4-trifluoromethoxyphenyl) phthalocyanine () and its zinc(II) phthalocyanine derivative () have been described and characterized by elemental analysis,¹H NMR, C NMR, F NMR, mass, UV-Vis and FT-IR. The newly prepared metal-free phthalocyanine and its zinc(II) counterpart are soluble in most organic solvents. The photophysical and photochemical properties such as aggregation, fluorescence, singlet oxygen generation and photodegradation under light irradiation of these phthalocyanines have been investigated in DMF. The hexadeca-substituted phthalocyanines ( and ) showed longer absorption and emission wavelength values when compared to that of reported phthalocyanine derivatives due to substitution of the all possible positions in the phthalocyanine framework. The zinc(II) phthalocyanine derivative does not only have a good singlet oxygen generation but also has other photophysicochemical properties that enables this phthalocyanine to be useful as a photosensitizer for cancer treatment using photodynamic therapy.
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http://dx.doi.org/10.3390/molecules24010077DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC6337579PMC
December 2018

Synthesis and organic solar cell performance of BODIPY and coumarin functionalized SWCNTs or graphene oxide nanomaterials.

Dalton Trans 2018 Jul;47(29):9617-9626

Gebze Technical University, Department of Chemistry, Gebze, Kocaeli 41400, Turkey.

The synthesis and characterization of new hybrid materials based on reduced graphene oxide (rGO) or single walled carbon nanotubes (SWCNTs) covalently functionalized by 4,4'-difluoro-8-(4-propynyloxy)-phenyl-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene (BODIPY) (2) or 7-(prop-2-yn-1-yloxy)-3-(3',4',5'-trimethoxyphenyl)-coumarin (4) as light harvesting groups have been described. The organic solar cell performances of these novel nanomaterials in P3HT:PCBM blends were investigated. These covalently bonded hybrid materials (reduced graphene oxide:BODIPY (GB), reduced graphene oxide:Coumarin (GC), SWCNTs:BODIPY (CB) and SWCNTs:Coumarin (CC)) were prepared by an azide-alkyne Huisgen cycloaddition (click) reaction between the azide bearing SWCNTs or rGO and terminal ethynyl functionalized BODIPY (2) or coumarin (4) derivatives. The formation of novel nanomaterials was confirmed by FT-IR, UV-Vis and Raman spectroscopies and thermogravimetric analysis. The best performance on P3HT:PCBM organic solar cells was produced by SWCNTs:Coumarin (CC) hybrids which were coated on an indium tin oxide coated polyethylene terephthalate film (ITO-PET). The reference device based on the P3HT:PCBM blend without CC showed a power conversion efficiency (PCE) of 1.16%, an FF of 35% and a short-circuit current density (Jsc) of 5.51 mA cm-2. The reference device with CC hybrids within the P3HT:PCBM blend increased the values significantly to 1.62% for PCE, 40% for FF and 6.8 mA cm-2 for Jsc.
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http://dx.doi.org/10.1039/c8dt01588kDOI Listing
July 2018

Changes in Melatonin, Cortisol, and Body Temperature, and the Relationship Between Endogenous Melatonin Levels and Analgesia Consumption in Patients Undergoing Bariatric Surgery.

Obes Surg 2018 10;28(10):3186-3192

Department of Anaesthesiology and Reanimation, Inonu University, School of Medicine, Malatya, Turkey.

Background: Melatonin has analgesic, anti-inflammatory, sedative, and anxiolytic properties. However, the relationship between endogenous melatonin levels and postoperative analgesic requirements has not been well elucidated in patients undergoing bariatric surgery. We studied endogenous melatonin levels, cortisol levels, body temperatures, and the relationship between the level of endogenous melatonin and postoperative morphine consumption.

Methods: The trial was conducted among 30 patients who were scheduled for laparoscopic bariatric surgery. Their ages were between 18 and 65 years and their BMIs were above 40 kg/m. Secretion of melatonin, cortisol, and body temperature was monitored before the anesthetic induction, at 2 h intraoperatively, and at 2, 6, 10, (2:00 A.M.) and 24 h postoperatively. For each patient, morphine consumption was assessed at postoperative visits. The primary outcomes were to measure endogenous melatonin levels and to examine the relationship between these levels and morphine consumption. The secondary outcome was to observe the changes in cortisol and body temperature.

Results: There was a significant decrease in melatonin levels when preoperative melatonin levels were compared with intraoperative and all postoperative follow-up periods (p < 0.05). When the correlation between plasma melatonin levels and the postoperative morphine consumption of the patients was inspected, there was a significant correlation in all of the follow-up periods (p < 0.05). When preoperative cortisol levels were compared with intraoperative and postoperative cortisol levels, there was a significant difference in the follow-up periods, except two periods (p < 0.05). Body temperatures were similar in all measurement periods.

Conclusions: Endogenous melatonin secretion was significantly decreased in the intraoperative and postoperative periods. Furthermore, there was a significant inverse correlation between changes in endogenous melatonin levels and morphine consumption.

Trial Registration: Clinical Trial Number NCT03107702 from A service of the U.S. National Institutes of Health, clinicaltrials.gov.
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http://dx.doi.org/10.1007/s11695-018-3313-xDOI Listing
October 2018

Quaternized Zn(II) phthalocyanines for photodynamic strategy against resistant periodontal bacteria.

Z Naturforsch C J Biosci 2018 Apr;73(5-6):221-228

Institute of Organic Chemistry with Centre of Phytochemistry, Bulgarian Academy of Sciences, Acad. G. Bonchev, str., Bl. 9, 1113 Sofia, Bulgaria.

Photodynamic inactivation (PDI) has been featured as an effective strategy in the treatment of acute drug-resistant infections. The efficiency of PDI was evaluated against three periodontal pathogenic bacteria that were tested as drug-resistant strains. In vitro studies were performed with four water-soluble cationic Zn(II) phthalocyanines (ZnPc1-4) and irradiation of a specific light source (light-emitting diode, 665 nm) with three doses (15, 36 and 60 J/cm2). The well detectable fluorescence of ZnPcs allowed the cellular imaging, which suggested relatively high uptakes of ZnPcs into bacterial species. Complete photoinactivation was achieved with all studied ZnPc1-4 for Enterococcus faecalis (E. faecalis) at a light dose of 15 J/cm2. The photodynamic response was high for Prevotella intermedia (P. intermedia) after the application of 6 μM of ZnPc1 and a light dose of 36 J/cm2 and for 6 μM of ZnPc2 at 60 J/cm2. P. intermedia was inactivated with ZnPc3 (4 log) and ZnPc4 (2 log) with irradiation at an optimal dose of 60 J/cm2. Similar photoinactivation results (2 log) were achieved for Aggregatibacter actinomycetemcomitans (A. actinomycetemcomitans) treated with 6 μM ZnPc1 and ZnPc2 at a light dose of 60 J/cm2. The study suggested that PDI with quaternized Zn(II) phthalocyanines and specific light irradiation appears to be a very useful antimicrobial strategy for effective inactivation of drug-resistant periodontal pathogens.
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http://dx.doi.org/10.1515/znc-2017-0167DOI Listing
April 2018

Photophysicochemical, calf thymus DNA binding and in vitro photocytotoxicity properties of tetra-morpholinoethoxy-substituted phthalocyanines and their water-soluble quaternized derivatives.

J Biol Inorg Chem 2017 Dec 19;22(8):1251-1266. Epub 2017 Oct 19.

Department of Chemistry, Faculty of Science and Letters, Istanbul Technical University, 34469, Maslak, Istanbul, Turkey.

In this study, morpholinoethoxy-substituted metal-free (3), zinc(II) (4) and indium(III) (5) phthalocyanines were synthesized. These phthalocyanines were converted to their water-soluble quaternized derivatives (3Q-5Q) using excess methyl iodide as a quaternization agent. All these phthalocyanines (Pcs) were characterized by elemental analysis and different spectroscopic methods such as FT-IR, H NMR, UV-Vis and mass spectrometry. The photophysical and photochemical properties such as fluorescence and generation of singlet oxygen were investigated for determination of these phthalocyanines as photosensitizers in photodynamic therapy (PDT) applications. The binding properties of quaternized phthalocyanines (3Q-5Q) to calf thymus DNA (CT-DNA) were investigated by UV-Vis and fluorescence spectrophotometric methods. The quenching effect of all quaternized phthalocyanines on the fluorescence intensity of SYBR Green-DNA complex was determined. The mixtures of 3Q, 4Q or 5Q and DNA solutions were used to determine the change in T of double helix DNA with thermal denaturation profile. In addition, thermodynamic parameters considering their aggregation in buffer solution, which shows the spontaneity of the reactions between DNA and quaternized Pcs were investigated. On the other hand, in vitro phototoxicity and cytotoxicity behavior of the quaternized water-soluble phthalocyanine photosensitizers (3Q-5Q) were tested against the cervical cancer cell line named HeLa for evaluation of their suitability for treatment of cancer by PDT method. Peripherally tetra-substituted neutral and quaternized metal-free and metallophthalocyanines (MPcs) (Zn, In) bearing morpholinoethoxy groups were prepared. The binding of quaternized compounds (3Q-5Q) to CT-DNA were examined using UV-Vis, fluorescence spectra, thermal denaturation profiles and K values. Besides, thermodynamic studies indicated that binding of 3Q-5Q to DNA was spontaneous. On the other hand, in vitro phototoxicity and cytotoxicity behavior of the quaternized water-soluble phthalocyanine photosensitizers (3Q-5Q) were tested against the cervical cancer cell line named HeLa for evaluation of their suitability for treatment of cancer by PDT method.
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http://dx.doi.org/10.1007/s00775-017-1499-3DOI Listing
December 2017

Phthalocyanine-BODIPY dye: synthesis, characterization, and utilization for pattern recognition of CYFRA 21-1 in whole blood samples.

Anal Bioanal Chem 2017 Oct 29;409(26):6195-6203. Epub 2017 Aug 29.

Kosekoy Vocational School, Kocaeli University, PO Box 141, 41135, Kartepe, Kocaeli, Turkey.

Phthalocyanine-BODIPY dye (BODIPY = boron dipyrromethene) was synthesized, fully characterized, and used for molecular recognition of CYFRA 21-1, a lung cancer biomarker, from whole blood samples. Thin films of three magnesium oxides ((MgO) , where n = 8, 9, or 10)) were deposited on a paper substrate, and they were immersed in a solution of phthalocyanine-BODIPY dye (1.17 × 10 mol/L) for the design of stochastic sensors. Limits of determination of picograms per milliliter magnitude order were recorded for the proposed stochastic sensors. CYFRA 21-1 was reliably identified and determined with recoveries higher than 95% and RSD lower than 1% in whole blood samples.
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http://dx.doi.org/10.1007/s00216-017-0560-yDOI Listing
October 2017

G-quadruplex and calf thymus DNA interaction of quaternized tetra and octa pyridyloxy substituted indium (III) phthalocyanines.

J Photochem Photobiol B 2017 Oct 7;175:9-19. Epub 2017 Aug 7.

Department of Chemistry, Gebze Technical University, Gebze 41400, Kocaeli, Turkey.

The interactions of small molecules with G-quadruplex and double stranded DNA are important due to their potential biological and medical usages. In the present paper, the interactions of indium (III) phthalocyanines (quaternized 2,3,9,10,16,17,23,24-octakis-[(3-pyridyloxy) phthalocyaninato] chloroindium(III): OInPc and quaternized 2(3),9(10),16(17),23(24)-tetrakis-[(3-pyridyloxy) phthalocyaninato] chloroindium(III): TInPc) with hybrid G-quadruplex (Tel 21) and parallel G-quadruplexes (nucleolin, KRAS, c-MYC, vegf) were studied. The interactions of these phthalocyanines with ctDNA were also investigated. These interactions were measured by different spectroscopic techniques such as UV-Vis, fluorescence and circular dichroism. The UV-Vis spectroscopic data treated with Benesi-Hildebrand equation and Benesi-Hildebrand constants (K) were calculated. These constants were found higher for octa peripheral pyridyloxy substituted phthalocyanine, OInPc. Besides, UV-Vis analysis showed that the interaction of G-quadruplexes with tetra peripheral pyridyloxy substituted phthalocyanine derivative (TInPc) resulted in removal of central indium (III) atom from the cavity of phthalocyanine macrocycle. The UV-Vis melting studies as well as fluorescence replacement techniques were also employed for clarification of mechanism. The binding mode of molecules with ct DNA was also supported with viscosity measurements. From the results, the stabilization and destabilization of G-quadruplex depending on the concentration of the OInPc and TInPc showed that these two indium (III) phthalocyanines have the potential of both the elucidation role of G-quadruplexes in gene expression and the usage in cancer therapy.
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http://dx.doi.org/10.1016/j.jphotobiol.2017.08.008DOI Listing
October 2017

Axially substituted silicon(IV) phthalocyanine and its quaternized derivative as photosensitizers towards tumor cells and bacterial pathogens.

Bioorg Med Chem 2017 10 1;25(20):5415-5422. Epub 2017 Aug 1.

Department of Chemistry, Gebze Technical University, Kocaeli 41400, Turkey. Electronic address:

Axially di-(alpha,alpha-diphenyl-4-pyridylmethoxy) silicon(IV) phthalocyanine (3) and its quaternized derivative (3Q) were synthesized and tested as photosensitizers against tumor and bacterial cells. These new phthalocyanines were characterized by elemental analysis, and different spectroscopic methods such as FT-IR, UV-Vis, MALDI-TOF and H NMR. The photophysical properties such as absorption and fluorescence, and the photochemical properties such as singlet oxygen generation of both phthalocyanines were investigated in solutions. The obtained values were compared to the values obtained with unsubstituted silicon(IV) phthalocyanine dichloride (SiPcCl). The addition of two di-(alpha,alpha-diphenyl-4-pyridylmethanol) groups as axial ligands showed an improvement of the photophysical and photochemical properties and an increasement of the singlet oxygen quantum yield (Φ) from 0.15 to 0.33 was determined. The photodynamic efficacy of synthesized photosensitizers (3 and 3Q) were evaluated with promising photocytotoxicity (17% cell survival for 3 and 28% for 3Q) against the cervical cancer cell line (HeLa). The photodynamic inactivation of pathogenic bacterial strains Streptococcus mutans, Staphylococcus aureus, and Pseudomonas aeruginosa suggested a high susceptibility with quaternized derivative (3Q). The both Gram-positive bacterial strains were fully photoinactivated with 11μM 3Q and mild light dose 50J.cm. In case of P. aeruginosa the effect was negligible for concentrations up to 22μM 3Q and light dose 100J.cm. The results suggested that the novel axially substituted silicon(IV) phthalocyanines have promising characteristic as photosensitizer towards tumor cells. The quaternized derivative 3Q has high potential for photoinactivation of pathogenic bacterial species.
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http://dx.doi.org/10.1016/j.bmc.2017.07.065DOI Listing
October 2017

A subphthalocyanine-pyrene dyad: electron transfer and singlet oxygen generation.

Photochem Photobiol Sci 2017 Oct;16(10):1512-1518

Department of Chemistry, Faculty of Science, Kafrelsheikh University, Kafrelsheikh 33516, Egypt.

A light harvesting subphthalocyanine-pyrene dyad has been synthesized and characterized by linking pyrene (Py) with subphthalocyanine (SubPc) at its axial position with the B-O bond through the para position of the benzene group. Upon photoexcitation at the pyrene unit of the dyad, an efficient electron transfer from the singlet-excited state of Py to SubPc was observed. The electron transfer features were also observed by exciting the SubPc entity, but with slower rates (∼10 s). From the electrochemical measurements, the negative driving forces for charge separation via both the singlet states of Py and SubPc in the polar solvents indicate that the electron transfer is thermodynamically feasible. Interestingly, the examined compounds showed relatively high efficiency for producing the singlet oxygen (Φ = ∼0.70). The collected data suggested the usefulness of the examined subphthalocyanine-pyrene dyad as a model of light harvesting system, as well as a sensitizer for photodynamic therapy.
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http://dx.doi.org/10.1039/c7pp00166eDOI Listing
October 2017