scholarly journals Core Modulation of Porphyrins for Chemical Sensing

2021 ◽  
Vol 5 (1) ◽  
pp. 32
Author(s):  
Karolis Norvaiša ◽  
Mathias Otto Senge
Keyword(s):  
Inner Core ◽  
Weak Interactions ◽  
Binding Pocket ◽  
2D Nmr ◽  
Proton Exchange ◽  
Core System ◽  
X Ray Crystallography ◽  
Coordination Sites ◽  
Nmr Techniques ◽  
Symmetry Operations

The inner core system of metal-free (‘free base’) porphyrins has continually served as a ligand for various metal ions, but it was only recently studied in organocatalysis due its highly tunable basicity. Highly conjugated porphyrin systems offer spectrophotometric sensitivity toward geometrical and/or electronic changes and, thus, utilizing the porphyrin core for the selective detection of substrates in solution offers significant potential for a multitude of applications. However, solvation and dilution drastically affect weak interactions by dispersing the binding agent to its surroundings. Thus, the spectroscopic detection of N–H···X-type binding in porphyrin solutions is almost impossible without especially designing the binding pocket. Here, we present the first report on the spectroscopic detection of N–H···X-type interplay in porphyrins formed by weak interactions. Protonated 2,3,7,8,12,13,17,18-octaethyl-5,10,15,20-tetrakis(2-aminophenyl) porphyrin contains coordination sites for the selective binding of charge-bearing analytes, revealing characteristic spectroscopic responses. While electronic absorption spectroscopy proved to be a particularly useful tool for the detection of porphyrin–analyte interactions in the supramolecular complexes, X-ray crystallography helped to pinpoint the orientation, flexibility, and encapsulation of substrates in the corresponding atropisomers. This charge-assisted complexation of analytes in the anion-selective porphyrin inner core system is ideal for the study of atropisomers using high-resolution NMR, since it reduces the proton exchange rate, generating static proton signals. Therefore, we were able to characterize all four rotamers of the nonplanar 2,3,7,8,12,13,17,18-octaethyl-5,10,15,20-tetrakis(2-aminophenyl) porphyrin by performing 1D and 2D NMR spectroscopic analyses of host-guest systems consisting of benzenesulfonic acid (BSA) and each porphyrin atropisomer. Lastly, a detailed assignment of the symmetry operations that are unique to porphyrin atropisomers allowed us to accurately identify the rotamers using NMR techniques only. Overall, the N–H···X-type interplay in porphyrins formed by weak interactions that form restricted H-bonding complexes is shown to be the key to unravelling the atropisomeric enigma.

Reactions of calix[4]arenes with 1,3-dibromopropane and 1,5-dibromopentane. Identification of products using 1D and 2D NMR techniques, and X-ray crystallography

2013 ◽  
Vol 1054-1055 ◽  
pp. 271-281 ◽  
Author(s):  
Paul F. Hudrlik ◽  
Shimelis T. Hailu ◽  
Anne M. Hudrlik ◽  
Ray J. Butcher
Keyword(s):  
2D Nmr ◽  
X Ray ◽  
X Ray Crystallography ◽  
Nmr Techniques

The scope of the β-halogenation of triarylcorroles

2016 ◽  
Vol 20 (01n04) ◽  
pp. 465-474 ◽  
Author(s):  
Sara Nardis ◽  
Giuseppe Pomarico ◽  
Manuela Stefanelli ◽  
Sara Lentini ◽  
Daniel O. Cicero ◽  
...  
Keyword(s):  
Inner Core ◽  
2D Nmr ◽  
Silver Ion ◽  
Free Base ◽  
Reaction Products ◽  
Nmr Analysis ◽  
X Ray ◽  
X Ray Crystallography ◽  
Halogen Atoms

Functionalization of corrole at its peripheral positions is an intriguing field of research, since the unusual reactivity of this macrocycle usually makes it difficult to predict the reaction products. We have investigated the introduction of halogen atoms at the corrole β-positions by using haloacids as reagents. Different behavior, in terms of number and position of the units introduced, was observed: chlorination yielded mono and disubstituted corrole, whereas bromination only afforded mono-substitution, even if on different positions. Iodination did not occur on the corrole free base, while the protection of the inner core by chelation with silver ion gave better results and a symmetric diiodinated corrole was isolated. 2D NMR analysis and X-ray crystallography provided useful information about the site of these corrole functionalizations.

Isolation of New Glycosides from Anemarrhena Asphodeloides Rhizome and Screening of their Anticancer Activity

2019 ◽  
Vol 16 (6) ◽  
pp. 474-477 ◽  
Author(s):  
Pham Van Khang ◽  
Nguyen Thi Hien Lan ◽  
Le Quang Truong ◽  
Mai Thi Minh Chau ◽  
Mai Xuan Truong ◽  
...  
Keyword(s):  
Anticancer Activity ◽  
Spectral Data ◽  
Cell Lines ◽  
Cancer Cell ◽  
Spectroscopic Analysis ◽  
2D Nmr ◽  
Ic50 Values ◽  
Nmr Techniques ◽  
Inhibitory Activities ◽  
Anemarrhena Asphodeloides

In this report, two new steroidal glycosides were isolated and determined from n-butanol fraction of A.asphodeloides. The structures were confirmed in comparison with the spectral data of known compounds by using different spectroscopic analysis approaches including 1D & 2D-NMR techniques and HRMS. The anti-proliferation screening against cancer cell lines A549 and HeLa indicated that compound 1 exhibited good inhibitory activities with IC50 values of 0.79 and 0.55 µg/mL, respectively.

Nuclear Magnetic Resonance Spectroscopic Behaviour of Some Selective Natural Flavonoids: A Look Through

2020 ◽  
Vol 17 (2) ◽  
pp. 185-196
Author(s):  
Shyamal K. Jash ◽  
Dilip Gorai ◽  
Lalan C. Mandal ◽  
Rajiv Roy
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Natural Products ◽  
Magnetic Resonance ◽  
Hard Core ◽  
2D Nmr ◽  
Vital Role ◽  
Spectral Technique ◽  
Nmr Techniques ◽  
Significant Class ◽  
Nuclear Magnetic

Flavonoids are considered as a significant class of compounds among the natural products, exhibiting a variety of structural skeletons as well as multidirectional biological potentials. In structural elucidations of natural products, Nuclear Magnetic Resonance (NMR) spectroscopy has been playing a vital role; the technique is one of the sharpest tools in the hands of natural products chemists. The present resume deals with hard-core applications of such spectral technique, particularly in structural elucidation of flavonoids; different NMR techniques including 1H-NMR, 13C-NMR, and 2D-NMR [viz. 1H-1H COSY, COLOC, HMBC, HMQC] are described in detail.

scholarly journals Sulfanyl Porphyrazines with Morpholinylethyl Periphery—Synthesis, Electrochemistry, and Photocatalytic Studies after Deposition on Titanium(IV) Oxide P25 Nanoparticles

Molecules ◽  
2021 ◽  
Vol 26 (8) ◽  
pp. 2280
Author(s):  
Tomasz Koczorowski ◽  
Wojciech Szczolko ◽  
Anna Teubert ◽  
Tomasz Goslinski
Keyword(s):  
Diclofenac Sodium ◽  
2D Nmr ◽  
Oxide Nanoparticles ◽  
Electrochemical Studies ◽  
Macrocyclic Compounds ◽  
Active Pharmaceutical Ingredients ◽  
Pharmaceutical Ingredients ◽  
Vis Spectroscopy ◽  
Singlet Oxygen Quencher ◽  
Nmr Techniques

The syntheses, spectral UV–Vis, NMR, and electrochemical as well as photocatalytic properties of novel magnesium(II) and zinc(II) symmetrical sulfanyl porphyrazines with 2-(morpholin-4-yl)ethylsulfanyl peripheral substituents are presented. Both porphyrazine derivatives were synthesized in cyclotetramerization reactions and subsequently embedded on the surface of commercially available P25 titanium(IV) oxide nanoparticles. The obtained macrocyclic compounds were broadly characterized by ESI MS spectrometry, 1D and 2D NMR techniques, UV–Vis spectroscopy, and subjected to electrochemical studies. Both hybrid materials, consisting of porphyrazine derivatives embedded on the titanium(IV) oxide nanoparticles’ surface, were characterized in terms of particle size and distribution. Next, they were subjected to photocatalytic studies with 1,3-diphenylisobenzofuran, a known singlet oxygen quencher. The applicability of the obtained hybrid material consisting of titanium(IV) oxide P25 nanoparticles and magnesium(II) porphyrazine derivative was assessed in photocatalytic studies with selected active pharmaceutical ingredients, such as diclofenac sodium salt and ibuprofen.

scholarly journals Phenylhydrazone and Quinazoline Derivatives from the Cold-Seep-Derived Fungus Penicillium oxalicum

Marine Drugs ◽  
2020 ◽  
Vol 19 (1) ◽  
pp. 9
Author(s):  
Ya-Ping Liu ◽  
Sheng-Tao Fang ◽  
Zhen-Zhen Shi ◽  
Bin-Gui Wang ◽  
Xiao-Nian Li ◽  
...  
Keyword(s):  
Deep Sea ◽  
Spectroscopic Data ◽  
2D Nmr ◽  
Penicillium Oxalicum ◽  
Marine Phytoplankton ◽  
Cold Seep ◽  
Phytoplankton Species ◽  
X Ray ◽  
X Ray Crystallography ◽  
Quinazoline Derivatives

Three new phenylhydrazones, penoxahydrazones A–C (compounds 1–3), and two new quinazolines, penoxazolones A (compound 4) and B (compound 5), with unique linkages were isolated from the fungus Penicillium oxalicum obtained from the deep sea cold seep. Their structures and relative configurations were assigned by analysis of 1D/2D NMR and mass spectroscopic data, and the absolute configurations of 1, 4, and 5 were established on the basis of X-ray crystallography or ECD calculations. Compound 1 represents the first natural phenylhydrazone-bearing steroid, while compounds 2 and 3 are rarely occurring phenylhydrazone tautomers. Compounds 4 and 5 are enantiomers that feature quinazoline and cinnamic acid units. Some isolates exhibited inhibition of several marine phytoplankton species and marine-derived bacteria.

scholarly journals Fusarins G–L with Inhibition of NO in RAW264.7 from Marine-Derived Fungus Fusarium solani 7227

Marine Drugs ◽  
2021 ◽  
Vol 19 (6) ◽  
pp. 305
Author(s):  
Guangyuan Luo ◽  
Li Zheng ◽  
Qilin Wu ◽  
Senhua Chen ◽  
Jing Li ◽  
...  
Keyword(s):  
Fusarium Solani ◽  
2D Nmr ◽  
Inflammatory Activity ◽  
Raw264.7 Cells ◽  
Spectroscopic Methods ◽  
X Ray ◽  
X Ray Crystallography ◽  
Structure Activity ◽  
Ic50 Values ◽  
New Compounds

Six new fusarin derivatives, fusarins G–L (1–6), together with five known compounds (5–11) were isolated from the marine-derived fungus Fusarium solani 7227. The structures of the new compounds were elucidated by means of comprehensive spectroscopic methods (1D and 2D NMR, HRESIMS, ECD, and ORC) and X-ray crystallography. Compounds 5–11 exhibited potent anti-inflammatory activity by inhibiting the production of NO in RAW264.7 cells activated by lipopolysaccharide, with IC50 values ranging from 3.6 to 32.2 μM. The structure–activity relationships of the fusarins are discussed herein.

scholarly journals Weak Interactions in Cocrystals of Isoniazid with Glycolic and Mandelic Acids

Crystals ◽  
2021 ◽  
Vol 11 (4) ◽  
pp. 328
Author(s):  
Raquel Álvarez-Vidaurre ◽  
Alfonso Castiñeiras ◽  
Antonio Frontera ◽  
Isabel García-Santos ◽  
Diego M. Gil ◽  
...  
Keyword(s):  
Density Functional ◽  
Glycolic Acid ◽  
Weak Interactions ◽  
Three Dimensional ◽  
Functional Theory ◽  
Molecular Systems ◽  
X Ray Crystallography ◽  
Hydroxycarboxylic Acids ◽  
Non Covalent Interactions ◽  
Covalent Interactions

This work deals with the preparation of pyridine-3-carbohydrazide (isoniazid, inh) cocrystals with two α-hydroxycarboxylic acids. The interaction of glycolic acid (H2ga) or d,l-mandelic acid (H2ma) resulted in the formation of cocrystals or salts of composition (inh)·(H2ga) (1) and [Hinh]+[Hma]–·(H2ma) (2) when reacted with isoniazid. An N′-(propan-2-ylidene)isonicotinic hydrazide hemihydrate, (pinh)·1/2(H2O) (3), was also prepared by condensation of isoniazid with acetone in the presence of glycolic acid. These prepared compounds were well characterized by elemental analysis, and spectroscopic methods, and their three-dimensional molecular structure was determined by single crystal X-ray crystallography. Hydrogen bonds involving the carboxylic acid occur consistently with the pyridine ring N atom of the isoniazid and its derivatives. The remaining hydrogen-bonding sites on the isoniazid backbone vary based on the steric influences of the derivative group. These are contrasted in each of the molecular systems. Finally, Hirshfeld surface analysis and Density-functional theory (DFT) calculations (including NCIplot and QTAIM analyses) have been performed to further characterize and rationalize the non-covalent interactions.

scholarly journals Synthesis and Physicochemical Properties of [(1R,2S,5R)-2-isopropyl-5-methylcyclohexyloxy]-thiophen-5-yl-substituted Tetrapyrazinoporphyrazine with Magnesium(II) Ion

2021 ◽  
Vol 11 (6) ◽  
pp. 2576
Author(s):  
Sebastian Lijewski ◽  
Jiří Tydlitát ◽  
Beata Czarczynska-Goslinska ◽  
Milan Klikar ◽  
Jadwiga Mielcarek ◽  
...  
Keyword(s):  
Quantum Yield ◽  
Singlet Oxygen ◽  
2D Nmr ◽  
Nmr Studies ◽  
Oxygen Formation ◽  
Nmr Techniques ◽  
Flash Column Chromatography ◽  
Photochemical Stability ◽  
Singlet Oxygen Formation ◽  
Very High

Tetrapyrazinoporphyrazine with peripheral menthol-thiophenyl substituents was synthesized using Linstead conditions and purified by flash column chromatography. The optimized synthetic and purification procedures allowed us to obtain a new macrocycle with 36% yield. Tetrapyrazinoporphyrazine derivative was characterized by UV–Vis and NMR spectroscopy, as well as MS spectrometry. Complex NMR studies using 1D and 2D NMR techniques allowed the analysis of the bulky menthol-thiophenyl substituted periphery of the new macrocycle. Further, photochemical stability and singlet oxygen quantum yield were determined by indirect method with diphenylisobenzofuran. The new tetrapyrazinoporphyrazine revealed low generation of singlet oxygen with a quantum yield of singlet oxygen formation at 2.3% in dimethylformamide. In turn, the macrocycle under irradiation with visible light presented very high stability with quantum yield for photostability of 9.59 × 10−6 in dimethylformamide, which figures significantly exceed the border for its classification as a stable porphyrinoid (10−4–10−5).

scholarly journals X-ray crystallography reveals molecular recognition mechanism for sugar binding in a melibiose transporter MelB

2021 ◽  
Vol 4 (1) ◽  
Author(s):  
Lan Guan ◽  
Parameswaran Hariharan
Keyword(s):  
Molecular Recognition ◽  
Binding Pocket ◽  
Cation Binding ◽  
Recognition Mechanism ◽  
X Ray ◽  
X Ray Crystallography ◽  
Sugar Binding ◽  
Sugar Specificity ◽  
Major Facilitator ◽  
Mfs Transporters

AbstractMajor facilitator superfamily_2 transporters are widely found from bacteria to mammals. The melibiose transporter MelB, which catalyzes melibiose symport with either Na+, Li+, or H+, is a prototype of the Na+-coupled MFS transporters, but its sugar recognition mechanism has been a long-unsolved puzzle. Two high-resolution X-ray crystal structures of a Salmonella typhimurium MelB mutant with a bound ligand, either nitrophenyl-α-d-galactoside or dodecyl-β-d-melibioside, were refined to a resolution of 3.05 or 3.15 Å, respectively. In the substrate-binding site, the interaction of both galactosyl moieties on the two ligands with MelBSt are virturally same, so the sugar specificity determinant pocket can be recognized, and hence the molecular recognition mechanism for sugar binding in MelB has been deciphered. The conserved cation-binding pocket is also proposed, which directly connects to the sugar specificity pocket. These key structural findings have laid a solid foundation for our understanding of the cooperative binding and symport mechanisms in Na+-coupled MFS transporters, including eukaryotic transporters such as MFSD2A.

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