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15 pages, 2488 KiB

Open AccessArticle

Synthesis of New Chiral β-Carbonyl Selenides with Antioxidant and Anticancer Activity Evaluation—Part I

by Anna Laskowska, Agata J. Pacuła-Miszewska, Magdalena Obieziurska-Fabisiak, Aneta Jastrzębska, Angelika Długosz-Pokorska, Katarzyna Gach-Janczak and Jacek Ścianowski

Materials 2024, 17(4), 899; https://doi.org/10.3390/ma17040899 - 15 Feb 2024

Viewed by 710

Abstract

A series of unsymmetrical phenyl β-carbonyl selenides with o-amido function substituted on the nitrogen atom with chiral alkyl groups was obtained. The compounds form a series of enantiomeric and diastereomeric pairs and present the first examples of this type of chiral [...] Read more.

A series of unsymmetrical phenyl β-carbonyl selenides with o-amido function substituted on the nitrogen atom with chiral alkyl groups was obtained. The compounds form a series of enantiomeric and diastereomeric pairs and present the first examples of this type of chiral Se derivatives. All obtained selenides were further evaluated as antioxidants and anticancer agents to define the influence of the particular stereochemistry of the attached functional groups on the bioactivity of the molecules. The highest H₂O₂ reduction potential was observed for N-(cis-2-hydroxy-1-indanyl)-2-((2-oxopropyl)selanyl)benzamide, and the best radical scavenging properties for N-(-1-hydroxy-2-butanyl)-2-((2-oxopropyl)selanyl)benzamide. Also, both enantiomers of the N-(1-hydroxy-2-butanyl) selenide expressed the highest cytotoxic potential towards human promyelocytic leukemia HL-60 cell line with similar IC₅₀ values 14.4 ± 0.5 and 16.2 ± 1.1 µM, respectively. On the other hand, breast cancer cell line MCF-7 was most sensitive to N-((R)-(-)-1-hydroxy-2-butanyl)- 2-((2-oxopropyl)selanyl)benzamide (IC50 of 35.7 ± 0.6 µM). The structure–activity dependence of the obtained Se derivatives was discussed, and the most potent compounds were selected. Full article

(This article belongs to the Special Issue Research of Organic Molecules and Materials for Biological Application)

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13 pages, 5397 KiB

Open AccessArticle

New Water-Soluble (Iminomethyl)benzenesulfonates Derived from Biogenic Amines for Potential Biological Applications

by Anna Kmieciak, Marek P. Krzemiński, Anastasiia Hodii, Damian Gorczyca and Aneta Jastrzębska

Materials 2024, 17(2), 520; https://doi.org/10.3390/ma17020520 - 22 Jan 2024

Viewed by 724

Abstract

In this paper, a highly efficient and straightforward method for synthesizing novel Schiff bases was developed by reacting selected biogenic amines with sodium 2-formylbenzene sulfonate and sodium 3-formylbenzene sulfonate. ¹H and ¹³C NMR, IR spectroscopy, and high-resolution mass spectrometry were used [...] Read more.

In this paper, a highly efficient and straightforward method for synthesizing novel Schiff bases was developed by reacting selected biogenic amines with sodium 2-formylbenzene sulfonate and sodium 3-formylbenzene sulfonate. ¹H and ¹³C NMR, IR spectroscopy, and high-resolution mass spectrometry were used to characterize the new compounds. The main advantages of the proposed procedure include simple reagents and reactions carried out in water or methanol and at room temperature, which reduces time and energy. Moreover, it was shown that the obtained water-soluble Schiff bases are stable in aqueous solution for at least seven days. Additionally, the antioxidant and antimicrobial activity of synthesized Schiff bases were tested. Full article

(This article belongs to the Special Issue Research of Organic Molecules and Materials for Biological Application)

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16 pages, 1474 KiB

Open AccessArticle

Synthesis and Characterization of Novel Amphiphilic N-Benzyl 1,4-Dihydropyridine Derivatives—Evaluation of Lipid Monolayer and Self-Assembling Properties

by Anna Krapivina, Davis Lacis, Martins Rucins, Mara Plotniece, Karlis Pajuste, Arkadij Sobolev and Aiva Plotniece

Materials 2023, 16(12), 4206; https://doi.org/10.3390/ma16124206 - 6 Jun 2023

Cited by 2 | Viewed by 1469

Abstract

Liposomes and other nanoparticles have been widely studied as innovative nanomaterials because of their unique properties. Pyridinium salts, on the basis of 1,4-dihydropyridine (1,4-DHP) core, have gained significant attention due to their self-assembling properties and DNA delivery activity. This study aimed to synthesize [...] Read more.

Liposomes and other nanoparticles have been widely studied as innovative nanomaterials because of their unique properties. Pyridinium salts, on the basis of 1,4-dihydropyridine (1,4-DHP) core, have gained significant attention due to their self-assembling properties and DNA delivery activity. This study aimed to synthesize and characterize original N-benzyl substituted 1,4-dihydropyridines and evaluate the influence on structure modifications on compound physicochemical and self-assembling properties. Studies of monolayers composed of 1,4-DHP amphiphiles revealed that the mean molecular areas values were dependent on the compound structure. Therefore, the introduction of N-benzyl substituent to the 1,4-DHP ring enlarged the mean molecular area by almost half. All nanoparticle samples obtained by ethanol injection method possessed positive surface charge and average diameter of 395–2570 nm. The structure of the cationic head-group affects the size of the formed nanoparticles. The diameter of lipoplexes formed by 1,4-DHP amphiphiles and mRNA at nitrogen/phosphate (N/P) charge ratios of 1, 2, and 5 were in the range of 139–2959 nm and were related to the structure of compound and N/P charge ratio. The preliminary results indicated that more prospective combination are the lipoplexes formed by pyridinium moieties containing N-unsubstituted 1,4-DHP amphiphile 1 and pyridinium or substituted pyridinium moieties containing N-benzyl 1,4-DHP amphiphiles 5a–c at N/P charge ratio of 5, which would be good candidates for potential application in gene therapy. Full article

(This article belongs to the Special Issue Research of Organic Molecules and Materials for Biological Application)

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20 pages, 4685 KiB

Open AccessArticle

Polygonum cuspidatum Loaded Nanostructured Lipid Carriers for Dual Inhibition of TNF-α- and IL-6 Cytokines and Free Radical Species

by Teodora-Alexandra Iordache, Nicoleta Badea, Mirela Mihaila, Simona Crisan, Anca Lucia Pop and Ioana Lacatusu

Materials 2023, 16(9), 3492; https://doi.org/10.3390/ma16093492 - 1 May 2023

Cited by 2 | Viewed by 1509

Abstract

The main objective of this study was the testing of natural compounds, such as Polygonum cuspidatum (PgnC) loaded into nanostructured lipid carriers (NLC), which can act as a “double-edged sword” aimed at simultaneously combating dangerous free radicals and inhibiting pro-inflammatory cytokines. Resveratrol-rich PgnC [...] Read more.

The main objective of this study was the testing of natural compounds, such as Polygonum cuspidatum (PgnC) loaded into nanostructured lipid carriers (NLC), which can act as a “double-edged sword” aimed at simultaneously combating dangerous free radicals and inhibiting pro-inflammatory cytokines. Resveratrol-rich PgnC extract was paired with another phytochemical, Diosgenin (DSG), in NLC. The lipid nanocarriers carrying both herbals (NLC-DSG-PgnC) had spherical diameters (100 ± 2 50 nm), a polydispersity index of ~0.15, and electrokinetic potentials greater than −46.5 mV. Entrapment efficiencies of 65% for PgnC and 87% for DSG were determined by chromatographic and UV-Vis spectroscopy assays. Cell cytotoxicity analysis proved that 50 µg/mL of NLC-PgnC and dual-NLC ensured a biocompatible effect like the untreated cells. The dual-NLC assured a much slower in vitro release of DSG and PgnC (67% PgnC and 48% DSG) than the individual-NLC (78% PgnC and 47% DSG) after 4 h of experiments. NLC encapsulating PgnC presented a superior ability to capture cationic radicals: 74.5 and 77.9%. The chemiluminescence results pointed out the non-involvement of DSG in stopping oxygenated free radicals, while the antioxidant activity was maintained at a level higher than 97% for dual-NLC. NLC-DSG-PgnC ensured a promising capacity for inhibition of pro-inflammatory cytokine IL-6, ranging from 91.9 to 94.9%. Full article

(This article belongs to the Special Issue Research of Organic Molecules and Materials for Biological Application)

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16 pages, 883 KiB

Open AccessArticle

The Selection of the Best Derivatization Reagents for the Determination of Polyamines in Home-Made Wine Samples

by Anna Kmieciak, Aneta Jastrzębska, Karolina Szymańska, Marek P. Krzemiński, Tadeusz M. Muzioł, Marzanna Kurzawa and Edward Szłyk

Materials 2023, 16(4), 1474; https://doi.org/10.3390/ma16041474 - 9 Feb 2023

Cited by 3 | Viewed by 1310

Abstract

The procedures of putrescine, spermine, spermidine, and cadaverine derivatization using 2-chloro-1,3-dinitro-5-(trifluoromethyl)benzene, 1-fluoro-2-nitro-4-(trifluoromethyl) benzene, and 3,5-bis-(trifluoromethyl)phenyl isothiocyanate for chromatographic determination in home-made wine samples are compared in the present study. The procedures discussed were compared regarding simplicity, linearity, precision, and accuracy. The polyamines derivatives [...] Read more.

The procedures of putrescine, spermine, spermidine, and cadaverine derivatization using 2-chloro-1,3-dinitro-5-(trifluoromethyl)benzene, 1-fluoro-2-nitro-4-(trifluoromethyl) benzene, and 3,5-bis-(trifluoromethyl)phenyl isothiocyanate for chromatographic determination in home-made wine samples are compared in the present study. The procedures discussed were compared regarding simplicity, linearity, precision, and accuracy. The polyamines derivatives were isolated and characterized by X-ray crystallography and ¹H, ¹³C, and ¹⁹F NMR spectroscopy. The obtained structures of aliphatic amines showed that all amino groups, four in spermine, two in putrescine and cadaverine, and three in spermidine, regardless of the applied reagent, were substituted. The applicability of the described procedures was tested during the chromatographic analysis of the compounds’ content in home-made wines. For this purpose, a simple and environmentally friendly sample preparation procedure was developed. The obtained results present the derivatization of polyamines with 1-fluoro-2-nitro-4-(trifluoromethyl)benzene as a better choice for the determination of these compounds in food samples. Full article

(This article belongs to the Special Issue Research of Organic Molecules and Materials for Biological Application)

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11 pages, 1130 KiB

Open AccessArticle

Simple and Effective Derivatization of Amino Acids with 1-Fluoro-2-nitro-4-(trifluoromethyl)benzene in a Microwave Reactor for Determination of Free Amino Acids in Kombucha Beverages

by Aneta Jastrzębska, Zuzanna Gralak, Kamil Brzuzy, Anna Kmieciak, Marek P. Krzemiński, Rafał Burdziński, Marzanna Kurzawa and Edward Szłyk

Materials 2022, 15(20), 7365; https://doi.org/10.3390/ma15207365 - 20 Oct 2022

Cited by 2 | Viewed by 1729

Abstract

Kombucha is a fermentation product of sweetened tea with a symbiotic culture of acetic acid and yeast bacteria, consumed worldwide for its health-promoting properties. Few reports can be found about free amino acids among the health-promoting compounds found and determined in kombucha. These [...] Read more.

Kombucha is a fermentation product of sweetened tea with a symbiotic culture of acetic acid and yeast bacteria, consumed worldwide for its health-promoting properties. Few reports can be found about free amino acids among the health-promoting compounds found and determined in kombucha. These compounds influence the sensory properties of kombucha, and they are precursors of bioactive compounds, which have a significant role as neurotransmitters and are involved in biological functions. The presented studies proposed a convenient, simple, and “more green” procedure of the synthesis of amino acid derivatives, assisted by microwave energy, followed by chromatographic determination. The structure of 1-Fluoro-2-nitro-4-(trifluoromethyl)benzene was used as a suitable reagent for the derivatization of free amino acids in fermented kombucha beverages prepared from selected dry fruit such as Crataegus L., Morus alba L., Sorbus aucuparia L., Berberis vulgaris L., Rosa canina L., and black tea. The obtained results were discussed regarding the tested beverages’ application as a source of amino acids in one’s daily diet. The obtained results point out that the proposed microwave-assisted derivatization procedure prior to HPLC analyses allows for a significant time reduction and the limitation of using organic reagents. Full article

(This article belongs to the Special Issue Research of Organic Molecules and Materials for Biological Application)

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20 pages, 3414 KiB

Open AccessArticle

Spectroscopic Characterization and Antioxidant Properties of Mandelic Acid and Its Derivatives in a Theoretical and Experimental Approach

by Monika Parcheta, Renata Świsłocka, Grzegorz Świderski, Marzena Matejczyk and Włodzimierz Lewandowski

Materials 2022, 15(15), 5413; https://doi.org/10.3390/ma15155413 - 5 Aug 2022

Cited by 5 | Viewed by 1746

Abstract

The following article discusses the antioxidant properties of mandelic acid and its hydroxy and methoxy derivatives. The antioxidant capacity of these compounds is determined by DPPH, FRAP, CUPRAC and ABTS. The mechanisms underlying the antioxidant properties are described by BDE, IP, PDE, ETE [...] Read more.

The following article discusses the antioxidant properties of mandelic acid and its hydroxy and methoxy derivatives. The antioxidant capacity of these compounds is determined by DPPH, FRAP, CUPRAC and ABTS. The mechanisms underlying the antioxidant properties are described by BDE, IP, PDE, ETE and PA calculation method values and referenced to experimental data. Thermochemistry, HOMO/LUMO energies, dipole moments, charge distribution, IR, RAMAN, NMR frequencies, binding lengths and angles were calculated using the B3LYP method and the 6-311++G(d,p) basis set. The structure of mandelic acid and its derivatives was determined experimentally using IR and RAMAN spectroscopy. Full article

(This article belongs to the Special Issue Research of Organic Molecules and Materials for Biological Application)

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19 pages, 5032 KiB

Open AccessArticle

Differences in the Structure and Antimicrobial Activity of Hydrazones Derived from Methyl 4-Phenylpicolinimidate

by Katarzyna Gobis, Małgorzata Szczesio, Andrzej Olczak, Izabela Korona-Głowniak, Ewa Augustynowicz-Kopeć, Ida Mazernt-Politowicz, Dagmara Ziembicka and Marek L. Główka

Materials 2022, 15(9), 3085; https://doi.org/10.3390/ma15093085 - 24 Apr 2022

Cited by 3 | Viewed by 1552

Abstract

Four novel methyl 4-phenylpicolinoimidate derivatives of hydrazone have been synthesized and evaluated for their antimicrobial activity, including tuberculostatic activity. The compounds obtained are condensates of hydrazonamide or hydrazide with 5-nitro-2-furaldehyde or 5-nitro-2-thiophenecarboxaldehyde. The antimicrobial activity of the tested compounds varied. Compound 3b exhibited [...] Read more.

Four novel methyl 4-phenylpicolinoimidate derivatives of hydrazone have been synthesized and evaluated for their antimicrobial activity, including tuberculostatic activity. The compounds obtained are condensates of hydrazonamide or hydrazide with 5-nitro-2-furaldehyde or 5-nitro-2-thiophenecarboxaldehyde. The antimicrobial activity of the tested compounds varied. Compound 3b exhibited significant activity against the tested Gram-positive bacteria (7.8–250 µg/mL). The results of structural tests revealed that the compound is the only one obtained in the form of a Z isomer. Tuberculostatic activity tests showed higher activity of derivatives 3a and 4a containing nitrofuran systems (MICs 3.1–12.5 µg/mL). This research allowed us to identify hydrazone 3b as a starting point for further optimization in the search for antimicrobial drugs. Likewise, compound 4a appears to be a good guiding structure for use in future research on new anti-tuberculosis drugs. Full article

(This article belongs to the Special Issue Research of Organic Molecules and Materials for Biological Application)

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22 pages, 6246 KiB

Open AccessArticle

Stereoselective Synthesis and Anticancer Activity of 2,6-Disubstituted trans-3-Methylidenetetrahydropyran-4-ones

by Tomasz Bartosik, Joanna Drogosz-Stachowicz, Anna Janecka, Jacek Kędzia, Barbara Pacholczyk-Sienicka, Jacek Szymański, Katarzyna Gach-Janczak and Tomasz Janecki

Materials 2022, 15(9), 3030; https://doi.org/10.3390/ma15093030 - 21 Apr 2022

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Abstract

In this report, we present efficient and stereoselective syntheses of 2,6-disubstituted trans-3-methylidenetetrahydropyran-4-ones and 2-(4-methoxyphenyl)-5-methylidenetetrahydropyran-4-one that significantly broaden the spectrum of the available methylidenetetrahydropyran-4-ones with various substitution patterns. Target compounds were obtained using Horner–Wadsworth–Emmons methodology for the introduction of methylidene group onto the [...] Read more.

In this report, we present efficient and stereoselective syntheses of 2,6-disubstituted trans-3-methylidenetetrahydropyran-4-ones and 2-(4-methoxyphenyl)-5-methylidenetetrahydropyran-4-one that significantly broaden the spectrum of the available methylidenetetrahydropyran-4-ones with various substitution patterns. Target compounds were obtained using Horner–Wadsworth–Emmons methodology for the introduction of methylidene group onto the pyranone ring. 3-Diethoxyphosphoryltetrahydropyran-4-ones, which were key intermediates in this synthesis, were prepared by fully or highly stereoselective addition of Gilman or Grignard reagents to 3-diethoxyphosphoryldihydropyran-4-ones. Addition occurred preferentially by axial attack of the Michael donors on the dihydropyranone ring. Relative configurations and conformations of the obtained adducts were assigned using a detailed analysis of the NMR spectra. The obtained methylidenepyran-4-ones were evaluated for cytotoxic activity against two cancer cell lines (HL-60 and MCF-7). 2,6-Disubstituted 3-methylidenetetrahydropyran-4-ones with isopropyl and phenyl substituents in position 2 were more cytotoxic than analogs with n-butyl substituent. Two of the most cytotoxic analogs were then selected for further investigation on the HL-60 cell line. Both analogs induced morphological changes characteristic of apoptosis in cancer cells, significantly inhibited proliferation and induced apoptotic cell death. Both compounds also generated DNA damage, and one of the analogs arrested the cell cycle of HL-60 cells in the G2/M phase. In addition, both analogs were able to inhibit the activity of topoisomerase IIα. Based on these findings, the investigated analogs may be further optimized for the development of new and effective topoisomerase II inhibitors. Full article

(This article belongs to the Special Issue Research of Organic Molecules and Materials for Biological Application)

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14 pages, 1684 KiB

Open AccessArticle

Attachment of Chiral Functional Groups to Modify the Activity of New GPx Mimetics

by Anna Laskowska, Agata Joanna Pacuła-Miszewska, Angelika Długosz-Pokorska, Anna Janecka, Andrzej Wojtczak and Jacek Ścianowski

Materials 2022, 15(6), 2068; https://doi.org/10.3390/ma15062068 - 11 Mar 2022

Cited by 8 | Viewed by 1516

Abstract

A series of new chiral benzisoselenazol-3(2H)-ones and their corresponding diselenides bearing an o-amido function substituted on the nitrogen atom with various aliphatic and aromatic moieties were synthesized. All derivatives representing pairs of enantiomers or diastereoisomers were obtained to thoroughly evaluate [...] Read more.

A series of new chiral benzisoselenazol-3(2H)-ones and their corresponding diselenides bearing an o-amido function substituted on the nitrogen atom with various aliphatic and aromatic moieties were synthesized. All derivatives representing pairs of enantiomers or diastereoisomers were obtained to thoroughly evaluate the three-dimensional structure–activity correlation. First, bensisoselenazol-3(2H)-ones were synthesized by reacting 2-(chloroseleno)benzoyl chloride with an appropriate enantiomerically pure amine. Then, the Se–N bond was cleaved by a reduction–oxidation procedure using sodium borohydride and then air oxidation to obtain the corresponding diselenides. All derivatives were tested as antioxidants and anticancer agents. In general, the diselenides were more reactive peroxide scavengers, with the highest activity observed for 2,2′-diselenobis[N-(1S,2S)-(-)-trans-2-hydroksy-1-indanylbezamide]. The most cytotoxic derivative towards human promyelocytic leukemia HL-60 and breast cancer MCF-7 cell lines was N-[(1S,2R)-(-)-cis-2-hydroksy-1-indanyl]-1,2-benzizoselenazol-3(2H)-one. The structure–activity relationship of the obtained organoselenium derivatives was discussed. Full article

(This article belongs to the Special Issue Research of Organic Molecules and Materials for Biological Application)

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21 pages, 3601 KiB

Open AccessArticle

Synthesis, Crystal Structure, and Biological Evaluation of Novel 5-Hydroxymethylpyrimidines

by Marcin Stolarczyk, Agnieszka Matera-Witkiewicz, Aleksandra Wolska, Magdalena Krupińska, Aleksandra Mikołajczyk, Anna Pyra and Iwona Bryndal

Materials 2021, 14(22), 6916; https://doi.org/10.3390/ma14226916 - 16 Nov 2021

Cited by 2 | Viewed by 1369

Abstract

Pyrimidine displays a wide array of bioactivities, and thence, it is still considered a potent unit of new drug research. Its derivative, 5-hydroxymethylpyrimidine, can be found as a scaffold of nontypical nitrogen bases in DNA and as a core of some natural bioactive [...] Read more.

Pyrimidine displays a wide array of bioactivities, and thence, it is still considered a potent unit of new drug research. Its derivative, 5-hydroxymethylpyrimidine, can be found as a scaffold of nontypical nitrogen bases in DNA and as a core of some natural bioactive compounds. In this study, we obtained a series of 5-hydroxymethylpyrimidines that vary in the 4-position by the reduction of proper esters. All compounds were characterized by spectroscopic analysis, and single-crystal X-ray diffraction was performed for some of them. Biological investigations estimated cytotoxic properties against normal (RPTEC) and cancer (HeLa, HepaRG, Caco-2, AGS, A172) cell lines. It was found that the derivatives with an aliphatic amino group at the 4-position are generally less toxic to normal cells than those with a benzylsulfanyl group. Moreover, compounds with bulky constituents exhibit better anticancer properties, though at a moderate level. The specific compounds were chosen due to their most promising IC50 concentration for in silico study. Furthermore, antimicrobial activity tests were performed against six strains of bacteria and one fungus. They demonstrated that only derivatives with at least three carbon chain amino groups at the 4-position have weak antibacterial properties, and only the derivative with 4-benzylsulfanyl constituent exhibits any antifungal action. Full article

(This article belongs to the Special Issue Research of Organic Molecules and Materials for Biological Application)

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24 pages, 4357 KiB

Open AccessArticle

Mesoporous Networks of N-Vinylpyrrolidone with (di)Methacrylates as Precursors of Ecological Molecular Imprinted Polymers

by Svetlana V. Kurmaz, Natalia V. Fadeeva, Anna I. Gorshkova, Sergey A. Kurochkin, Eugenia I. Knerelman, Galina I. Davydova, Vladimir I. Torbov, Nadezhda N. Dremova, Dmitry V. Konev, Vladimir A. Kurmaz, Vladislav M. Ignatiev and Nina S. Emelyanova

Materials 2021, 14(22), 6757; https://doi.org/10.3390/ma14226757 - 9 Nov 2021

Cited by 6 | Viewed by 1724

Abstract

Mesoporous polymer networks were prepared via the cross-linking radical copolymerization of non-toxic hydrophilic N-vinylpyrrolidone (VP) with triethylene glycol dimethacrylate (TEGDM) and poly(ethylene glycol) methyl ester methacrylate (PEGMMA) in bulk, using appropriate soluble and thermodynamically compatible macromolecular additives with a branched structure as [...] Read more.

Mesoporous polymer networks were prepared via the cross-linking radical copolymerization of non-toxic hydrophilic N-vinylpyrrolidone (VP) with triethylene glycol dimethacrylate (TEGDM) and poly(ethylene glycol) methyl ester methacrylate (PEGMMA) in bulk, using appropriate soluble and thermodynamically compatible macromolecular additives with a branched structure as porogens. The branched copolymers of various monomer compositions were obtained by radical copolymerization in toluene, controlled by 1-decanethiol, and these materials were characterized by a wide set of physical chemical methods. The specific surface areas and surface morphology of the polymer networks were determined by nitrogen low-temperature adsorption or Rose Bengal (RB) sorption, depending on the copolymer compositions and scanning electron microscopy. The electrochemical properties of RB before and after its encapsulation into a branched VP copolymer were studied on a glassy carbon electrode and the interaction between these substances was observed. Quantum chemical modeling of RB-VP or RB-copolymer complexes has been carried out and sufficiently strong hydrogen bonds were found in these systems. The experimental and modeling data demonstrate the high potency of such mesoporous polymer networks as precursors of molecularly imprinted polymers for the recognition of fluorescent dyes as nanomarkers for biomedical practice. Full article

(This article belongs to the Special Issue Research of Organic Molecules and Materials for Biological Application)

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23 pages, 6072 KiB

Open AccessArticle

Lipid Nanoparticles Loaded with Selected Iridoid Glycosides as Effective Components of Hydrogel Formulations

by Marta Dąbrowska and Izabela Nowak

Materials 2021, 14(15), 4090; https://doi.org/10.3390/ma14154090 - 22 Jul 2021

Cited by 6 | Viewed by 1933

Abstract

One possibility of improving active ingredient penetration into deeper skin layers to enhance the cosmetic product effectiveness, is the application of lipid nanoparticles. The aim of the study presented in this paper was to evaluate the potential of hydrogel formulations enriched with iridoid [...] Read more.

One possibility of improving active ingredient penetration into deeper skin layers to enhance the cosmetic product effectiveness, is the application of lipid nanoparticles. The aim of the study presented in this paper was to evaluate the potential of hydrogel formulations enriched with iridoid glycosides-loaded lipid nanoparticles. Lipid nanocarriers were produced using an emulsification-ultrasonication method based on multiple emulsions. The encapsulation efficiency was determined at the level of 89% and 77% for aucubin and catalpol, respectively. The next stage was the incorporation of the obtained dispersions of lipid nanoparticles into hydrogel formulations, followed by determination of their physicochemical properties, shelf-life stability, and application properties (in vivo tests). The introduction of lipid nanoparticles increased the stabilization of the consistency of the obtained hydrogel formulations, and was confirmed by viscosity measurements. No effect of lipid nanoparticle incorporation on shelf-life stability of the hydrogels was detected. In vivo studies showed improvements in moisture content of the epidermis, transepidermal water loss, skin topography, and macrorelief parameters. In particular, a synergistic effect of the active ingredients and lipid nanoparticles on the anti-wrinkle effect, moisturizing effect, and regeneration of the protective barrier of the stratum corneum was evidenced. The attractiveness of aucubin and catalpol as cosmetic raw materials in hydrogel formulations was evidenced, especially when the iridoid glycosides were applied in the form of lipid nanoparticles. Full article

(This article belongs to the Special Issue Research of Organic Molecules and Materials for Biological Application)

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16 pages, 2185 KiB

Open AccessArticle

Steryl Sinapate as a New Antioxidant to Improve Rapeseed Oil Quality during Accelerated Shelf Life

by Dobrochna Rabiej-Kozioł, Marek P. Krzemiński and Aleksandra Szydłowska-Czerniak

Materials 2021, 14(11), 3092; https://doi.org/10.3390/ma14113092 - 4 Jun 2021

Cited by 3 | Viewed by 1986

Abstract

In recent years, steryl esters have become an attractive for the cosmetic, pharmaceutical, and food industries. Hence, the effect of exogenous antioxidant, β-sitosteryl sinapate on oxidative stability and antioxidant activity (AA) of refined rapeseed oil was evaluated by the accelerated shelf-life test. Oxidative [...] Read more.

In recent years, steryl esters have become an attractive for the cosmetic, pharmaceutical, and food industries. Hence, the effect of exogenous antioxidant, β-sitosteryl sinapate on oxidative stability and antioxidant activity (AA) of refined rapeseed oil was evaluated by the accelerated shelf-life test. Oxidative parameters of refined rapeseed oil—peroxide value (PV), anisidine value (p-AnV), acid value (AV), and spectrophotometric indices (K₂₃₂, K₂₆₈)—increased during storage. However, the addition of β-sitosteryl sinapate caused a decrease of the primary and secondary oxidation products in the supplemented oils in comparison with the control sample. Moreover, oils with steryl ester had higher AA than oil without the synthetic antioxidant. The accelerated storage negatively affected the antioxidant potential of refined and enriched oils causing the AA decrease by 25–54% and 7–15%, respectively. Studies have consistently demonstrated beneficial associations between the presence of β-sitosteryl sinapate in oil samples and the inhibition of their oxidative degradation under the accelerated conditions. Additionally, the possibility of using the synchronous fluorescence (SF) spectroscopy and excitation–emission matrix (EEM) fluorescence spectroscopy for identification and observing changes in main fluorescent components present in non-supplemented and supplemented rapeseed oils during the accelerated storage was attempted. Full article

(This article belongs to the Special Issue Research of Organic Molecules and Materials for Biological Application)

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17 pages, 3247 KiB

Open AccessEditor’s ChoiceArticle

Promising Green Technology in Obtaining Functional Plant Preparations: Combined Enzyme-Assisted Supercritical Fluid Extraction of Flavonoids Isolation from Medicago Sativa Leaves

by Aneta Krakowska-Sieprawska, Katarzyna Rafińska, Justyna Walczak-Skierska, Anna Kiełbasa and Bogusław Buszewski

Materials 2021, 14(11), 2724; https://doi.org/10.3390/ma14112724 - 21 May 2021

Cited by 13 | Viewed by 2345

Abstract

To elaborate a complete extraction protocol for the enhanced release of biologically active compounds from plant cells, this study aimed to optimize together the parameters of the supercritical fluid extraction (SFE) process (temperature, pressure, and percentage of cosolvent) and enzymatic treatment of plant [...] Read more.

To elaborate a complete extraction protocol for the enhanced release of biologically active compounds from plant cells, this study aimed to optimize together the parameters of the supercritical fluid extraction (SFE) process (temperature, pressure, and percentage of cosolvent) and enzymatic treatment of plant material (pH, enzyme concentration, time, and temperature) by response surface methodology (RSM). Medicago sativa L. was selected as a plant material due to its richness in phenolics and flavonoids. HPLC-MS/MS analysis allowed evaluating the content of individual bioactive compounds in obtained extracts. The total content of polyphenolic compounds in the extract obtained after two-step optimization was much higher (546 ± 21 µg/g) than in the extract obtained from non-hydrolyzed material (275 ± 23 µg/g) and in the extract obtained by maceration (162 ± 20 µg/g). Furthermore, it was evidenced that extract with the highest content of polyphenolic compounds can support the cellular antioxidant system both as a free radical scavenger and by stimulating the antioxidant enzyme system. Full article

(This article belongs to the Special Issue Research of Organic Molecules and Materials for Biological Application)

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14 pages, 2343 KiB

Open AccessArticle

Cytotoxic Activity of Piperazin-2-One-Based Structures: Cyclic Imines, Lactams, Aminophosphonates, and Their Derivatives

by Jakub Iwanejko, Mahzeiar Samadaei, Matthias Pinter, Daniel Senfter, Sibylle Madlener, Andrzej Kochel, Nataliya Rohr-Udilova and Elżbieta Wojaczyńska

Materials 2021, 14(9), 2138; https://doi.org/10.3390/ma14092138 - 22 Apr 2021

Cited by 6 | Viewed by 2037

Abstract

N-Heterocycles are considered as desirable scaffolds for the development of novel lead compounds for anticancer drug research. Among them, phosphorus-containing amino-derivatives play a crucial role. A series of imines and products of their further reactions with P-nucleophiles were obtained starting from [...] Read more.

N-Heterocycles are considered as desirable scaffolds for the development of novel lead compounds for anticancer drug research. Among them, phosphorus-containing amino-derivatives play a crucial role. A series of imines and products of their further reactions with P-nucleophiles were obtained starting from vicinal bisamines. Reaction of ethylenediamine and α-carbonyl esters yielded in novel unexpected products, which structures were confirmed by crystallographic measurements. The cytotoxic activity evaluation was done on a variety of cell lines including HUH7, AKH12, DAOY, UW228-2, D283, D425, and U251. Human umbilical vein endothelial cells (HUVECs) were used as control. Two of the tested compounds, bearing TADDOL-derived, and trifluoromethyl substituents showed a significant effect on cell viability, though comparable to nonmalignant cells. Full article

(This article belongs to the Special Issue Research of Organic Molecules and Materials for Biological Application)

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10 pages, 1737 KiB

Open AccessArticle

Intramolecular C-N Bond Formation via Thermal Arene C-H Bond Activation Supported by Au(III) Complexes

by Julianna Mruk, Agata J. Pacuła-Miszewska, Leszek Pazderski, Joanna Drogosz-Stachowicz, Anna E. Janecka and Jacek Ścianowski

Materials 2021, 14(7), 1676; https://doi.org/10.3390/ma14071676 - 29 Mar 2021

Viewed by 1682

Abstract

One of the main tactics to access C-N bonds from inactivated C-H functionalities is direct transition metal-supported aminations. Due to the often harsh reaction conditions, the current goal in the field is the search for more mild and sustainable transformations. Herein, we present [...] Read more.

One of the main tactics to access C-N bonds from inactivated C-H functionalities is direct transition metal-supported aminations. Due to the often harsh reaction conditions, the current goal in the field is the search for more mild and sustainable transformations. Herein, we present the first solvent-free thermally induced C-N bond formation driven by Au(III) salts. The general structure of the products was confirmed by ¹H, ¹³C, ¹⁵N NMR, TGA-DTA and ATR/FT-IR analysis. Additionally, all derivatives were tested as catalysts in a three-component coupling reaction between phenylacetylene, benzaldehyde and piperidine and as anticancer agents on HL-60 and MCF-7 cell lines. Full article

(This article belongs to the Special Issue Research of Organic Molecules and Materials for Biological Application)

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17 pages, 1373 KiB

Open AccessArticle

Platinum(II) Complexes with Bulky Disubstitute Triazolopyrimidines as Promising Materials for Anticancer Agents

by Iwona Łakomska, Dariusz Śmiłowicz, Mateusz Jakubowski, Jerzy Sitkowski and Andrzej Wojtczak

Materials 2020, 13(23), 5312; https://doi.org/10.3390/ma13235312 - 24 Nov 2020

Cited by 4 | Viewed by 2110

Abstract

Herein, we present dicarboxylate platinum(II) complexes of the general formula [Pt(mal)(DMSO)(L)] and [Pt(CBDC)(DMSO)(L)], where L is dbtp 5,7-ditertbutyl-1,2,4-triazolo[1,5-a]pyrimidine) or ibmtp (7-isobutyl-5-methyl-1,2,4- triazolo[1,5-a]pyrimidine), as prospective prodrugs. The platinum(II) complexes were synthesized in a one-pot reaction between cis-[PtCl [...] Read more.

Herein, we present dicarboxylate platinum(II) complexes of the general formula [Pt(mal)(DMSO)(L)] and [Pt(CBDC)(DMSO)(L)], where L is dbtp 5,7-ditertbutyl-1,2,4-triazolo[1,5-a]pyrimidine) or ibmtp (7-isobutyl-5-methyl-1,2,4- triazolo[1,5-a]pyrimidine), as prospective prodrugs. The platinum(II) complexes were synthesized in a one-pot reaction between cis-[PtCl₂(DMSO)₂], silver malonate or silver cyclobutane-1,1-dicarboxylate and triazolopyrimidines. All platinum(II) compounds were characterized by FT-IR, and ¹H, ¹³C, ¹⁵N and ¹⁹⁵Pt NMR; and their square planar geometries with one monodentate N(3)-bonded 5,7-disubstituted-1,2,4-triazolo[1,5-a]pyrimidine, one S-bonded molecule of dimethyl sulfoxide and one O,O-chelating malonato (1, 2) or O,O-chelating cyclobutane-1,1-dicarboxylato (3, 4) was determined. Additionally, [Pt(CBDC)(dbtp)(DMSO)] (3) exhibited (i) substantial in vitro cytotoxicity against the lung adenocarcinoma epithelial cell line (A549) (IC₅₀ = 5.00 µM) and the cisplatin-resistant human ductal breast epithelial tumor cell line (T47D) (IC₅₀ = 6.60 µM); and (ii) definitely exhibited low toxicity against normal murine embryonic fibroblast cells (BALB/3T3). Full article

(This article belongs to the Special Issue Research of Organic Molecules and Materials for Biological Application)

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15 pages, 2244 KiB

Open AccessEditor’s ChoiceArticle

New Polyphenol-Containing LDL Nano-Preparations in Oxidative Stress and DNA Damage: A Potential Route for Cell-Targeted PP Delivery

by Hanna Lewandowska and Monika Kalinowska

Materials 2020, 13(22), 5106; https://doi.org/10.3390/ma13225106 - 12 Nov 2020

Cited by 5 | Viewed by 1712

Abstract

Low-density lipoprotein (LDL) preparations of the chosen polyphenols (PPs) were prepared for the first time in the literature. The solubility of the PPs in the lipidic core of the LDL increased with the increase of their lipophilicity. The anti-/pro-oxidative properties and toxicity of [...] Read more.

Low-density lipoprotein (LDL) preparations of the chosen polyphenols (PPs) were prepared for the first time in the literature. The solubility of the PPs in the lipidic core of the LDL increased with the increase of their lipophilicity. The anti-/pro-oxidative properties and toxicity of LDL-entrapped PPs toward A 2780 human ovarian cancer cells were examined. The obtained preparations were found to be stable in PBS, and characterized by low toxicity. A binding affinity study revealed that the uptake of PP-loaded LDL particles is non-receptor-specific under experimental conditions. The antioxidative potential of the obtained PPs-doped LDL preparations was shown to be higher than for the PPs themselves, probably due to facilitating transport of LDL preparations into the cellular milieu, where they can interact with the cellular systems and change the redox status of the cell. The PPs-loaded LDL displayed the highest protective effect against Fenton-type reaction induced oxidative DNA damage. Full article

(This article belongs to the Special Issue Research of Organic Molecules and Materials for Biological Application)

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13 pages, 447 KiB

Open AccessArticle

Synthesis of Steryl Hydroxycinnamates to Enhance Antioxidant Activity of Rapeseed Oil and Emulsions

by Dobrochna Rabiej-Kozioł, Marek P. Krzemiński and Aleksandra Szydłowska-Czerniak

Materials 2020, 13(20), 4536; https://doi.org/10.3390/ma13204536 - 13 Oct 2020

Cited by 10 | Viewed by 1747

Abstract

In recent years, steryl esters have found potential applications in food, pharmaceutical and cosmetic industries. Therefore, three hydroxycinnamate steryl esters (HSEs): β-sitosteryl sinapate (β-SSA), β-sitosteryl caffeate (β-SCA), and β-sitosteryl ferulate (β-SFA) were synthesized by chemical approach and their antioxidant activity (AA) were analyzed [...] Read more.

In recent years, steryl esters have found potential applications in food, pharmaceutical and cosmetic industries. Therefore, three hydroxycinnamate steryl esters (HSEs): β-sitosteryl sinapate (β-SSA), β-sitosteryl caffeate (β-SCA), and β-sitosteryl ferulate (β-SFA) were synthesized by chemical approach and their antioxidant activity (AA) were analyzed by 2,2-diphenyl-1-picrylhydrazyl (DPPH) and 2,2′-azinobis-(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS) assays. The values of inhibitory concentration (IC₅₀) of each ester needed to inhibit 50% of the DPPH radical (IC_50(DPPH) = 238.9, 78.3, 290.0 µmol/L for β-SSA, β-SCA, and β-SFA, respectively) and ABTS radical cation (IC_50(ABTS) = 174.6, 106.7, 206.0 µmol/L for β-SSA, β-SCA, and β-SFA, respectively) were estimated and compared with antioxidant potential of phenolic acids. Moreover, the effect of HSEs addition in the concentrations range between 0.01% and 0.5% on the AA of refined rapeseed oil, mayonnaise and margarine was evaluated. Chemical structures of the synthesized HSEs and their concentrations strongly affect the AA of fat products. Oil and emulsions supplemented with higher concentrations of HSEs had significantly higher AA than control samples. Unfortunately, lower concentrations of HSEs (0.01% and 0.02%) did not increase the AA of fat products. However, steryl phenolates added in higher amounts can be considered as potential antioxidants delaying the oxidation processes of studied fats. Full article

(This article belongs to the Special Issue Research of Organic Molecules and Materials for Biological Application)

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18 pages, 4295 KiB

Open AccessArticle

Synthesis of Magnetic Molecularly Imprinted Polymer Sorbents for Isolation of Parabens from Breast Milk

by Martyna Pajewska-Szmyt, Ewelina Biniewska, Bogusław Buszewski and Renata Gadzała-Kopciuch

Materials 2020, 13(19), 4328; https://doi.org/10.3390/ma13194328 - 29 Sep 2020

Cited by 7 | Viewed by 2158

Abstract

Magnetic molecularly imprinted polymers (MMIPs) are an invaluable asset in the development of many methods in analytical chemistry, particularly sample preparation. Novel adsorbents based on MMIPs are characterized by high selectivity towards a specific analyte due to the presence of a specific cavity [...] Read more.

Magnetic molecularly imprinted polymers (MMIPs) are an invaluable asset in the development of many methods in analytical chemistry, particularly sample preparation. Novel adsorbents based on MMIPs are characterized by high selectivity towards a specific analyte due to the presence of a specific cavity on their polymer surface, enabling the lock–key model interactions to occur. In addition, the magnetic core provides superparamagnetic properties that allow rapid separation of the sorbent from the sample solution. Such a combination of imprinted polymers with a magnetic core has an innovative influence on the development of separation techniques. Hence, the present study describes the synthesis of MMIPs with 17β-estradiol used as a template molecule in the production of imprinted polymers. The as-prepared sorbent was used for a sorption/desorption study of five parabens from breast milk samples. The obtained results were characterized by sorption efficiency exceeding 92%, which shows the high affinity of the analytes to the functional groups on the sorbent. The final determination of the selected analytes was done with high-performance liquid chromatography using a fluorometric detector. The determined linearity ranges for selected parabens were characterized by high determination coefficients (r² from 0.9992 to 0.9999), and the calculated limit of detection (LOD) and limit of quantification (LOQ) for the identified compounds were low (LOD from 1.1–2.7 ng mL⁻¹; LOQ from 3.6–8.1 ng mL⁻¹), which makes their quantitative analysis in real samples feasible. Full article

(This article belongs to the Special Issue Research of Organic Molecules and Materials for Biological Application)

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16 pages, 1122 KiB

Open AccessArticle

Synthesis, Selected Transformations, and Biological Activity of Alkoxy Analogues of Lepidilines A and C

by Grzegorz Mlostoń, Małgorzata Celeda, Wiktor Poper, Mateusz Kowalczyk, Katarzyna Gach-Janczak, Anna Janecka and Marcin Jasiński

Materials 2020, 13(18), 4190; https://doi.org/10.3390/ma13184190 - 21 Sep 2020

Cited by 6 | Viewed by 2648

Abstract

Condensation of diacetyl monooxime with formaldimines derived from alkoxyamines in glacial acetic acid at room temperature leads to corresponding 2-unsubstituted imidazole N-oxides bearing an alkoxy substituent at the N(1) atom of the imidazole ring. Subsequent O-benzylation afforded, depending on the type [...] Read more.

Condensation of diacetyl monooxime with formaldimines derived from alkoxyamines in glacial acetic acid at room temperature leads to corresponding 2-unsubstituted imidazole N-oxides bearing an alkoxy substituent at the N(1) atom of the imidazole ring. Subsequent O-benzylation afforded, depending on the type of alkylating agent, either symmetric or nonsymmetric alkoxyimidazolium salts considered as structural analogues of naturally occurring imidazole alkaloids, lepidilines A and C. Some of the obtained salts were tested as precursors of nucleophilic heterocyclic carbenes (NHCs), which in situ reacted with elemental sulfur to give the corresponding N-alkoxyimidazole-2-thiones. The cytotoxic activity of selected 4,5-dimethylimidazolium salts bearing either two benzyloxy or benzyloxy and 1-adamantyloxy groups at N(1) and N(3) atoms was evaluated against HL-60 and MCF-7 cell lines using the MTT (3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyltetrazolium bromide) assay. Notably, in two cases of alkoxyimidazolium salts, no effect of the counterion exchange (Br⁻ → PF₆⁻) on the biological activity was observed. Full article

(This article belongs to the Special Issue Research of Organic Molecules and Materials for Biological Application)

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26 pages, 1954 KiB

Open AccessArticle

Synthesis, Absolute Configuration, Antibacterial, and Antifungal Activities of Novel Benzofuryl β-Amino Alcohols

by Agnieszka Tafelska-Kaczmarek, Renata Kołodziejska, Marcin Kwit, Bartosz Stasiak, Magdalena Wypij and Patrycja Golińska

Materials 2020, 13(18), 4080; https://doi.org/10.3390/ma13184080 - 14 Sep 2020

Cited by 4 | Viewed by 2063

Abstract

A series of new benzofuryl α-azole ketones was synthesized and reduced by asymmetric transfer hydrogenation (ATH). Novel benzofuryl β-amino alcohols bearing an imidazolyl and triazolyl substituents were obtained with excellent enantioselectivity (96–99%). The absolute configuration (R) of the products [...] Read more.

A series of new benzofuryl α-azole ketones was synthesized and reduced by asymmetric transfer hydrogenation (ATH). Novel benzofuryl β-amino alcohols bearing an imidazolyl and triazolyl substituents were obtained with excellent enantioselectivity (96–99%). The absolute configuration (R) of the products was confirmed by means of electronic circular dichroism (ECD) spectroscopy supported by theoretical calculations. Selected benzofuryl α-azole ketones were also successfully asymmetrically bioreduced by fungi of Saccharomyces cerevisiae and Aureobasidium pullulans species. Racemic and chiral β-amino alcohols, as well as benzofuryl α-amino and α-bromo ketones were evaluated for their antibacterial and antifungal activities. From among the synthesized β-amino alcohols, the highest antimicrobial activity was found for (R)-1-(3,5-dimethylbenzofuran-2-yl)-2-(1H-imidazol-1-yl)ethan-1-ol against S. aureus ATCC 25923 (MIC = 64, MBC = 96 μg mL⁻¹) and (R)-1-(3,5-dimethylbenzofuran-2-yl)-2-(1H-1,2,4-triazol-1-yl)ethan-1-ol against yeasts of M. furfur DSM 6170 (MIC = MBC = 64 μg mL⁻¹). In turn, from among the tested ketones, 1-(benzofuran-2-yl)-2-bromoethanones (1–4) were found to be the most active against M. furfur DSM 6170 (MIC = MBC = 1.5 μg mL⁻¹) (MIC—minimal inhibitory concentration, MBC—minimal biocidal concentration). Full article

(This article belongs to the Special Issue Research of Organic Molecules and Materials for Biological Application)

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20 pages, 5883 KiB

Open AccessArticle

Silk Fibroin/Collagen/Chitosan Scaffolds Cross-Linked by a Glyoxal Solution as Biomaterials toward Bone Tissue Regeneration

by Sylwia Grabska-Zielińska, Alina Sionkowska, Catarina C. Coelho and Fernando J. Monteiro

Materials 2020, 13(15), 3433; https://doi.org/10.3390/ma13153433 - 4 Aug 2020

Cited by 33 | Viewed by 3890

Abstract

In this study, three-dimensional materials based on blends of silk fibroin (SF), collagen (Coll), and chitosan (CTS) cross-linked by glyoxal solution were prepared and the properties of the new materials were studied. The structure of the composites and the interactions between scaffold components [...] Read more.

In this study, three-dimensional materials based on blends of silk fibroin (SF), collagen (Coll), and chitosan (CTS) cross-linked by glyoxal solution were prepared and the properties of the new materials were studied. The structure of the composites and the interactions between scaffold components were studied using FTIR spectroscopy. The microstructure was observed using a scanning electron microscope. The following properties of the materials were measured: density and porosity, moisture content, and swelling degree. Mechanical properties of the 3D materials under compression were studied. Additionally, the metabolic activity of MG-63 osteoblast-like cells on materials was examined. It was found that the materials were characterized by a high swelling degree (up to 3000% after 1 h of immersion) and good porosity (in the range of 80–90%), which can be suitable for tissue engineering applications. None of the materials showed cytotoxicity toward MG-63 cells. Full article

(This article belongs to the Special Issue Research of Organic Molecules and Materials for Biological Application)

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12 pages, 5474 KiB

Open AccessArticle

Modification of Collagen Properties with Ferulic Acid

by Beata Kaczmarek, Katarzyna Lewandowska and Alina Sionkowska

Materials 2020, 13(15), 3419; https://doi.org/10.3390/ma13153419 - 3 Aug 2020

Cited by 17 | Viewed by 2785

Abstract

Collagen materials are widely used in biomedicine and in cosmetics. However, their properties require improvement for several reasons. In this work, collagen solution as well as collagen films were modified by the addition of ferulic acid (FA). Thin collagen films containing FA were [...] Read more.

Collagen materials are widely used in biomedicine and in cosmetics. However, their properties require improvement for several reasons. In this work, collagen solution as well as collagen films were modified by the addition of ferulic acid (FA). Thin collagen films containing FA were obtained by solvent evaporation. The properties of collagen solution have been studied by steady shear tests. The structure and surface properties of collagen thin films were studied. It was found that for collagen solution with 5% addition of FA, the apparent viscosity was the highest, whereas the collagen solutions with other additions of FA (1%, 2%, and 10%), no significant difference in the apparent viscosity was observed. Thin films prepared from collagen with 1 and 2% FA addition were homogeneous, whereas films with 5% and 10% FA showed irregularity in the surface properties. Mechanical properties, such as maximum tensile strength and elongation at break, were significantly higher for films with 10% FA than for films with smaller amount of FA. Young modulus was similar for films with 1% and 10% FA addition, but bigger than for 2% and 5% of FA in collagen films. The cross-linking of collagen with ferulic acid meant that prepared thin films were elastic with better mechanical properties than collagen films. Full article

(This article belongs to the Special Issue Research of Organic Molecules and Materials for Biological Application)

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28 pages, 13109 KiB

Open AccessArticle

Crosslinking of Chitosan with Dialdehyde Chitosan as a New Approach for Biomedical Applications

by Katarzyna Wegrzynowska-Drzymalska, Patrycja Grebicka, Dariusz T. Mlynarczyk, Dorota Chelminiak-Dudkiewicz, Halina Kaczmarek, Tomasz Goslinski and Marta Ziegler-Borowska

Materials 2020, 13(15), 3413; https://doi.org/10.3390/ma13153413 - 3 Aug 2020

Cited by 62 | Viewed by 6944

Abstract

Materials based on natural high molecular compounds are particularly interesting for biomedical applications. It is known that the cross-linking agent used for preparation of biomacromolecule-based materials is as important as used biopolymer. Therefore, natural cross-linkers containing reactive carbonyl groups are of great interest [...] Read more.

Materials based on natural high molecular compounds are particularly interesting for biomedical applications. It is known that the cross-linking agent used for preparation of biomacromolecule-based materials is as important as used biopolymer. Therefore, natural cross-linkers containing reactive carbonyl groups are of great interest especially for modifying properties of natural polysaccharides. One of the most popular cross-linking agents is glutaraldehyde. Nevertheless, the unreacted particles can be released from the cross-linked material and cause cytotoxic effects. This can be eliminated when using a cross-linker based e.g., on polysaccharides. This article describes quick and efficient synthesis of dialdehyde chitosan (DACS) and its application for the preparation of chitosan films. Materials obtained with different amount of DACS were fully characterized in terms of structure and surface morphology. Thermal and mechanical properties as well as hydrophilic character were also examined. The results obtained were compared with the materials obtained by cross-linking chitosan with low molecular weight glutaraldehyde and high molecular weight cross-linking agent based on polysaccharide–dialdehyde starch. Toxicity of all obtained materials was tested using the Microtox^® test. It has been shown that due to better mechanical, thermal and surface properties as well as lower toxicity, dialdehyde chitosan is a very promising crosslinking agent. Full article

(This article belongs to the Special Issue Research of Organic Molecules and Materials for Biological Application)

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29 pages, 4786 KiB

Open AccessArticle

The Influence of Different Forms of Silver on Selected Pathogenic Bacteria

by Bogusław Buszewski, Agnieszka Rogowska, Viorica Railean-Plugaru, Michał Złoch, Justyna Walczak-Skierska and Paweł Pomastowski

Materials 2020, 13(10), 2403; https://doi.org/10.3390/ma13102403 - 23 May 2020

Cited by 8 | Viewed by 3105

Abstract

The application of silver nanoparticles as an antibacterial agent is becoming more common. Unfortunately, their effect on microorganisms is still not fully understood. Therefore, this paper attempts to investigate the influence of silver ions, biologically synthesized silver nanoparticles and nanoparticles functionalized with antibiotics [...] Read more.

The application of silver nanoparticles as an antibacterial agent is becoming more common. Unfortunately, their effect on microorganisms is still not fully understood. Therefore, this paper attempts to investigate the influence of silver ions, biologically synthesized silver nanoparticles and nanoparticles functionalized with antibiotics on molecular bacteria profiles. The initial stage of research was aimed at the mechanism determination involved in antibiotics sorption onto nanoparticles’ surface. For this purpose, the kinetics study was performed. Next, the functionalized formulations were characterized by Fourier transform infrared spectroscopy (FT-IR), dynamic light scattering (DLS) and a zeta potential study. The results reveal that functionalization is a complex process, but does not significantly affect the stability of biocolloids. Furthermore, the antimicrobial assays, in most cases, have shown no increases in antibacterial activity after nanoparticle functionalization, which suggests that the functionalization process does not always generate the improved antimicrobial effect. Finally, the matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) technique was employed to characterize the changes in the molecular profile of bacteria treated with various antibacterial agents. The recorded spectra proved many differences in bacterial lipids and proteins profiles compared to untreated cells. In addition, the statistical analysis of recorded spectra revealed the strain-dependent nature of stress factors on the molecular profile of microorganisms. Full article

(This article belongs to the Special Issue Research of Organic Molecules and Materials for Biological Application)

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16 pages, 3033 KiB

Open AccessArticle

Octahydroquinoxalin-2(1H)-One-Based Aminophosphonic Acids and Their Derivatives—Biological Activity towards Cancer Cells

by Jakub Iwanejko, Elżbieta Wojaczyńska, Eliza Turlej, Magdalena Maciejewska and Joanna Wietrzyk

Materials 2020, 13(10), 2393; https://doi.org/10.3390/ma13102393 - 22 May 2020

Cited by 7 | Viewed by 2120

Abstract

In the search for new antitumor agents, aminophosphonic acids and their derivatives based on octahydroquinoxalin-2(1H)-one scaffold were obtained and their cytotoxic properties and a mechanism of action were evaluated. Phosphonic acid and phosphonate moieties increased the antiproliferative activity in comparison to [...] Read more.

In the search for new antitumor agents, aminophosphonic acids and their derivatives based on octahydroquinoxalin-2(1H)-one scaffold were obtained and their cytotoxic properties and a mechanism of action were evaluated. Phosphonic acid and phosphonate moieties increased the antiproliferative activity in comparison to phenolic Mannich bases previously reported. Most of the obtained compounds revealed a strong antiproliferative effect against leukemia cell line (MV-4-11) with simultaneous low cytotoxicity against normal cell line (mouse fibroblasts-BALB/3T3). The most active compound was diphenyl-[(1R,6R)-3-oxo-2,5-diazabicyclo[4.4.0]dec-4-yl]phosphonate. Preliminary evaluation of the mechanism of action showed the proapoptotic effect associated with caspase 3/7 induction. Full article

(This article belongs to the Special Issue Research of Organic Molecules and Materials for Biological Application)

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12 pages, 2670 KiB

Open AccessArticle

Seleninic Acid Potassium Salts as Water-Soluble Biocatalysts with Enhanced Bioavailability

by Magdalena Obieziurska, Agata J. Pacuła, Anna Laskowska, Angelika Długosz-Pokorska, Anna Janecka and Jacek Ścianowski

Materials 2020, 13(3), 661; https://doi.org/10.3390/ma13030661 - 2 Feb 2020

Cited by 9 | Viewed by 2644

Abstract

Organoselenium compounds are well-known glutathione peroxidase (GPx) mimetics that possess antioxidants/prooxidant properties and are able to modulate the concentration of reactive oxygen species (ROS), preventing oxidative stress in normal cells or inducing ROS formation in cancer cells leading to apoptosis. The purpose of [...] Read more.

Organoselenium compounds are well-known glutathione peroxidase (GPx) mimetics that possess antioxidants/prooxidant properties and are able to modulate the concentration of reactive oxygen species (ROS), preventing oxidative stress in normal cells or inducing ROS formation in cancer cells leading to apoptosis. The purpose of this study was the synthesis of potent GPx mimics with antioxidant and anticancer activity along with improved bioavailability, as a result of good solubility in protic solvents. As a result of our research, glutathione peroxidase (GPx) mimetics in the form of water-soluble benzeneseleninic acid salts were obtained. The procedure was based on the synthesis of 2-(N-alkylcarboxyamido)benzeneselenenic acids, through the oxidation of benzisoselenazol-3(2H)-ones or analogous arenediselenides with an amido group, which were further converted to corresponding potassium salts by the treatment with potassium tert-butanolate. All derivatives were tested as potential antioxidants and anticancer agents. The areneseleninic acid salts were significantly better peroxide scavengers than analogous acids and the well-known organoselenium antioxidant ebselen. The highest activity was observed for the 2-(N-ethylcarboxyamido)benzeneselenenic acid potassium salt. The strongest cytotoxic effect against breast cancer (MCF-7) and human promyelocytic leukemia (HL-60) cell lines was found for 2-(N-cyclohexylcarboxyamido)benzeneselenenic acid potassium salt and the 2-(N-ethylcarboxyamido)benzeneselenenic acid, respectively. The structure–activity correlations, including the differences in reactivity of benzeneseleninic acids and corresponding salts were evaluated. Full article

(This article belongs to the Special Issue Research of Organic Molecules and Materials for Biological Application)

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Jump to: Research

23 pages, 4617 KiB

Open AccessEditor’s ChoiceReview

Biological Inspirations: Iron Complexes Mimicking the Catechol Dioxygenases

by Karolina Kałduńska, Anna Kozakiewicz, Magdalena Wujak and Andrzej Wojtczak

Materials 2021, 14(12), 3250; https://doi.org/10.3390/ma14123250 - 12 Jun 2021

Cited by 4 | Viewed by 2847

Abstract

Within the broad group of Fe non-heme oxidases, our attention was focused on the catechol 1,2- and 2,3-dioxygenases, which catalyze the oxidative cleavage of aromatic rings. A large group of Fe complexes with N/O ligands, ranging from N₃ to N₂O [...] Read more.

Within the broad group of Fe non-heme oxidases, our attention was focused on the catechol 1,2- and 2,3-dioxygenases, which catalyze the oxidative cleavage of aromatic rings. A large group of Fe complexes with N/O ligands, ranging from N₃ to N₂O₂S, was developed to mimic the activity of these enzymes. The Fe complexes discussed in this work can mimic the intradiol/extradiol catechol dioxygenase reaction mechanism. Electronic effects of the substituents in the ligand affect the Lewis acidity of the Fe center, increasing the ability to activate dioxygen and enhancing the catalytic activity of the discussed biomimetic complexes. The ligand architecture, the geometric isomers of the complexes, and the substituent steric effects significantly affect the ability to bind the substrate in a monodentate and bidentate manner. The substrate binding mode determines the preferred mechanism and, consequently, the main conversion products. The preferred mechanism of action can also be affected by the solvents and their ability to form the stable complexes with the Fe center. The electrostatic interactions of micellar media, similar to SDS, also control the intradiol/extradiol mechanisms of the catechol conversion by discussed biomimetics. Full article

(This article belongs to the Special Issue Research of Organic Molecules and Materials for Biological Application)

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28 pages, 9865 KiB

Open AccessReview

Peptides and Peptidomimetics as Inhibitors of Enzymes Involved in Fibrillar Collagen Degradation

by Patrycja Ledwoń, Anna Maria Papini, Paolo Rovero and Rafal Latajka

Materials 2021, 14(12), 3217; https://doi.org/10.3390/ma14123217 - 10 Jun 2021

Cited by 9 | Viewed by 3363

Abstract

Collagen fibres degradation is a complex process involving a variety of enzymes. Fibrillar collagens, namely type I, II, and III, are the most widely spread collagens in human body, e.g., they are responsible for tissue fibrillar structure and skin elasticity. Nevertheless, the hyperactivity [...] Read more.

Collagen fibres degradation is a complex process involving a variety of enzymes. Fibrillar collagens, namely type I, II, and III, are the most widely spread collagens in human body, e.g., they are responsible for tissue fibrillar structure and skin elasticity. Nevertheless, the hyperactivity of fibrotic process and collagen accumulation results with joints, bone, heart, lungs, kidneys or liver fibroses. Per contra, dysfunctional collagen turnover and its increased degradation leads to wound healing disruption, skin photoaging, and loss of firmness and elasticity. In this review we described the main enzymes participating in collagen degradation pathway, paying particular attention to enzymes degrading fibrillar collagen. Therefore, collagenases (MMP-1, -8, and -13), elastases, and cathepsins, together with their peptide and peptidomimetic inhibitors, are reviewed. This information, related to the design and synthesis of new inhibitors based on peptide structure, can be relevant for future research in the fields of chemistry, biology, medicine, and cosmeceuticals. Full article

(This article belongs to the Special Issue Research of Organic Molecules and Materials for Biological Application)

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37 pages, 1577 KiB

Open AccessFeature PaperReview

Biologically Active Compounds of Plants: Structure-Related Antioxidant, Microbiological and Cytotoxic Activity of Selected Carboxylic Acids

by Beata Godlewska-Żyłkiewicz, Renata Świsłocka, Monika Kalinowska, Aleksandra Golonko, Grzegorz Świderski, Żaneta Arciszewska, Edyta Nalewajko-Sieliwoniuk, Monika Naumowicz and Włodzimierz Lewandowski

Materials 2020, 13(19), 4454; https://doi.org/10.3390/ma13194454 - 8 Oct 2020

Cited by 51 | Viewed by 6905

Abstract

Natural carboxylic acids are plant-derived compounds that are known to possess biological activity. The aim of this review was to compare the effect of structural differences of the selected carboxylic acids (benzoic acid (BA), cinnamic acid (CinA), p-coumaric acid (p-CA), caffeic [...] Read more.

Natural carboxylic acids are plant-derived compounds that are known to possess biological activity. The aim of this review was to compare the effect of structural differences of the selected carboxylic acids (benzoic acid (BA), cinnamic acid (CinA), p-coumaric acid (p-CA), caffeic acid (CFA), rosmarinic acid (RA), and chicoric acid (ChA)) on the antioxidant, antimicrobial, and cytotoxic activity. The studied compounds were arranged in a logic sequence of increasing number of hydroxyl groups and conjugated bonds in order to investigate the correlations between the structure and bioactivity. A review of the literature revealed that RA exhibited the highest antioxidant activity and this property decreased in the following order: RA > CFA ~ ChA > p-CA > CinA > BA. In the case of antimicrobial properties, structure-activity relationships were not easy to observe as they depended on the microbial strain and the experimental conditions. The highest antimicrobial activity was found for CFA and CinA, while the lowest for RA. Taking into account anti-cancer properties of studied NCA, it seems that the presence of hydroxyl groups had an influence on intermolecular interactions and the cytotoxic potential of the molecules, whereas the carboxyl group participated in the chelation of endogenous transition metal ions. Full article

(This article belongs to the Special Issue Research of Organic Molecules and Materials for Biological Application)

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