Advancing oral health: Harnessing the potential of chitosan and polyphenols in innovative mouthwash formulation.

This paper explores the therapeutic perspectives of polyphenols and chitosan as potential anticancer agents in the mouthwash formulations. Taking into account the high incidence of squamous cell carcinoma (SCC) among oral cancers, this discussion will concentrate on the potential advantages of these compounds in oral care, focusing on their impact on improving oral health and cancer prevention. According to the data, it appears that the mixture of BACs extract and chitosan may increase the efficiency of the apoptosis of cancer cells while reducing the undesired side effects. The cytotoxicity assays demonstrate a significant reduction in squamous carcinoma cell viability after incubation with BACs extract, with a marked decrease observed over 24-72 hours up to 76%. The anti-cancer properties of the BAC extract are related to luteolin, which is a predominant compound. The addition of 0.025% chitosan reduced the metabolic activity of cancer cells by 37.5%, suggesting a synergistic interaction between the compounds. This research highlights the potential of BACs and chitosan in modulating important molecular targets associated with cancer cell.

Biocoordination reactions in copper(II) ions and phosphocholine systems including pyrimidine nucleosides and nucleotides.

The complexation reactions of phosphocholine and pyrimidine nucleosides as well as nucleotides with copper(II) ions were studied in the water system. Using potentiometric methods and computer calculations, the stability constants of the species were determined. Using spectroscopic methods such as UV-vis, EPR, 13C NMR, 31P NMR, FT-IR and CD, the coordination mode was established for complexes created in pH range 2.5-11.0. These studies will lead to a better understanding the role of copper(II) ions in living organisms and explain the interactions between them and the studied bioligands. The differences and similarities between nucleosides and nucleotides in the studied systems were also described, which testify to the significant influence of phosphate groups on the processes of metal ion complexation and interactions between ligands.

Synthesis and evaluation of radiolabeled porphyrin derivatives for cancer diagnoses and their nonradioactive counterparts for photodynamic therapy.

Radioiodinated porphyrin derivatives and the corresponding nonradioactive iodine introduced compounds, [125I]I-TPPOH ([125I]3), [125I]I-l-tyrosine-TPP ([125I]9), I-TPPOH (3), and I-l-tyrosine-TPP (9) were designed, synthesized, and evaluated by in vitro and in vivo experiments. In cytotoxicity assays, 3 and 9 exhibited significant cytotoxicity under light conditions but did not show significant cytotoxicity without light irradiation. Biodistribution experiments with [125I]3 and [125I]9 showed similar distribution patterns with high retention in tumors. In photodynamic therapeutic (PDT) experiments, 3 and 9 at a dose of 13.6 µmol kg-1 weight with 50 W single light irradiation onto the tumor area significantly inhibited tumor growth. These results indicate that the iodinated porphyrin derivatives [123/natI]3 and [123/natI]9 are promising cancer theranostic agents.

Coordination Chemistry of Phosphate Groups in Systems Including Copper(II) Ions, Phosphoethanolamine and Pyrimidine Nucleotides.

The activity of phosphate groups of phosphoethanolamine and pyrimidine nucleotides (thymidine 5-monophosphate, cytidine 5-monophosphate and uridine 5'monophosphate) in the process of complexation metal ions in aqueous solution was studied. Using the potentiometric method with computer calculation of the data and spectroscopic methods such as UV-Vis, EPR, 13C and 31P NMR as well as FT-IR, the overall stability constants of the complexes as well as coordination modes were obtained. At lower pH, copper(II) ions are complexed only by phosphate groups, whereas the endocyclic nitrogen atom of nucleotides has been identified as a negative center interacting with the -NH3+ groups of phosphoethanolamine.

Christmas Tree Bio-Waste as a Power Source of Bioactive Materials with Anti-Proliferative Activities for Oral Care.

According to the American Cancer Society, roughly 54,000 new cases of oral cavity or oropharyngeal cancers have been detected in the United States of America in 2021, and they will cause about 10,850 deaths. The main therapies for cancer management, such as surgery and radio- and chemotherapy, have some own benefits, albeit they are often destructive for surrounding tissues; thus, deep investigations into non-surgical treatments for oral cavities are needed. Biologically active compounds (BACs) extracted from European Spruce needles were analyzed to determine the total phenolic and flavonoid content and were used as additional ingredients for oral hygiene products. An anti-proliferation investigation was carried out using extracts containing BACs with the use of several cell lines (cancer and a normal one). ESI-MS studies on BACs showed that luteolin, a natural flavonoid compound with anti-tumorigenic properties against various types of tumors, is the predominant component of the extracts. MTT, BrdU, and LIVE/DEAD studies demonstrated that BAC extracts obtained from Christmas tree needles possess anticancer properties against squamous cell carcinoma (with epithelial origins). We proved that BAC extracts contain high amounts of luteolin, which induces cytotoxicity toward cancer cells; along with their high selectivity, robustness, and nontoxicity, they are very promising materials in oral health applications.

Synthesis and evaluation of radiogallium-labeled long-chain fatty acid derivatives as myocardial metabolic imaging agents.

Since long-chain fatty acids work as the primary energy source for the myocardium, radiolabeled long-chain fatty acids play an important role as imaging agents to diagnose metabolic heart dysfunction and heart diseases. With the aim of developing radiogallium-labeled fatty acids, herein four fatty acid-based tracers, [67Ga]Ga-HBED-CC-PDA, [67Ga]Ga-HBED-CC-MHDA, [67Ga]Ga-DOTA-PDA, and [67Ga]Ga-DOTA-MHDA, which are [67Ga]Ga-HBED-CC and [67Ga]Ga-DOTA conjugated with pentadecanoic acid (PDA) and 3-methylhexadecanoic acid (MHDA), were synthesized, and their potential for myocardial metabolic imaging was evaluated. Those tracers were found to be chemically stable in 0.1 M phosphate buffered saline. Initial [67Ga]Ga-HBED-CC-PDA, [67Ga]Ga-HBED-CC-MHDA, [67Ga]Ga-DOTA-PDA, and [67Ga]Ga-DOTA-MHDA uptakes in the heart at 0.5 min postinjection were 5.01 ± 0.30%ID/g, 5.74 ± 1.02%ID/g, 5.67 ± 0.22%ID/g, and 5.29 ± 0.10%ID/g, respectively. These values were significantly lower than that of [123I]BMIPP (21.36 ± 2.73%ID/g). For their clinical application as myocardial metabolic imaging agents, further structural modifications are required to increase their uptake in the heart.

Influence of d-Electron Divalent Metal Ions in Complex Formation with L-Tartaric and L-Malic Acids.

Binary complexes of α-hydroxy acids (L-Tartaric acid and L-Malic acid) with d-electron metal ions (copper, cobalt, nickel) were investigated. Potentiometric measurements have been performed in aqueous solution with computer analysis of the data for determination of the stability constants of complexes formed in the studied systems. The coordination mode of the complexes was defined using spectroscopic methods: electron paramagnetic resonance (EPR), ultraviolet-visible (UV-Vis), circular dichroism (CD), and infrared (IR). Results of the equilibrium studies have provided evidence for the formation of dimers with copper(II) ions and monomers with cobalt(II) and nickel(II) ions.

The Influence of pH on Complexation Process of Copper(II) Phosphoethanolamine to Pyrimidine Nucleosides.

The influence of pH on the complex formation of phosphoethanolamine and pyrimidine nucleosides (uridine, cytidine and thymidine) with copper(II) ions was studied. All investigations were performed in aqueous solution. The overall stability constants of the complexes and non-covalent compounds were obtained using the potentiometric method with computer calculation of the data. Moreover, equilibrium constants of the reaction were determined. The mode of coordination was obtained using spectroscopic methods. Analysis of the potentiometric and spectroscopic data confirmed the involvement and effectiveness of phosphate groups in species formation as well as the influence of pH on the mode of coordination of the investigated biomaterials. In the next step, studied complexes will be applied as potential biomaterials with biological applications.

The Effect of pH on the Size of Silver Nanoparticles Obtained in the Reduction Reaction with Citric and Malic Acids.

In colloidal methods, the morphology of nanoparticles (size and shape) as well as their stability can be controlled by changing the concentration of the substrate, stabilizer, adding inorganic salts, changing the reducer/substrate molar ratio, and changing the pH and reaction time. The synthesis of silver nanoparticles was carried out according to the modified Lee and Meisel method in a wide pH range (from 2.0 to 11.0) using citric acid and malic acid, without adding any additives or stabilizers. Keeping the same reaction conditions as the concentration of acid and silver ions, temperature, and heating time, it was possible to determine the relationship between the reaction pH, the type of acid, and the size of the silver nanoparticles formed. Obtained colloids were analyzed by UV-Vis spectroscopy and investigated by means of Transmission Electron Microscope (TEM). The study showed that the colloids reduced with citric acid and malic acid are stable over time for a minimum of seven weeks. We observed that reactions occurred for citric acid from pH 6.0 to 11.0 and for malic acid from pH 7.0 to 11.0. The average size of the quasi-spherical nanoparticles changed with pH due to the increase of reaction rate.

Thermodynamic and Spectroscopic Studies of the Complexes Formed in Tartaric Acid and Lanthanide(III) Ions Binary Systems.

Binary complexes of tartaric acid with lanthanide(III) ions were investigated. The studies have been performed in aqueous solution using the potentiometric method with computer analysis of the data for detection of the complexes set, determination of the stability constants of these compounds. The mode of the coordination of complexes found was determined using spectroscopy, which shows: Infrared, circular dichroism, ultraviolet, visible as well as luminescence spectroscopy. The overall stability constants of the complexes as well as the equilibrium constants of the reaction were determined. Analysis of the equilibrium constants of the reactions and spectroscopic data allowed the effectiveness of the carboxyl groups in the process of complex formation.

New coordination compounds of citric acid and polyamines with lanthanide ions - potential application in monitoring the treatment of cancer diseases.

Non-covalent interaction in the binary systems of polyamines (putrescine, spermidine, spermine) with citric acid and complex formation in the binary as well as ternary systems of lanthanide(III) ions, citric acid and polyamine have been investigated. The studies were performed in aqueous solution. The overall stability constants of the complexes were determined using the potentiometric method with computer analysis of the data. Only mononuclear type of complexes were found in the ternary systems and polyamines were located in the outer as well as inner coordination sphere. Non-covalent interaction between biogenic amines and citric acid in the binary and ternary systems were confirmed on the basis of the equilibrium constants analysis and spectroscopic studies.

Carboxyl groups of citric acid in the process of complex formation with bivalent and trivalent metal ions in biological systems.

Binary complexes of citric acid (H3L - protonated form, H2L and HL - partly protonated forms, L - fully deprotonated) with d- and f-electron metal ions were investigated. The studies have been performed in aqueous solution using the potentiometric method with computer analysis of the data, electron paramagnetic resonance, infrared, visible as well as luminescence spectroscopies. The overall stability constants of the complexes were determined. Analysis of the equilibrium constants of the reactions and spectroscopic data has allowed determination of the type of coordination and effectiveness of the carboxyl groups in the process of complex formation. On the basis of potentiometric titration for d-electron were found dimeric and monomeric type of complexes and for f-electron four type of complexes: MHL, ML, ML(OH) and ML(OH)2.

Coordination properties of N,N'-bis(5-methylsalicylidene)-2-hydroxy-1,3-propanediamine with d- and f-electron ions: crystal structure, stability in solution, spectroscopic and spectroelectrochemical studies.

Template reaction between 5-methylsalicylaldehyde and 2-hydroxy-1,3-propanediamine in the presence of copper ion led to dinuclear and mononuclear copper(ii) complexes [Cu2L(CH3COO)(CH3OH)](CH3OH) (1) and [CuHL](CH3OH) (2), where H3L is N,N'-bis(5-methylsalicylidene)-2-hydroxy-1,3-propanediamine. The result of the reactions between 5-methylsalicylaldehyde and 2-hydroxy-1,3-propanediamine in the presence of lanthanide ions and/or copper(ii) ion was N,N'-bis(5-methylsalicylidene)-2-hydroxy-1,3-propanediamine (H3L B) or [CuHL](CH3OH) (2), respectively. Structures of the compounds were determined by single-crystal X-ray diffraction and physicochemical methods. The microstructures and phase compositions of crystals were studied by scanning electron microscopy (SEM). In dinuclear complex [Cu2L(CH3COO)(CH3OH)](CH3OH) (1), two copper(ii) ions are bond to one H3L ligand and one acetate ion. Coordination modes of the two copper centers are different: the geometry of copper 1 is almost ideal square-planar, while that for copper 2 can be described as tetragonal pyramidal. In complex [CuHL](CH3OH) (2), the copper(ii) ion is four coordinated and the coordination, rather than square-planar, can be described as flattened tetrahedral. Formation of complexes between copper(ii) or lanthanide ions with N,N'-bis(5-methylsalicylidene)-2-hydroxy-1,3-propanediamine (H3L) was also studied in solution by pH potentiometry. It should be mentioned that the complexes of lanthanide ions exist only in solution. Additionally, the salen-type ligand H3L and its dinuclear and mononuclear copper(ii) complexes were studied by cyclic voltammetry, and their spectroelectrochemical properties were examined.

Smart Capsules for Lead Removal from Industrial Wastewater.

Ground and especially drinking water could be contaminated by heavy metal ions such as lead and chromium, or the metalloid arsenic, discarded from industrial wastewater. These heavy metal ions are regarded as highly toxic pollutants which could cause a wide range of health problems in case of a long-term accumulation in the body. Thus, there have been many efforts to reduce the concentration of lead ions in effluent wastewater. They have included the establishment of stringent permissible discharge levels and management policies, the application of various pollution-control technologies, and the development of adsorbent materials for lead reduction. According to Science [1] encapsulation, developed approximately 65 years ago, has been defined as a major interdisciplinary research technology. Encapsulation has been used to deliver almost everything from advanced drugs to unique consumer sensory experiences. In this chapter we review the art of encapsulation technology as a potential breakthrough solution for a recyclable removal system for lead ions. Moreover, in order to provide the readers with a comprehensive and in-depth understanding of recent developments and innovative applications in this field, we highlight some remarkable advantages of encapsulation for heavy metal remove, such as simplicity of preparation, applicability for a wide range of selective extractants, large special interfacial area, ability for concentration of metal ions from dilute solutions, and less leakage of harmful components to the environment.

PVDF Membrane Morphology-Influence of Polymer Molecular Weight and Preparation Temperature.

In this study, we successfully prepared nine non-woven, supported polyvinylidene fluoride (PVDF) membranes, using a phase inversion precipitation method, starting from a 15 wt % PVDF solution in N-methyl-2-pyrrolidone. Various membrane morphologies were obtained by using (1) PVDF polymers, with diverse molecular weights ranging from 300 to 700 kDa, and (2) different temperature coagulation baths (20, 40, and 60 ± 2 °C) used for the film precipitation. An environmental scanning electron microscope (ESEM) was used for surface and cross-section morphology characterization. An atomic force microscope (AFM) was employed to investigate surface roughness, while a contact angle (CA) instrument was used for membrane hydrophobicity studies. Fourier transform infrared spectroscopy (FTIR) results show that the fabricated membranes are formed by a mixture of TGTG' chains, in α phase crystalline domains, and all-TTTT trans planar zigzag chains characteristic to ß phase. Moreover, generated results indicate that the phases' content and membrane morphologies depend on the polymer molecular weight and conditions used for the membranes' preparation. The diversity of fabricated membranes could be applied by the End User Industries for different applications.

Concentration and Fractionation of Polyphenols by Membrane Operations.

BACKGROUND: This review aims to present the relevant background information and current research status in concentration of polyphenols using membrane technologies. The potential implementation of membrane separation to bioactive compounds like soluble phenolics from aqueous and organic solvent solutions is gaining increasing interest in the recent years. This review does not pretend to cover the abundant published literature on the subject, but to be representative for the observed tendencies in membrane processes applications for concentration of polyphenols derived from natural products. The first part of the article includes general information regarding the polyphenols and the traditional methods for their separation (such as: thin layer chromatography; paper chromatography; gas chromatography; high performance liquid chromatography; capillary electrophoresis), while the second part presents a review of different membrane processes applied for concentration of polyphenols. Three main sources for such implementations are discussed: (1) aqueous or organic solvent extracts from plant material, (2) fruits, and (3) recovery of polyphenols from industrial waste liquids. A diversity of membrane processes are considered in a large scope of implementations ranging from lab-scale studies to pilot and semiindustrial scale operations. CONCLUSION: Membrane technology is an excellent candidate to make a paradigm shift in biological active compounds fractionation/separation processes. Presented results clearly demonstrate that membrane processes are of great advantages over traditionally used methods; however, characterization of separated polyphenols has to be improved. Most of citied authors concentrated their investigation only on the total amount of polyphenols determination. Exhaustive studies including: antioxidant activities, retention index, total soluble solids, or volume reduction factor, have been only carried out by a few authors.

Complexing ability of (-)-cytisine--synthesis, spectroscopy and crystal structures of the new copper and zinc complexes.

For the first time the NMR spectra of quinolizidine alkaloid with Cu(II) are studied. Structures of new complexes of (-)-cytisine with Cu(+2) and Zn(+2) cations are visualized, discussed in detail and characterized by spectroscopic methods: ESI-MS, NMR, UV-vis, EPR and crystallographic methods. In solution metal coordinates through the protonated nitrogen atoms of secondary amino groups (in piperidine ring) of cytisine molecule. While in solid state the most stable structures of the complexes are those in which the coordination of Cu(II) and Zn(II) salts is realized solely through the lactam carbonyl oxygen atom.

Spectroscopic, potentiometric and quantum-mechanical studies of S-(-)-nicotine complexes with Cu(II) ion.

Copper(II)-nicotine complexes with chelating perchlorate, nitrate, acetate and formate ligands have been synthesized and characterized in solid state by elemental analysis and FT-IR spectroscopy. Coordination of Cu(II) by nicotine molecule has been also studied in water solution of various pH by potentiometry and spectroscopic (VIS, EPR and NMR) methods. Furthermore, quantum-mechanical calculations helped elucidate the experimental data as they provided some information on the energetic of the possible interaction modes of Cu(II) with nicotine. The studies showed that nicotine acts as a monodentate ligand utilizing for this purpose the pyridine nitrogen atom. In the Cu(II)/Nicotine system the MHL and ML type complexes were formed in 1:1 metal:ligand ratio.

Equilibrium study on the interaction of phytic acid with polyamines and metal ions.

Interaction of phytic acid (myo-inositolhexakisphosphoric acid, IP) and polyamines (A = en, tn, Put, dien, 2,3-tri, 3,3-tri, Spd, 3,3,3-tet, spermine(Spm)) have been studied by potentiometric and (31)P-NMR techniques. The non-covalent interactions have led to the formation of stable molecular complexes of (IP)H(n)(A) type at the 1:1 molar ratio of the ligands, but of different numbers of protons. The IP protonation constants, stability constants of the molecular complexes and metal (Mg(2+)) complexes have been determined. The structural and pH dependences of stability constants showed the interactions between IP and A have the acid-base character determining their effectiveness, although the IP structure (5ax1eq, 5eq1ax) in molecular complexes should be also taken into account. (31)P NMR study showed in the presence of Spm (31)P highfield shifts and high pH shift of signal broadening due to chemical exchange between 5ax1eq and 5eq1ax. The preferable binding of Spm to IP over Mg(2+) in neutral pH indicated the importance of polyamine as a stabilizer of phosphate compounds.

The effect of spermine concentration on the solution structure of complexes formed in copper(II)/adenosine 5'-triphosphate/phosphoserine system.

Quaternary systems of copper(II) complexes with adenosine 5'-triphosphate, O-phospho L-serine and with equimolar or excessive amount of spermine have been investigated. The studies have been performed in aqueous solution. Types of complexes and the overall stability constants have been determined using the potentiometric method with computer analysis of the data. On the basis of the results of spectroscopic studies (nuclear magnetic resonance, visible, circular dichroism, Raman, infrared and electron paramagnetic resonance spectroscopies) as well as equilibrium studies, the mode of interactions has been proposed. The reaction centers in the systems studied are the phosphate, carboxyl and amine groups from phosphorylated serine, heterocyclic nitrogen atom from purine ring and phosphate groups from adenosine 5'-triphosphate as well as amine groups from polyamine. The influence of change in the concentration of the polyamine (spermine) on the mode of coordination is discussed. It has been shown that in the physiological conditions an increase in the polyamine concentration changes the mode of metal bonding in the CuH(3)(ATP)(Ser-P)(Spm) complexes (isomer I - coordination {2N,O(x)}, isomer II - coordination {3N,O(x)} and significant differences in sites of interaction).