Water-soluble Zinc Research Articles

Pivotal Role of the Intracellular Microenvironment in the High Photodynamic Activity of Cationic Phthalocyanines.

To investigate the influence of phthalocyanine aggregation on their photodynamic activity, a series of six cationic water-soluble zinc(II) phthalocyanines bearing from four to sixteen 4-((diethylmethylammonium)methyl)phenoxy substituents was synthesized. Depending on their structure, the phthalocyanines have different aggregation behaviors in phosphate buffer solutions ranging from fully assembled to monomeric states. Remarkably, independent of aggregation in buffer, very high photodynamic efficiencies against the tumor cell lines MCF-7 and MDA-MB-231 in the nanomolar range were found for all investigated phthalocyanine, and the IC50(light) varied from 27 to 358 nM (3.5 J/cm2, 660 nm) with IC50(dark)/IC50(light) ratios up to ∼3700. This is due to the intracellular disassembly of aggregated phthalocyanines with the formation of monomeric photoactive forms, as demonstrated by fluorescence microscopy. Indeed, the interaction of aggregated phthalocyanines with serum proteins in a buffer resulted in the disassembly of nonluminescent aggregate species with the release of photoactive monomers bound to protein macromolecules.

Effect of foliar application of water soluble fertilizer, sulphur, zinc and boron on growth, yield and economics of garlic (Allium sativum L.) in a vertisol

Effect of foliar application of water soluble fertilizer, sulphur, zinc and boron on growth, yield and economics of garlic (Allium sativum L.) in a vertisol

Visible-light Driven Unsaturated Dicarboxylate Production from Gaseous CO<sub>2</sub> and Pyruvate with the System of Water-soluble Zinc Porphyrin and Dual-biocatalysts

Visible-light Driven Unsaturated Dicarboxylate Production from Gaseous CO<sub>2</sub> and Pyruvate with the System of Water-soluble Zinc Porphyrin and Dual-biocatalysts

Synthesis and cholinesterases inhibitory effects of water soluble zinc(II) and silicon(IV) phthalocyanines bearing ({8‐[3‐(dimethylamino)phenoxy]octyl}oxy) groups

Alzheimer's disease, is one of the irreversible neurodegenerative disorders among older people, causes behavior, memory, and thinking problems. This study aim is to synthesize of 4‐({8‐[3‐(dimethylamino)phenoxy]octyl}oxy)phthalonitrile, zinc(II) phthalocyanine and its water soluble derivative containing ({8‐[3‐(dimethylamino)phenoxy]octyl}oxy) substituents at the peripheral positions first time. To determine the potential of water soluble silicon(IV) and zinc(II) phthalocyanines for use in AD, spectrophotometric assays were performed to determine their acetylcholinesterase/butyrylcholinesterase inhibitory effects. In addition, their DNA nuclease properties were evaluated by agarose gel electrophoresis. The results showed that the compounds inhibited acetylcholinesterase/butyrylcholinesterase. They did not damage pBR322 plasmid DNA depending on time and concentration. As a result of the experiments, it is revealed that the compounds may be the potential for use as cholinesterase inhibitors, which is a promising approach for the treatment of Alzheimer's disease.

Synthesis, characterization, DNA interaction, molecular docking, and α‐glucosidase inhibition studies of 3‐(pyrimidin‐2‐ylthio) groups substituted water soluble zinc (II) phthalocyanine

In this work, 3‐(pyrimidin‐2‐ylthio)phthalonitrile (n‐MP1), non‐peripherally 3‐(pyrimidin‐2‐ylthio) groups substituted Zn (II) phthalocyanine (n‐MP2), and its water soluble derivative (n‐MP3) have been firstly synthesized and characterized with spectral data. The interaction of the n‐MP3 complex with DNA was examined in vitro using UV–visible titrimetric and thermal denaturation assays and in silico by performing molecular docking studies. In addition, the antidiabetic activity of n‐MP3 was revealed spectroscopically by studying α‐glucosidase inhibition activities. The spectroscopic results indicated that n‐MP3 effectively binds to CT‐DNA with a Kb value of 2.0 × 105 M−1 and interacts with CT‐DNA via noncovalent binding mode. Besides, docking studies divulged that n‐MP3 exhibits a stronger binding tendency (BE: −10.64 kcal/mol) with DNA than the control compounds, (7.78 kcal/mol for ethidium bromide and −6.21 kcal/mol for cisplatin). Consequently, due to its strong DNA binding activity, n‐MP3 may be suitable for antimicrobial and anticancer applications after further toxicological test systems. Also, n‐MP3 complex inhibited the activity of α‐glucosidase with the IC50 value of 1.44 ± 0.08 μM, whereas IC50 value of acarbose was 237.24 ± 1.80 μM. Therefore, it can be said that n‐MP3 is a very effective α‐glucosidase inhibitor.

Inhibitory effect of acetyl-CoA on a visible light–driven NADH regeneration system composed a of water-soluble zinc porphyrin and a rhodium complex

Abstract Acetyl-CoA was found to act as an inhibitor of reduced nicotinamide adenine dinucleotide (NADH) production by a visible light redox system consisting of a water-soluble zinc porphyrin, Zn tetrakis(4-N,N,N-trimethylaminophenyl)porphyrin, and a rhodium complex [Cp*Rh(bpy)(H2O)]2+ (Cp* = pentamethylcyclopentadienyl, bpy = 2,2′-bipyridyl).

Effect of adenosine monophosphate on visible-light driven nicotinamide mononucleotide reduction in a system of water-soluble zinc porphyrin and colloidal rhodium nanoparticles

Effect of adenosine monophosphate on visible-light driven nicotinamide mononucleotide reduction in a system of water-soluble zinc porphyrin and colloidal rhodium nanoparticles dispersed with polyvinylpyrrolidone was clarified.

An effective visible-light driven fumarate production from gaseous CO2 and pyruvate by the cationic zinc porphyrin-based photocatalytic system with dual biocatalysts.

Fumaric acid is a useful unsaturated dicarboxylic acid that serves as a precursor for the biodegradable plastics poly(butylene succinate) and poly(propylene fumarate). Currently, fumaric acid is mainly synthesised from petroleum resources such as benzene. It is therefore desirable to develop methods to produce fumaric acid from renewable resources such as those derived from biomass. In this work, an effective visible-light driven fumarate production from gaseous CO2 and pyruvate with the system consisting of triethanolamine, cationic water-soluble zinc porphyrin, zinc tetrakis(4-N,N,N-trimethylaminophenyl)porphyrin, pentamethylcyclopentadienyl coordinated rhodium(III) 2,2'-bipyridyl complex, NAD+, malate dehydrogenase (NAD+-dependent oxaloacetate-decarboxylating) and fumarase was developed.

A photo/biocatalytic system for visible-light driven l-alanine production from ammonia and pyruvate

Visible-light driven l-alanine, biodegradable nylon precursor, from biobased material pyruvate and ammonium ions with the system consisting of triethanolamine, water-soluble zinc porphyrin, pentamethylcyclopentadienyl coordinated rhodium complex, NAD+ and l-alanine dehydrogenase is developed.

Noncovalent Stabilization of Water-Soluble Zinc Phthalocyaninate in Graphene Oxide Hydrosol

Noncovalent Stabilization of Water-Soluble Zinc Phthalocyaninate in Graphene Oxide Hydrosol

In situ doping of lithium iron phosphate with excellent water-soluble zinc salt was used to improve its magnification performance

It has always been an important research direction for improving the intrinsic conductivity of Lithium iron phosphate materials. Doping can not only improve the intrinsic conductivity but also induce lattice distortion to increase the diffusion rate of lithium ions to improve the electrochemical performance. Zn-doped LiFe1-xZnxPO4 (x = 0, 0.025, 0.05, 0.075) is prepared from LiOH·H2O, FeSO4·7H2O, H3PO4, ZnSO4·7H2O. The composition, structure, morphology and electrochemical performance of the material are characterized in detail by XRD, SEM, EDS, cyclic voltammetry test, AC impedance test and other methods. The results show that the nano-spherical LiFe0.075Zn0.025PO4 exhibits excellent capacity performance and rate performance without intentionally coating C. The initial discharge specific capacity of the positive electrode material is 153.6 mAh·g−1 at 0.2C. The material also exhibits excellent cycle performance, with a discharge-specific capacity of 148.6mAh g−1 and a capacity retention rate of 96.7% after 100 cycles at a current density of 0.2C. Compared with the undoped samples, the doped ZnSO4 improves the actual capacitance of the samples. The high specific capacity retention rate at large rate charge-discharge indicates that zinc doping improves the structural stability of the samples. The crystal structure is not significantly damaged during the large current charge discharge process, and the magnification performance is improved.

Noncovalent Stabilization of Water-Soluble Zinc Phthalocyaninate in Graphene Oxide Hydrosol

The possibility of stabilization of zinc(II) 2,3,9,10,16,17,23,24-octa[(3,5-sodium biscarboxylate)phenoxy] phthalocyaninate (ZnPc16) by its hybridization with the surface of graphene oxide (GO) sheets via van der Waals or coordination bonds with functional groups of the carbon matrix in the GO hydrosols has been investigated. A combination of physicochemical analysis methods (scanning electron microscopy, fluorescence microscopy, powder X-ray diffraction, and Raman spectroscopy) has been employed to confirm the integration of ZnPc16 with GO nanosheets and to study the morphology and structure of the obtained hybrid materials. Using electronic absorption spectroscopy, it has been found that, regardless of the hybridization method, the binding of the macrocycles to the inorganic particles increases the stability of ZnPc16 in an aqueous medium being irradiated with visible light. The analysis of spectral kinetic data has shown that, in contrast to the system obtained by direct integration of ZnPc16 and GO, the hybrid material formed by coordination bonding of the components via zinc acetate (Zn(OAc)2) as a binding metal cluster is able to exhibit photocatalytic properties in oxidative photodegradation of some model organic pollutant substrates (rhodamine 6G, 1,5-dihydroxynaphthalene, and 1,4-nitrophenol). The proposed colloid-chemical approach to the stabilization of photoactive water-soluble phthalocyaninates makes it possible to increase their resistance to photoinduced self-oxidation and can be adapted for various derivatives of tetrapyrrole compounds possessing photosensitizing properties.

Structural Effect of Water-Soluble Zinc Porphyrins in a Visible-Light Driven NADH Regeneration System Catalyzed by Rhodium Pentamethylcyclopentadienyl Complex

Abstract The effect of ionic substituents (4-sulfonatophenyl, 4-carboxyphenyl, 4-methylpyridyl, and 4-N,N,N-trimethylaminophenyl-groups) of water-soluble zinc porphyrin (ZnP) on the visible light-driven NADH regeneration by a system of triethanolamine, ZnP, and rhodium complex [Cp*Rh(bpy)(H2O)]2+ (Cp* = pentamethylcyclopentadienyl, bpy = 2,2′-bipyridyl) was studied to provide significant guidance for hybridization with a wide range of oxidoreductases.

Comparing PVP and Polymeric Micellar Formulations of a PEGylated Photosensitizing Phthalocyanine by NMR and Optical Techniques.

Phthalocyanines are ideal candidates as photosensitizers for photodynamic therapy (PDT) of cancer due to their favorable chemical and photophysical properties. However, their tendency to form aggregates in water reduces PDT efficacy and poses challenges in obtaining efficient forms of phthalocyanines for therapeutic applications. In the current work, polyvinylpyrrolidone (PVP) and micellar formulations were compared for encapsulating and monomerizing a water-soluble zinc phthalocyanine bearing four non-peripheral triethylene glycol chains (Pc1). 1H NMR spectroscopy combined with UV-vis absorption and fluorescence spectroscopy revealed that Pc1 exists as a mixture of regioisomers in monomeric form in dimethyl sulfoxide but forms dimers in an aqueous buffer. PVP, polyethylene glycol castor oil (Kolliphor RH40), and three different triblock copolymers with varying proportions of polyethylene and polypropylene glycol units (termed P188, P84, and F127) were tested as micellar carriers for Pc1. 1H NMR chemical shift analysis, diffusion-ordered spectroscopy, and 2D nuclear Overhauser enhancement spectroscopy was applied to monitor the encapsulation and localization of Pc1 at the polymer interface. Kolliphor RH40 and F127 micelles exhibited the highest affinity for encapsulating Pc1 in the micellar core and resulted in intense Pc1 fluorescence emission as well as efficient singlet oxygen formation along with PVP. Among the triblock copolymers, efficiency in binding and dimer dissolution decreased in the order F127 > P84 > P188. PVP was a strong binder for Pc1. However, Pc1 molecules are rather surface-attached and exist as monomer and dimer mixtures. The results demonstrate that NMR combined with optical spectroscopy offer powerful tools to assess parameters like drug binding, localization sites, and dynamic properties that play key roles in achieving high host-guest compatibility. With the corresponding adjustments, polymeric micelles can offer simple and easily accessible drug delivery systems optimizing phthalocyanines' properties as efficient photosensitizers.

The synthesis of novel water-soluble zinc (II) phthalocyanine based photosensitizers and exploring of photodynamic therapy activities on the PC3 cancer cell line.

In this study, Schiff base substituted phthalocyanine complexes (Zn1c, Zn2c) and their quaternized derivatives (Q-Zn1c, Q-Zn2c) were synthesized for the first time. Their structures have been characterized by FT-IR, 1H-NMR, UV-Vis, mass spectrometry and elemental analysis as well as. The photophysicochemical properties (fluorescence, singlet oxygen and photodegradation quantum yield) of these novel complexes were investigated in dimethylsulfoxide (DMSO) for both non-ionic and quaternized cationic phthalocyanine complexes and in aqueous solution for quaternized cationic phthalocyanine complexes. Water soluble cationic phthalocyanine compounds gave good singlet oxygen quantum yield (0.65 for Q-Zn1c, 0.66 for Q-Zn2c in DMSO; 0.65 for Q-Zn2c in aqueous solution). The binding of Q-Zn1c and Q-Zn2c to BSA/DNA was studied by using UV-Vis and fluorescence spectroscopy and these. Studies indicate that the mechanism of BSA quenching by quaternized zinc(II) phthalocyanines was static quenching. Quaternized zinc(II) phthalocyanines interacted with ct-DNA by intercalation. Quaternized zinc(II) phthalocyanines caused a decrease in cell viability and triggered apoptotic cell death after PDT was applied at a concentration that did not have a toxic effect on their own. Q-Zn1c and Q-Zn2c mediated PDT reduced the activity of SOD, CAT, GSH while increased MDA level in the prostate cancer cells. Furthermore, expression of apoptotic proteins after PDT was examined. The results revealed that the synthesized water soluble quaternized zinc(II) phthalocyanine complexes (Q-Zn1c and Q-Zn2c) are promising potential photosensitizers for PDT.

Assembling Artificial Photosynthetic Models in Water Using β-Cyclodextrin-Conjugated Phthalocyanines as Building Blocks.

Two water-soluble zinc(II) phthalocyanines substituted with two or four permethylated β-cyclodextrin (β-CD) moieties at the α positions have been utilized as building blocks for the construction of artificial photosynthetic models in water. The hydrophilic and bulky β-CD moieties not only can increase the water solubility of the phthalocyanine core and prevent its stacking in water but can also bind with a tetrasulfonated zinc(II) porphyrin (ZnTPPS) and/or sodium 2-anthraquinonesulfonate (AQ) in water through host-guest interactions. The binding interactions of these species have been studied spectroscopically, while the photoinduced processes of the resulting complexes have been investigated using steady-state and time-resolved spectroscopic methods. In the ternary complexes, the ZnTPPS units serve as light-harvesting antennas to capture the light energy and transfer it to the phthalocyanine core via efficient excitation energy transfer. The excited phthalocyanine is subsequently quenched by the electron-deficient AQ units through electron transfer. Femtosecond transient absorption spectroscopy provides clear evidence for the singlet-singlet energy transfer from the photo-excited ZnTPPS to the phthalocyanine core with a rate constant (kENT ) in the order of 109 s-1 . The population of phthalocyanine radical cations indicates the occurrence of electron transfer from the excited phthalocyanine to the AQ moieties, forming a charge-separated state.

Tetraquinoxalinoporphyrazine – π-extended NIR-absorbing photosensitizer with improved photostability

A novel ionogenic water-soluble zinc complex with π-extended ligand – tetraquinoxalinoporphyrazine bearing eight benzoate groups – ZnQPz(COONa)8 was synthesized by template condensation of a new building block, dipentyl 4,4'-(6,7-dicyanoquinoxalin-2,3-diyl)dibenzoate followed by alkaline hydrolysis of ester groups. The photophysical properties of the complex were studied and a significant bathochromic shift of the Q-band by 100 nm was observed as compared to conventional phthalocyanine complexes. However, in contrast to other NIR-absorbing π-extended derivatives with similar optical properties, ZnQPz(COONa)8 showed a high degree of photostability – its photobleaching rate in DMSO was about 3 times lower than that of the zinc tetra-15-crown-5-naphthalocyanate Zn[(15C5)4Nc]. The improved photostability together with the ability to generate singlet oxygen (ФΔ = 0.65 in aqueous DMSO) and absorb light in the near infrared region makes quinoxaline-porphyrazine a good candidate for use in photodynamic therapy.

NIR-Photocontrolled Aqueous RAFT Polymerization with Polymerizable Water-Soluble Zinc Phthalocyanine as Photocatalyst

In order to give an answer for the challenges of long wavelength-photocontrolled radical polymerization in aqueous solutions and to address the shortcomings of conventional near-infrared (NIR) photocatalysts (PCs) that are difficult to subject to post-treatment, we designed and synthesized a series of β-tetra-substituted water-soluble zinc phthalocyanines (β-TS-Zns) as the NIR PCs for reversible addition-fragmentation chain transfer (RAFT) polymerization successfully under irradiation with NIR (λmax = 730 nm) light at room temperature. Importantly, the NIR PCs can also be designed as polymerizable monomers and covalently loaded on the polymer chains, which are endowed with permanent NIR photocatalysis of the resultant polymers. Moreover, the polymerization can not only be carried out in water but also in phosphate buffer saline (PBS) solution, yielding polymers with controlled molar mass and narrow dispersities (Đ = 1.03-1.25). Therefore, this NIR-photocontrolled aqueous RAFT polymerization system may provide a charming strategy for possible applications in tissue engineering biomaterial in situ benefiting from the high penetration ability of NIR light.

Effect of water-soluble zinc porphyrin on the catalytic activity of fumarase for l-malate dehydration to fumarate

The sulfo group bonded to the water-soluble zinc porphyrin had a strong inhibition to the catalytic activity of FUM for l-malate dehydration to fumarate.

Combating hidden hunger caused by wheat and soil-drived zinc deficiency

Essential vitamins, proteins, and microelements are provided by nutrition, but inadequate and nutrient-poor diets can lead to hidden hunger. Zinc deficiency is a significant hidden resource that affects multiple bodily functions, including immune system function, growth, and development. The primary reasons for the prevalence of zinc deficiency in humans are grain-based products with low concentrations and low zinc solubility in the soil. Intensifying plant production and the inability to replace nutrients absorbed in excess from the soil leads to zinc deficiency in the soil. Consequently, substantial reductions in crop yields are observed, along with decreased zinc concentrations in harvested grains. A number of unsustainable strategies, including expensive medical supplements and zinc-enriched flour-based products to address zinc deficiency, are temporary solutions. Additionally, one such strategy is agronomic biofortification, which recommends utilizing water-soluble zinc fertilizers to increase the concentration of zinc in the plant and soil. A more sustainable and cost-effective approach involves employing traditional plant breeding and molecular techniques to develop new zinc-biofortified cultivars. By enriching wheat with zinc, it absorbs 20-40% more zinc from the soil. Here, this paper will discuss the role of zinc deficiency in wheat and soil and its impact on both crop yield and human nutrition, with a particular emphasis on biofortified wheat.