Zinc Phosphite Research Articles

Structural Variants and Ultralow Detection Ability for Tryptamine in Two Polymorphs of a Zincophosphite Framework.

Two organic-inorganic hybrid zinc phosphites incorporating 1,2,4,5-tetrakis(imidazol-1-ylmethyl)benzene (TIMB) molecules were synthesized under hydro(solvo)thermal methods and structurally characterized by single-crystal X-ray diffraction (SCXD). Interestingly, the solvent ratio of water to dimethylformamide induced the formation of a new compound of Zn2(TIMB)0.5(HPO3)2·3H2O (1) and our previously reported structure of Zn2(TIMB)0.5(HPO3)2·H2O (2). Additionally, their dehydrated crystals (1a and 2a) were prepared through heat treatment at 150 °C. SCXD and powder X-ray diffraction showed that all four compounds share the same framework formula of Zn2(TIMB)0.5(HPO3)2 but exhibit a huge difference in their inorganic components and final structures. In 1 and 1a, the inorganic units formed two-dimensional zincophosphite layers, while in 2 and 2a, they formed one-dimensional chains. The inorganic parts of 1 (1a) and 2 (2a) were bridged with TIMB linkers, resulting in 3D structures with rectangular and tubular windows, respectively. Furthermore, 1 was coated on the screen-printed carbon electron as a hybrid material, displaying excellent performance while having a linear relationship with an R2 value of 0.99 within the concentration range of 10-10 to 10-6 mol/L for detecting tryptamine (Try) molecules. Moreover, the results showed that 1 exhibits an ultralow limit of detection of 5.43 × 10-11 mol/L and high specificity toward Try over histamine, ascorbic acid, uric acid, and glucose. The synthesis, structural diversity, stability, and sensing ability are also discussed.

Front Cover: Genuine Pores in a Stable Zinc Phosphite for High H2 Adsorption and CO2 Capture (Chem. Eur. J. 32/2022)

Through the shattered glass is an amazing view of Keelung city where the National Taiwan Ocean University is located. Like breaking a hole in a vacuum box, a new stable mixed-ligand zinc phosphite (NTOU-9) presents interesting structural features and pore characteristics for gas adsorption. This material also showed good adsorption capacity for H2O, CO2, CO, CH4, N2, and H2, as well as selectivity for CO2 over CO, N2, and H2 at 298 K. The possible adsorption sites and selectivity were calculated by using density functional theory (DFT), the ideal adsorption solution theory (IAST), and fitting experimental pure-component adsorption data. More information can be found in the Research Article by C.-M. Wang and co-workers (DOI: 10.1002/chem.202200732).

Genuine Pores in a Stable Zinc Phosphite for High H2 Adsorption and CO2 Capture.

Invited for the cover of this issue are Chih-Min Wang and co-workers at Academia Sinica of Taiwan and National Taiwan Ocean University. The image depicts an unusual organic-inorganic hybrid zinc phosphite with interesting structural features and gas adsorption properties. Read the full text of the article at 10.1002/chem.202200732.

Genuine Pores in a Stable Zinc Phosphite for High H2 Adsorption and CO2 Capture.

An uncommon example of stable mixed-ligand zinc phosphite with genuine pores has been synthesized by using zinc metal, inorganic phosphite acid, thio-functionalized O-donor (2,5-thiophenedicarboxylate, TPDC), and tetradentate N-donor [1,2,4,5-tetrakis(imidazol-1-ylmethyl)benzene, TIMB] units assembled into one crystalline structure according to a hydro(solvo)thermal method. This is a very rare case of a metal phosphite incorporating both N- and O-donor ligands. The tetradentate TIMB linker bound to zinc atoms of the isolated zincophosphite hexamers to form a 3D open-framework structure by crosslinking structural components of 1D chains and 2D layers. Here, the TPDC ligand acts as a monodentate binding model to functionalize its porous structure with the uncoordinated S atom and COO- group. Interestingly, this compound demonstrates the highest H2 storage capacity among organic-inorganic hybrid metal phosphates (and phosphites), and a good CO2 capture at 298 K compared with the majority of crystalline materials. The possible adsorption sites and selectivity for CO2 over H2 , N2 , and CO at 298 K were calculated by using density functional theory (DFT), the ideal adsorption solution theory (IAST), and fitting experimental pure-component adsorption data.

Studies on the Genesis and Proton Conductivity of Imidazole-Based Linear and Open-Framework Zinc Phosphites.

Three new zinc phosphites, [HIm]2[Zn3(HPO3)4] (1), [Zn2(HPO3)2Im2] (2), and [Zn(HPO3)Im] (3) (Im = imidazole), have been synthesized from the hydro/solvothermal reaction of zinc acetate, dimethyl phosphite, and imidazole by varying the temperature and solvent of the reaction medium. The structure of 1 is built from vertex-sharing of four HPO3-capped Zn3P3 units and adopts an open framework with 12-ring channels stabilized by HIm cations via N-H···O hydrogen bonds. For 2, the inorganic skeleton is comprised of alternating ZnO4 and HPO3 tetrahedra, while the coordinatively associated ZnN2O2 fragments occupy the 12-ring hexagonal channels. Compound 3 adopts a ladder-type one-dimensional structure and exhibits N-H···O hydrogen-bonding interactions to afford a supramolecular assembly. A plausible rationale on the genesis of 1-3 has been put forth by reacting the preformed inorganic zinc phosphites Zn{OP(O)(OMe)H}2 or [Zn2(HPO3)2(H2O)4]·H2O with imidazole as the structure-directing ligand. Alternating-current impedance measurements reveal that 1 and 3 exhibit proton conductivities on the order of 10-3-10-4 S cm-1 between 25 and 100 °C under 35 and 77% relative humidity in repeated impedance cycles (Ea = 0.22-0.35 eV). On the contrary, the conduction property is completely impaired in 2 under similar conditions.

Amino acid-templated zinc phosphites: low-dimensional structures, fluorescence, and nonlinear optical properties

Two new zinc phosphites were prepared using the amino acid alanine as a structure-directing agent. They have tubular and ladder-like structures, exhibiting blue fluorescence upon UV light irradiation. Notably, the tubular structure is unprecedented in metal phosphite systems. The compound is a nonlinear optically active solid with a second-harmonic generation efficiency of about 1.2 times that of KH2PO4 (KDP).

Potassium, calcium, and zinc phosphites on white mold control in soybean

ABSTRACT White mold, caused by Sclerotinia sclerotiorum, is one the most devastating disease on soybean worldwide. Considering the potential of phosphites to protect plants against different diseases, this study investigated the possibility of using potassium (K), calcium (Ca), and zinc (Zn) phosphites for white mold control in soybean. The contact effect of the phosphites on fungal mycelial growth was evaluated in vitro. In the greenhouse study, plants were inoculated with S. sclerotiorum at 48 h after being sprayed with water (control), K, Ca, and Zn phosphites by using an agar plug (0.8 cm2) containing fungal mycelia. Lesion area of white mold and chlorophyll (Chl) a fluorescence parameters were evaluated on the leaflets of plants at 96 h after inoculation. The Chl a parameters were also evaluated in noninoculated leaflets at the same time. Fungal mycelial growth was abundant in the absence of phosphites, but inhibited in the presence of the three phosphites indicating their direct effect. The lesion area in the leaflets of plants sprayed with K, Ca, and Zn phosphites were 90, 98, and 68% lower, respectively, compared to plants sprayed with water. The functionality of the photosynthetic apparatus was more preserved on the leaflets of plants sprayed with phosphites due to the lower lesions size, especially for the Ca phosphite. In conclusion, the K, Ca, and Zn phosphites were effective in reducing white mold symptoms mainly through a contact effect on the fungal mycelial growth.

Phosphites of manganese and zinc potentiate the resistance of common bean against infection by Xanthomonas axonopodis pv. phaseoli

AbstractCommon bacterial blight (CBB), caused by Xanthomonas axonopodis pv. phaseoli var. fuscans (Xapf), negatively impact common bean production globally. Considering the potential of phosphites to protect plants against different diseases, this study investigated the potential of using manganese (Mn) and zinc (Zn) phosphites in common bean for CBB control. Plants were inoculated with Xapf 48 hr after being sprayed with water (control) and solutions (7.5 ml/L) of Mn and Zn phosphites. The area under common bacterial blight progress curve (AUCBBPC) was significantly lower by 34% and 59% for Mn and Zn phosphite treatments in comparison with the control treatment. The AUCBBPC was significantly reduced by 38% for Zn phosphite‐sprayed plants compared to Mn phosphite treatment. Phosphite‐sprayed plants displayed higher values for area under the curves of net CO2 assimilation rate, stomatal conductance to water vapour, transpiration rate and internal‐to‐ambient CO2 concentration ratio than non‐sprayed plants. This indicates the effect of Mn and Zn phosphites in attenuating the photochemical dysfunctions caused by Xapf infection. Moreover, plants sprayed with Mn phosphite displayed higher values for area under the curves of efficiency in capturing the excitation energy of open reaction centres of PSII and electron transport rate than those non‐sprayed indicating their capacity to preserve the capture and the use of the collected energy more efficiently. Lower AUCBBPC for Zn phosphite‐sprayed plants resulted in higher concentrations of total chlorophylls. The Zn phosphite‐sprayed plants showed higher values for area under the curves of β‐1,3‐glucanase, phenylalanine ammonia‐lyase, polyphenoloxidase, ascorbate peroxidase and superoxide dismutase activities. The Zn phosphite spray primed the plants to enhance their defence response and antioxidant capacity to reduce Xapf‐triggered oxidative stress with the preservation of the photosynthetic apparatus more efficiently.

Increased phosphorus availability to corn resulting from the simultaneous applications of phosphate rock, calcareous rock, and biochar to an acid sandy soil

Phosphorus (P) deficiency is one of the main constraints on crop production in Arenosols (acid sandy soil). The high cost of P fertilizers may represent an insurmountable obstacle in many poor countries, leaving the exploitation of their own calcareous and phosphate rocks as the only low-cost and long-term alternative. Biochar is suggested to have positive effects on soil properties; however, there is no published research on the synergistic effects of biochar and rocky materials in modifying soil properties. The aim of this study was to investigate the chemical and biochemical responses of an acid Arenosol treated with phosphate rock (PR), calcareous rock (CR), and biochar (BC), and the implications for corn yield. A soil from Marracuene District, Mozambique was used, where corn was grown for 90 d with the soil treated with: no addition (control), water-soluble zinc phosphite fertilizer (WSP), PR, WSP+CR, WSP+BC, WSP+CR+BC, PR+BC, and PR+CR+BC. Biochar was produced by pyrolysis of babycorn peels for 4 h at 450 °C and applied at 11 g kg−1. The soil pHH2O increased from about 4.54 in the control to 7.38 in the PR+CR+BC treatment. Easily oxidizable organic carbon, cation exchange capacity, and available P were higher in the treatments containing BC than in the control. The treatments containing CR and/or BC led to the highest activities of alkaline phosphomonoesterase, phosphodiesterase, and α-glucosidase, which increased P availability and gave the greatest biomass and yields. We suggest that biochar provides additional soluble P and supplies adsorption sites for phosphate, preventing its evolution to unavailable forms. Thus, PR applied together with BC contributed to an 840% yield increase compared to the control. The treatments containing WSP and BC facilitated phosphite oxidation to phosphate and increased crop yield.

A thio-functionalized zinc phosphite with a large-channel framework and enhanced removal ability of mercury ion from aqueous solutions

The first example of a thio-functionalized zincophosphite material (NTOU-2S) incorporating the 2,5-thiophenedicarboxylate (TPDC) ligands was synthesized using a hydro(solvo)thermal method and structurally characterized by single-crystal X-ray diffraction. Interestingly, the perspective view of the crystal structure for NTOU-2S is similar to our previous report of NTOU-2 but the carboxylate organic ligands (TPDC for NTOU-2S; 1,4-benzenedicarboxylate, BDC, for NTOU-2) in both compounds adopt different types of bis-monodentate coordination models (the unusual cis bonding versus a trans linkage) to bridge the metal atoms of inorganic tubes in the formation of large-channel zincophosphite frameworks, resulting in structural and functional diversities. The thiophene-based compound also displayed higher thermal stability and removal ability for the softer Hg2+ cations from water solutions than the performance of sulfur-free NTOU-2. In addition, the synthesis, structural characteristics, removal properties of heavy metal cations, and thermal and chemical stabilities for both compounds were also reported.

Two new inorganic-organic hybrid zinc phosphites and their derived ZnO/ZnS heterostructure for efficient photocatalytic hydrogen production.

Two novel inorganic–organic hybrid zinc phosphites, namely, [Zn(1,2-bimb)0.5(HPO3)]n (1) and [Zn(1,4-bmimb)0.5(HPO3)]n (2), (1,2-bimb = 1,2-bis(imidazol-1ylmethyl)benzene; 1,4-bmimb = 1,4-bis((2-methyl-1H-imidazol-1yl)methyl)benzene) were synthesized for the first time by hydrothermal reaction. Compound 1 generates a three-dimensional (3D) pillared-layer structure with a 2-nodal 3,4-connected 3,4T15 topology. While compound 2 exhibits a 2D hybrid zinc phosphite sheet with a 3,4-connected 3,4L83 topology network. Utilizing compound 1 and compound 2 as templates and Na2S as an etching agent, a series of highly efficient ZnO/ZnS photocatalysts were obtained. The optimized 1-160 sample demonstrates the highest evolution rate of 22.6 mmol g−1 h−1, exceeding the rate of commercial ZnS samples by more than 14.5 times. The remarkable photocatalytic activity should be attributed to the unique heterojunction structure which shortens the free path of charge carriers and enhances the charge separation efficiency. This work provides a facile strategy for preparing photocatalysts with efficient photocatalytic hydrogen production derived from inorganic–organic hybrid material.

The effects of different dimensional organic amines on synthetic zinc phosphites/phosphates

Three different dimensional zinc phosphites and zinc phosphates, [C7H18N]2[Zn(HPO3)2] (1), [C6H9N2][Zn2(PO4)(HPO3)] (2), and [C6H14N2][Zn2(PO4)2] (3) were hydro(solvo)thermally synthesized from organic amines with the same number of nonhydrogen atoms and different dimensionalities and sizes. Structural analysis indicates that compound 1 shows a one-dimensional (1D) chain structure; compound 2 is an inorganic–organic hybrid two-dimensional (2D) material; compound 3 is a three-dimensional (3D) open-framework zinc phosphate EDI zeolite. The mechanisms of 1D chain-like n-heptamine, 2D planar 3-aminomethylpyridine, and 3D triethylenediamine on the synthetic process were analyzed. The n-heptamine has only one function: a protonated template in compound 1, while 3-aminomethylpyridine has two functions: a protonated template and binding ligand in the synthesis of compound 2. The triethylenediamine has three functions in compound 3: a protonated template, space-filling agent, and structure-directing agent. Thus, the three organic amines play different roles in the three compounds. They were analyzed by XRD, SEM, TGA, FT-IR, ICP, and CHN analyses.

A Highly Stable Dual Functional Zinc Phosphite Carboxylate as Luminescent Sensor of Fe3+ and Cr2O72–

One new organic–inorganic hybrid zinc phosphite carboxylate, namely, [H2N(CH3)2]2[Zn2L(HPO3)2] (1), where H2L= 2′,3′,5′,6′-tetramethyl-[1,1′:4′,1″-terphenyl]-4,4″-dicarboxylic acid, was synthesized...

Phosphites attenuate Sclerotinia sclerotiorum-induced physiological impairments in common bean

Phosphites, marketed as foliar fertilizers and resistance activators, have been shown to be useful for the control of diseases in many profitable crops. Despite the importance of white mold, caused by Sclerotinia sclerotiorum, to reduce common bean yield, knowledge of the phosphites´ effect on disease control at the physiological level is still missing. In this study, the leaf gas exchange and chlorophyll a fluorescence parameters variable-to-maximum chlorophyll a fluorescence ratio (Fv/Fm), photochemical yield [Y(II)], yield for dissipation by down-regulation [Y(NPQ)], yield for non-regulated dissipation [Y(NO)], and electron transport rate (ETR) as well as the concentrations of photosynthetic pigments in common bean plants that were sprayed with zinc (Zn) or copper (Cu) phosphites and challenged or not with S. sclerotiorum were determined. Based on the in vitro assays, Zn and Cu phosphites inhibited fungal mycelial growth in a dose-dependent manner, but the Cu phosphite showed to be more fungitoxic. Lesion area and white mold severity were reduced by Zn and Cu phosphites, but the Zn phosphite was more effective. Fungal infection dramatically decreased the values of net carbon assimilation rate, stomatal conductance to water vapor and transpiration rate on non-sprayed plants. Increases in internal CO2 concentration indicated that fungal-induced photosynthetic impairments were chiefly governed by biochemical limitations, but these impairments were greatly abrogated in the Zn and Cu phosphite-sprayed plants. Similarly, the photochemical dysfunctions stemmed from S. sclerotiorum infection were limited in the Zn and Cu phosphite-sprayed plants. Concentrations of chlorophyll a + b and carotenoids decreased on inoculated plants, but lower reductions were recorded on Zn and Cu phosphites-sprayed plants. In conclusion, the potential of Zn and Cu phosphites in attenuate the S. sclerotiorum-induced physiological impairments in common bean leaflets was demonstrated and may be an effective mean for managing this disease under field conditions.

Biochemical responses of common bean to white mold potentiated by phosphites

Considering that the mechanisms for phosphite-afforded disease control remain elusive, this study investigated whether zinc (Zn) and copper (Cu) phosphites could possible potentiate common bean resistance to white mold, caused by Sclerotinia sclerotiorum, through the stimulation of biochemical defence responses. Lesion area and disease severity were decreased by phosphites spray, but Zn phosphite outcompeted Cu phosphite. Histopathological observations revealed fewer fungal hyphae and less collapse of the mesophyll cells in the Zn and Cu phosphite-sprayed plants compared to water-sprayed ones. The S. sclerotiorum-triggered accumulation of reactive oxygen species, oxalic acid (a fungal secreted toxin) and malondialdehyde (an indicator of cellular damage) were constrained as a result of Zn and Cu phosphites spray. Activities of antioxidant enzymes (superoxide dismutase, peroxidase, ascorbate peroxidase and glutathione-S-transferase at 12 h after inoculation (hai) and catalase at 60 and 84 hai) were higher for Zn and Cu phosphites-sprayed plants than for water-sprayed ones. Activities of defence-related enzymes chitinase (CHI) at 12 hai, β-1,3-glucanase (GLU) and polyphenoloxidase (PPO) were higher at 12–84 hai for Zn, and Cu phosphites sprayed plants, phenylalanine ammonia-lyase at 36–84 hai for the Zn phosphite sprayed ones, CHI at 12–36 hai, GLU at 12–60 hai, PPO at 36 hai and PAL and lipoxygenase at 12 hai for the Cu phosphite sprayed ones upon inoculation with S. sclerotiorum relative to their water-sprayed counterparts. Concentrations of total soluble phenols and lignin-thioglycolic acid derivatives were not affected by Cu phosphite spray on infected plants but were higher and lower, respectively, for Zn phosphite sprayed plants at 60 hai compared to water-sprayed ones. Taken together, the findings from the present study shed light on the biochemical defence mechanisms involved in the Zn and Cu phosphites-mediated suppression of white mold in common bean.

Frontispiece: A Highly Stable Framework of Crystalline Zinc Phosphite with Selective Removal, Recovery, and Turn‐On Sensing Abilities for Mercury Cations in Aqueous Solutions

Frontispiece: A Highly Stable Framework of Crystalline Zinc Phosphite with Selective Removal, Recovery, and Turn‐On Sensing Abilities for Mercury Cations in Aqueous Solutions

A Highly Stable Framework of Crystalline Zinc Phosphite with Selective Removal, Recovery, and Turn-On Sensing Abilities for Mercury Cations in Aqueous Solutions.

A highly stable framework of organic-inorganic hybrid zinc phosphite (NTOU-4) and its cobalt analogue (NTOU-4a) were synthesized under the hydro(solvo)thermal conditions and structurally characterized by single-crystal X-ray diffraction. Their frameworks consisted of inorganic metallophosphite chains, in which the metal atoms were interlinked through 1H-1,2,4-triazole-3,5-diamine and 1,4-benzenedicarboxylate linkers to form new crystalline materials. It is extremely difficult to achieve the consolidation of three distinct coordinations of metal-carboxylate, metal-triazolate, and metal-phosphite bonds into one crystal, resulting in the synthesis of the first mixed-ligand terephthalate-metallophosphite solids in the absence of organic molecules as templates or space-filling counters in their structures. Interestingly, the zinc compound not only exhibits high thermal stability (up to 400 °C in air) and chemical resistance to seawater, aqueous solutions (pH 3-11), and organic solvents at boiling conditions, but also shows selective removal, recovery, and "turn-on" sensing abilities of toxic mercury ions in aqueous solutions. Furthermore, the synthesis, characterization, and the difference of the framework stabilities between isostructural zinc and cobalt compounds are also reported.

A Series of Organic-Inorganic Hybrid Zinc Phosphites Containing Extra-Large Channels.

A series of organic-inorganic hybrid zinc phosphites with extra-large channels were synthesized and characterized by single-crystal X-ray diffraction. This is an unusual example of introducing 1,4-benzenedicarboxylate and/or biphenyl-4,4'-dicarboxylate ligands into the organically templated metal phosphite system to build extra-large-channel zeolite-related materials via hydro(solvo)thermal reactions. Those frameworks are composed of carboxylate linkers and inorganic tubes of zinc phosphites, translating their channel windows from a square shape (NTOU-1) to rhombus forms (NTOU-2 and NTOU-3) via the replacement of organic amines or ligands under synthesis conditions otherwise identical with those used to prepare NTOU-1. The synthesis, structural diversity, photoluminescence, and adsorption properties for dye molecules and lanthanide ions are also reported.

An organic-inorganic hybrid zinc phosphite framework with room temperature phosphorescence.

A novel room temperature phosphorescent material has been developed by the use of luminescent organic rigid poly-imidazole moieties coordinating to a zinc phosphite framework, which shows excellent thermal and mechanical stability.

Inorganic–organic hybrid zinc phosphites with fluorescence/phosphorescence dual emission performances

A strategy to prepare room temperature fluorescence/phosphorescence dual emission materials is explored by coordinating N-containing organic chromophores to metal phosphite frameworks.