Phosphoric Acids Research Articles

Efficacy of Cytoreg in the treatment of diabetic foot disease.

Complications from diabetic foot wounds, including bacterial infection, ulceration and gangrene, are major causes of hospitalisation and are responsible for 85% of amputations in patients with diabetes. Given that orally administered investigational therapeutic Cytoreg (Cytorex de Venezuela SA, Venezuela), a defined aqueous mixture of hydrofluoric, hydrochloric, sulfuric, phosphoric, citric and oxalic acids, has been shown to increase levels of arterial blood oxygen in a Wistar rat model, oral and oral+topical Cytoreg were tested on patients with diabetic foot ulcers (DFUs) under a humanitarian, compassionate-use protocol. All patients received oral Cytoreg (5.0 ml concentrate in fruit juice) for 30 days; half also received weekly wound washing with Cytoreg concentrate in isotonic saline (1:50 volume/volume) (oral+topical group). In addition to standard clinical observations, wounds were monitored against the Saint Elian checklist system for the diabetic foot. A total of 10 patients took part in the study. Complete wound closure was observed in 4/5 patients in the oral+topical group; in the remaining patient, necrotic and fibrin tissues on the wound edges were eliminated. Half (2/4) of the patients receiving oral-only Cytoreg experienced complete wound closure; one patient in this group was removed prematurely because of an unrelated illness and was not replaced. During the study, no significant differences were observed between groups in either the oxygen saturation of the affected tissues or in insulin and glycaemia levels (p<0.05). Significant increases in arterial haemoglobin and arterial oxygen partial pressure (p<0.05) were observed, and significant decreases were measured in the levels of glycosylated haemoglobin, aspartate aminotransferase, glutamic-pyruvic transaminase, creatine and urea (p<0.05). The results of this study justify an expanded clinical study for the treatment of DFUs with Cytoreg.

Acid leaching of vivianite separated from sewage sludge for recovering phosphorus and iron

This paper examines the acid leaching efficiencies of Fe and P from vivianite slurry (VS, Fe3(PO4)2·8H2O), which is magnetically separated from anaerobic digested sludge, and elaborates on Fe and P reuse routes. The characteristics and dissolution behavior of raw VS in hydrochloric, sulfuric, phosphoric, oxalic, and citric acids are investigated. Results reveal that the primary impurities in VS are organic matter, other phosphate compounds, and Mg present in the vivianite crystal structure. Hydrochloric and sulfuric acids could effectively extract P (90%) from VS at an optimal hydrogen-to-phosphorus (H⁺/P) ratio of 2.5, compared with sewage sludge ash (SSA) that normally needs an H⁺/P ratio greater than 3. Hence, VS can be employed as an alternative P resource following a similar recovery route used with SSA. However, in comparison to SSA, VS use can decrease acid consumption in P extraction and the requirement for the extensive purification of cationic impurities. Furthermore, oxalic acid effectively facilitates the separation of P and Fe in VS by precipitating Fe as insoluble ferrous oxalate in acidic conditions, leading to a high Fe recovery rate of 95%. The recovery and reuse of Fe through the oxalic acid route further improves the feasibility of VS as an alternate resource.

Valorization of carbonaceous co-product obtained from iron ore-catalyzed methane cracking as support for Pd catalysts in toluene hydrogenation reaction

Iron ore has been proven as an abundant and sustainable catalyst in the production of hydrogen by catalytic cracking of methane. One of the main challenges is the identification of suitable market niches for the utilization of the resulting iron-carbon hybrid in order to make this process economically viable. This study examines the feasibility of using the iron-carbon hybrid obtained from methane cracking as support of Pd catalysts for the hydrogenation of toluene (350 ºC, 35 bar of H2 at room temperature and 90 min). Before supporting Pd, Fe-C hybrid was subjected to different acid functionalization treatments (nitric and/or phosphoric acids). The results indicate that sequential oxidation with nitric acid, followed by phosphoric acid, is the most effective strategy for achieving the highest catalytic activity (1294 mmolToluene gPd⁻¹) and conversion (27 %). Toluene conversion was 1.8 and 14.2 times higher than with the catalysts treated with nitric and phosphoric acid separately. Therefore, this work proves the possibility of employing carbon/Fe hybrid materials obtained in iron ore catalyzed methane cracking as catalytic supports in industrial relevant reactions.

Double-Shell Encapsulation of Lead-Free Tin Halide Perovskite for Self-Powered Smart Windows.

Luminescent solar concentrators (LSC) have the potential application in building integrated photovoltaic (BIPV). 0D tin-based perovskites are a promising embedding phosphor in LSC due to the large Stokes shift and high photoluminescence quantum yield. But the instability and uncontrollable crystal growth are severe limiting their successful utilization in device fabrication. To tackle these issues, double-shell encapsulated configurations are presented, soft ligands of hypophosphorous acid and hard-shell of hollow mesoporous silica are simultaneously suppressing the oxidation of Sn2+ and restricting crystal growth within nano-matrix. The stable phosphor is subsequently embedded into LSC for harvesting solar energy and the resulting output power efficiently drives the combined electrochromic glass under natural light. These fabricated devices also offer the self-adaptable switch on/off functionality to regulate light absorption with variable solar irradiation intensity in real time. This approach is anticipated to open new avenues for utilizing lead-free perovskite nanomaterials in self-powered smart windows for BIPV.

Determination of the pKa Value of a Brønsted Acid by 19F NMR Spectroscopy.

Brønsted acids, such as phosphoric acids derived from chiral 1,1'-bi-2-naphthol (BINOL), are important catalysts in the formation of carbon-carbon and carbon-heteroatom bonds, for example. The catalytic activity of these Brønsted acids is strongly linked to their acidity, and as such, the evaluation of compounds to determine pKa values provides insight into their catalytic activity. Herein, a 19F{1H} NMR methodology is detailed to determine the pKa of a fluorinated binaphthyl-derived phosphinic acid, rac-1, in acetonitrile and in the presence of a fluorinated sulfonamide reference compound (2-4). The approach was tested initially using 2 and 3, with the ΔpKa (0.08) in strong agreement with previously reported values (6.6 for 2 and 6.68/6.73 for 3). Sigmoidal curves of normalised chemical shift change (Δδ) against equivalents of the base phosphazene P1-tBu added overlapped for 2 and 3, but in the case of rac-1 and either 2, 3 or 4, there was significant separation. A variety of different approaches for determining the ΔpKa were compared. Values of pKa determined when the normalised Δδ was 90% were optimal for 2 and 3, whereas a normalised Δδ of 75% was optimal for 4, resulting in the pKa of rac-1 being determined to be 8.47-8.71.

Asymmetric Aza Friedel-Crafts Reaction of 3,4-Dihydroisoquinolines with 1-Naphthols Catalyzed by Chiral Phosphoric Acids.

An efficient chiral phosphoric acid-catalyzed asymmetric aza Friedel-Crafts reaction of 3,4-dihydroisoquinolines and 1-naphthols is described. The reaction provides a general method for the synthesis of diverse chiral tetrahydroisoquinoline with 1-naphthol substituents at the C1-position in excellent yields and enantioselectivities. Based on the conducted mechanistic experiments, a plausible catalytic mechanism was proposed. Moreover, the practicability of the reaction is successfully demonstrated by its application on a gram scale.

Random Forest‐Based Prediction of Enantioselectivity in Thiol Addition to Imines Catalyzed by Chiral Phosphoric Acids

AbstractThis paper, for the first time, reports calculating molecular descripts from the combinations of catalysts and substrates, for enantioselectivity predictions in chiral phosphoric acid–catalyzed thiol addition to N‐acylimines. Ten molecular descriptors, together with random forest (RF) algorithm, were used to establish the quantitative structure–selectivity relationship (QSSR) model (RF Model I), yielding correlation coefficient of R=0.982, root mean square (rms) error of 0.604 kJ/mol (for 800 enantioselectivity ΔΔG from 32 catalysts in the training set), R=0.922, rms=1.075 kJ/mol (for 275 enantioselectivity ΔΔG from 11 new catalysts in the test set). The RF Model I was proved to be more accurate in enantioselectivity predictions, compared with the QSSR models reported in the literature and with the RF Model II and RF Model III in this work. Moreover, the RF Model I was based on simple Dragon descriptors and capable of extrapolative prediction for new catalysts. Therefore, it is reasonable deriving molecular descriptors from the combinations of catalysts and substrates (thiols and imines). This work provides a new method for the predictions of enantioselectivity ΔΔG.

Divergent asymmetric reactions of α-alkenyl ketones with β,γ-alkynyl-α-imino esters enabled by chiral phosphoric acids

Divergent asymmetric synthesis provides access to a wide range of isomers from the same starting material by modifying the reaction conditions, which plays an important role in the efficient construction of a structurally diverse molecular library for structure-activity relationship studies. In this work, we present the divergent asymmetric addition of α-alkenyl ketones with β,γ-alkynyl-α-imino esters enabled by chiral phosphoric acid catalysis. Despite the challenging presence of multiple reactive sites in both components, we successfully achieved the regioselective synthesis of both α-1,2-addition α-tertiary amines and γ-1,4-addition allenes with good to high regio-, diastereo- and enantioselectivities by modifying the reaction conditions. Moreover, the stereodivergent asymmetric synthesis of the four allene stereoisomers bearing contiguous central and axial chirality was achieved by adjusting the E/Z configuration of the α-alkenyl ketone substrates.

Impact of functional monomers, bioactive particles, and HEMA, on the adhesive performance of self-etch adhesive systems applied to simulated altered dentin

ObjectivesThis study aimed to evaluate how self-etching/universal dental adhesive systems (DASs) with differing compositions interact with sound (S), post-radiotherapy (irradiated; I), and artificially eroded (E) dentin in terms of bonding properties. Methods: The DASs tested were Adper Scotchbond Multipurpose (MP; control), Clearfil SE Bond (SE), FL Bond II (FL), Adper Single Bond Universal (SU) and BeautiBond Xtreme (BX). They were analyzed for initial and 6-month microtensile bond strength (µTBS, n = 12), mode of failure (40 x), scanning electron microscopy (SEM), surface wettability (W, n = 10), and degree of conversion (DC, n = 3) via Fourier-transform infrared spectroscopy (FTIR). Normal and homogeneous distribution of the data allowed their analyses through ANOVA and Tukey tests (p < 0.05). Results: All DASs except BX exhibited higher µTBS for S decreasing for I and E. BX demonstrated the greatest stability among the altered substrates. FL showed the most hydrophobic properties, likely due to its bioactive components. Universal DASs achieved higher DC, regardless of composition. Conclusions: HEMA-free formulation combined with carboxylic and phosphoric acids in BX, achieved the most stable performance for altered substrates. Clinical SignificanceSince radiotherapy and erosion affect dentin, their characteristics compromise adhesive performance and impair the achievement of durable and satisfactory restorations. The use of universal adhesives less dependent on calcium seems less susceptible to hydrolytic degradation and may be a promising option for maintaining adhesive stability over time.

Tin oxides@stannous pyrophosphate colloidal quantum dots as multifunctional electron transporting layer for efficient and stable perovskite solar cells

Perovskite solar cells (PSCs) are anticipated to spearhead the revolution in solar energy technology. Engineering the electron transporting layer (ETL)/perovskite heterointerface is known to be a key point for further high-performance PSCs because it determines the main charge transporting and energy losses. However, the most advanced SnO2 colloidal precursors tend to exhibit agglomeration and structural flaws, thereby deteriorating the morphology and electronic mass of the obtained ETL. Here, we polished the microstructure of the SnO2 surface by self-assembling SnO2@Sn2P2O7 quantum dots (SPOS), which is synthesized by the chemical reaction between hypophosphoric acid (H3PO2) and SnO2. The Sn2P2O7 was synthesized on the SnO2 surface, terminating the surface dangling bonds and resulting in steady SPOS quantum dots with smooth microstructure. The SPOS ETL with good optical and electrical properties as well as matched bandgap alignment with perovskite, yielding an improved power conversion efficiency of 23.35% for PSCs. Moreover, due to the suppression of defect-induced deprotonation reactions, the SPOS-PSCs exhibit favorablelongstability than the SnO2-PSCs. This work demonstrates that the surface reconstruction of the ETL is crucial for enhancing the power conversion efficiency and stability of PSCs.

Membrane transport of rare earth metal ions N, N’-bisdioctylphosphorylmethyl-1,4-diaminobutane by the active transport mechanism

The method of membrane extraction for rare earth elements (REE) using the carrier N, N’-bisdioctylphosphorylmethyl-1,4-diaminobutane (DPDA-8) ions, leveraging an active transport mechanism, has been optimized. The distribution of DPDA-8 within the membrane pores was confirmed using scanning electron microscopy (SEM). Both light and heavy REE extractions from a simulated solution using DPDA-8 and trioctylphosphine oxide (TOPO) in 1,2-dichlorobenzene were explored. The influence of feed solution pH, carrier and anion concentration, supported liquid membrane (SLM) type and stability, and cell temperature, among other parameters, were meticulously examined. The results indicate a decrease in permeability with a decrease in feed solution pH attributed to competitive acid transport through the membrane. Additionally, the formation of H-complexes between carriers and perchloric or phosphoric acids was investigated using Fourier Transform Infrared (FTIR) spectroscopy and X-ray diffraction (XRD) techniques. Changes in the stretching bands of amino and phosphine oxide groups in DPDA-8 were monitored and characterized. XRD analysis of the crystal structures of salts DPDA-6·ClO4 and DPDA-12·H2PO4 revealed a two-dimensional layered supramolecular organization with varying anion positions relative to hydrophobic fragments. The DPDA-8 carrier demonstrated significantly higher permeability values compared to TOPO, with differences in permeability exceeding twofold for certain metals. FTIR spectroscopy identified the main coordination centers of DPDA-8 during the liquid–liquid extraction of specific REEs.

One-Pot Multienzyme Cascades for Stereodivergent Synthesis of Tetrahydroquinolines.

The tetrahydroquinoline (THQ) framework is commonly found in natural products and pharmaceutically relevant molecules. Apart from the use of transition metal catalysts and chiral phosphoric acids, the chiral 2-substituted 1,2,3,4-THQs are synthesized using amine oxidase biocatalysts. However, the use of imine reductases (IREDs) in their asymmetric synthesis remained unexplored. In the current work, IREDs are employed in telescopic multienzyme cascades to catalyze the intramolecular reductive amination leading to chiral 2-alkyl and 2-aryl substituted-1,2,3,4-tetrahydroquinolines starting from inexpensive nitroalkenones. The cascades containing NtDBR (an ene reductase), NfsB (a nitro reductase) with either Na2S2O4 or V2O5, various IREDs, and glucose dehydrogenase (for NADPH regeneration) are used to synthesize a broad range of (R)/(S)-2-alkyl-substituted (THQs) (26 examples) with high yield (up to 93%) and excellent ee (up to 99%) in one-pot. The method further facilitates the one-pot biocatalytic synthesis of chiral 2-aryl substituted THQs (26 examples) from amino chalcones. Lastly, the asymmetric synthesis of several (R)- and (S)-THQ based intermediates of Hancock alkaloids showed the practical application of the newly developed biocatalytic cascades.

Filterless Near‐Infrared Narrowband Photodetectors Based on Mixed Metal Perovskite Single Crystals

AbstractIodine‐based Sn‐Pb mixed perovskite single crystals (SCs) are promising candidates for near‐infrared (NIR) narrowband photodetectors due to their low bandgaps. However, they are highly defective when grown in ambient air due to the extremely poor air stability of Sn2+ ions in precursor solutions. It is discovered that the oxidation of Sn2+ to Sn4+ ions not only consumes Sn2+ ions but also increases the precursor solution viscosity. The increased viscosity slows down the solute diffusion and hinders the anisotropic growth of SCs, leading to Sn‐Pb perovskite SCs with curved convex surfaces and unevenly distributed composition. By preventing the solute‐diffusion‐limited growth mode with hypophosphorous acid (H3PO2), high‐quality Sn‐Pb perovskite SCs can be robustly grown in ambient air with low trap density of 6.58 × 109 cm−3 and high carrier mobility‐lifetime product (µτ) of 1.5 × 10−3 cm2 V−1. Accordingly, a series of filterless NIR narrowband photodetectors with gradually tuned detection centers and dual detection modes has been achieved, delivering a maximum external quantum efficiency of 15.2% and detectivity of 1.19 × 1010 Jones.

Efficient sequestration of cesium ions using phosphoric acid-modified activated carbon fibers from aqueous solutions

In this study, acid-modified activated carbon fibers (ACF-Ps) were synthesized by phosphorylation. Three different types of ACF-based adsorbents functionalized with PO43−, P2O74−, or P3O105− ions, namely, ACF-P1, ACF-P2, and ACF-P3, were prepared by phosphorylating ACF with trisodium phosphate (Na3PO4), sodium dihydrogen pyrophosphate (Na2H2P2O5), and sodium tripolyphosphate (Na5P3O10), respectively, and utilized as adsorbents to remove cesium ions (Cs+) from aqueous solutions. Among the tested adsorbents, ACF-P3 exhibited the highest Cs+ adsorption capacity of 37.59 mg g−1 at 25 °C and pH 7 which is higher than that of ACF (5.634 mg g−1), ACF-P1 (19.38 mg g−1), and ACF-P2 (30.12 mg g−1) under the same experimental conditions. More importantly, the Cs+ removal efficiencies of ACF-P3 (82.90%), ACF-P2 (66.2%), ACF-P1 (34.2%) were 29.3-, 23.4-, and 12.11-fold higher than that of un-treated ACF (2.83%). The results suggested that the phosphorylation with Na5P3O10 is highly suitable for Cs+ adsorption which effectively functionalizes ACF with a greater number of phosphate functional groups. Adsorption and kinetic data well-fitted the Langmuir isotherm and pseudo-second-order model, respectively, which indicated the monolayer adsorption of Cs+ onto ACF-P1, ACF-P2, and ACF-P3 which were largely controlled by chemisorption. Overall, phosphoric acids containing different phosphate-based polyanions (PO43−, P2O74−, or P3O105−) enriched –OH and/or –COOH surface functional groups of ACF in addition to P-containing surface groups (PO, C–P–O, C–O–P, and P–O) and facilitated the Cs+ adsorption through surface complexation and electrostatic interactions.

Heterogeneous organo/metal cooperative catalysis: One-pot immobilization of Pd(PPh3)4 and chiral phosphoric acid to hollow mesoporous polystyrene nanospheres for efficient asymmetric α-allylation of aldehydes

The widely used combinations of palladium catalysts and chiral phosphoric acids face with the problems of cooperative catalysis and low-cost immobilization of binary catalysts in heterogeneous catalysis, due to the significant decline in the freedom of anchored catalysts. In this paper, the one-pot immobilization of both chiral phosphoric acid (TRIP) and Pd(PPh3)4 to hollow mesoporous polystyrene nanospheres (HMPNs) via Friedel-Crafts alkylation is developed to fabricate HMPNs-supported dual organo/metal catalysts (Pd(PPh3)4#TRIP@HMPNs) at a low cost. The efficient cooperative catalysis of anchored TRIP and Pd(PPh3)4 with good to excellent yields (8993 %) and enantioselectivities (8087 % ee) is achieved in the direct asymmetric α-allylation of aldehydes with allylic alcohols. The higher molar ratio of TRIP to Pd(PPh3)4 and a lower crosslinking degree of HMPNs are beneficial to the cooperative catalysis of the anchored catalysts. Overall, this paper showcases a success in solving the key problems in heterogeneous asymmetric metal/oragano catalysis.

Silica-Supported Chiral Phosphoric Acids Catalyzed C–H, C–C, and Sequential C–C/C–H Bond Formation in Flow

Silica-Supported Chiral Phosphoric Acids Catalyzed C–H, C–C, and Sequential C–C/C–H Bond Formation in Flow

Enantioselective N-H Bond Insertion Reaction of Anilines Enabled by Ruthenium and Chiral Phosphoric Acid Cooperative Catalysis.

The enantioselective carbene insertion into N-H bonds of anilines has been realized by cooperative catalysis of ruthenium complexes and chiral phosphoric acids, providing the expected α-aryl glycines in moderate to good yields with high enantioselectivity. Typically, by slightly modifying the reaction conditions, this approach allows the N-H bond insertion reaction to be effective for both α-aryl and α-alkyl diazoacetates for the first time with high enantioselectivity (up to 96% and 95% ee, respectively).

Acid resistance of alkali-activated binders based on clays from phosphate mining by-products

This paper outlines the results of studying the resistance of alkali-activated materials (AAM), based on calcined yellow clay from phosphate mine by-products as a precursor, to an acid attack (with sulfuric and phosphoric acids, 5 %, pH ≈ 0,8–2). Calcined yellow clay (YC850) is used as the source of aluminosilicates, containing montmorillonite, dolomite, and quartz. The alkali-activation of such materials allows the determination of an adequate valorization way and evaluating their durability leads to defining the range of application. The residual compressive strengths were measured after 1, 2, and 4 weeks of immersion in those acids. The deterioration suffered by the paste specimens was examined using different techniques.The degree of deterioration differs from one acid to another; in sulfuric acid, the strengths decrease from 47 MPa to 10.6 MPa presenting 77.4 %. While in phosphoric acid, the decrease was about 36.2 % (30 MPa) after 28 days of attack. This detriment in the strengths is associated with changes not only in the microstructure but also with the alteration of the reaction products, mainly the binding gels C-A-S-H and (C,N)-A-S-H, which undergoes dealumination and decalcification. What is more, the chemical attack involves several reactions; calcium coming from the precursor reacts with the sulfates (in the H2SO4 attack) inducing the precipitation of gypsum, which is responsible for the significant strength loss. In addition, the dissolution of crystalline minerals, such as periclase and gehlenite (present in the precursor) generates higher porosity explaining the obtained results.

Supermolecule polymer derived of carbon nitride with controllable nanosheet for enhancing the degradation performance of RhB and BPA

Using melamine-cyanuric acid (MCA) supramolecular polymer as a precursor, a method was employed to synthesize graphitic carbon nitride with a large specific surface area and controllable band structure. The band structure and morphology of graphitic carbon nitride (g-C3N4) are closely related to the type of solvent used. By treating it with hypophosphorous acid and subsequent high-temperature treatment for 10 h , the precursor material was calcined to produce graphitic carbon nitride with a hollow tubular morphology. Experimental results demonstrate that this material exhibits outstanding performance in photocatalytic degradation of Rhodamine B and Bisphenol A. This work provides a new and effective strategy for achieving visible-light photocatalytic degradation of organic compounds.

Unveiling the effect of hypophosphorous acid for the growth of high quality Cs3Cu2I5 single crystals

The zero-dimensional copper halide perovskite Cs3Cu2I5 displays extraordinary luminescence and scintillation characteristics, and high-quality crystals are extremely desirable for exploring the commercial applications. Currently, the most critical issue in the solution growth of Cs3Cu2I5 crystals is the easy oxidation of halides, which significantly hinders the optimization of crystal qualities. The hypophosphorous acid (H3PO2) has been applied to inhibit the oxidation, nevertheless, the related mechanism is elusive and has been largely ignored. Herein, Cs3Cu2I5 crystals have been grown from N, N-Dimethylformamide (DMF) solvent by the antisolvent vapor-assisted crystallization (AVC) method. It is verified that H3PO2 effectively prevents the oxidation of Cs3Cu2I5 by rapidly reducing Cu2+ and I3−, maintaining the stability of the precursor solution and continuously suppressing oxidation during the whole growth process. Meanwhile, by increasing the acidity of the solution, H3PO2 dissolve precursor colloids and efficiently enhance the solubility of halides. Thus, the addition of H3PO2 favors the rapid growth of centimeter-sized Cs3Cu2I5 crystals with well-defined crystallographic planes within several days. As excellent gamma ray scintillator, the crystal exhibits high light yield of 38000 photons/MeV, with energy resolution of 5.6 % under 662 keV radiation from a 137Cs source. This work deeply elucidates new insight into the critical effect of H3PO2 in the DMF based solution crystal growth, facilitating the preparation of large-size and high-performance copper halide perovskite crystals.