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1.
Compend Contin Educ Dent ; 45(5): 243-246; quiz 247, 2024 May.
Article in English | MEDLINE | ID: mdl-38900462

ABSTRACT

Adhesive dentistry is an essential component in the delivery of direct and indirect restorations. Ongoing discussions among scientists and clinicians have focused on whether or not current self-etch and universal adhesives adequately prepare enamel surfaces to achieve optimal bond strengths. To address these concerns, a selective enamel etch technique has been recommended. The definition of a selective enamel etch technique is as its name suggests. The clinician selectively etches the enamel of a cavity preparation by applying phosphoric acid etchant to the enamel surfaces of the preparation while refraining from applying the etchant to the dentin. This article explores the current research to help guide clinicians to achieve ideal outcomes when using dental adhesives. With few exceptions, the current scientific evidence recommends a selective enamel etch technique in conjunction with the clinician's adhesive system of choice.


Subject(s)
Acid Etching, Dental , Dental Bonding , Dental Enamel , Humans , Dental Enamel/drug effects , Acid Etching, Dental/methods , Dental Bonding/methods , Phosphoric Acids/chemistry , Dental Cavity Preparation/methods
2.
Chem Commun (Camb) ; 60(48): 6194-6197, 2024 Jun 11.
Article in English | MEDLINE | ID: mdl-38805249

ABSTRACT

We present a facile strategy to achieve color-tunability room-temperature phosphorescence (RTP) nanoprobes by doping mineral acids (i.e., boric acid and phosphoric acid) in an organic silicon scaffold through a cross-linking process. Such RTP nanoprobes exhibit inherent tunable phosphorescence (from 420-650 nm) with long lifetime (emission lasting for ∼5-15 s, RTP lifetime: ∼0.53-2.11 s) and high quantum yields (∼13.1-43.0%). Therefore, the as-prepared nanoprobes enable multiple imaging in live cells with a high signal-to-background ratio value of ∼52.


Subject(s)
Boric Acids , Phosphoric Acids , Temperature , Humans , Phosphoric Acids/chemistry , Boric Acids/chemistry , HeLa Cells , Optical Imaging , Nanoparticles/chemistry , Fluorescent Dyes/chemistry , Fluorescent Dyes/chemical synthesis , Color , Luminescent Measurements , Time Factors
3.
Clin Oral Investig ; 28(5): 271, 2024 Apr 25.
Article in English | MEDLINE | ID: mdl-38658431

ABSTRACT

OBJECTIVES: This in vitro study evaluated the effect of different colouring solutions and primer systems used in the bonding of brackets on enamel colour change and bond strength. MATERIALS AND METHODS: 120 premolar teeth were divided into four main groups; brackets were bonded with 37% orthophosphoric acid + Transbond XT Primer in Group 1, 3 M Single Bond Universal in Group 2, Transbond Plus SEP in Group 3, and G-Premio Bond in Group 4. Each group was divided into three subgroups, and the teeth were placed in a cup containing coffee and tea mixture, in a cup containing cola and in distilled water. A bond strength test was applied to all teeth. Colour measurements of all teeth were performed at 2 different times: before bonding and after the bond strength test. RESULTS: The average bond strength of the 37% orthophosphoric acid group was higher than that of the other groups. The effect of primer and solution groups on colour change was statistically significant (p = 0.001 and p = 0.023, respectively). CONCLUSIONS: In this study, the bond strength was clinically sufficient in all primer groups. The highest colour change was observed when the tea-coffee solution and Transbond Plus SEP primer were used. CLINICAL RELEVANCE: This study has identified enamel discoloration and bond strength from different colouring solutions and primer systems used for bonding braces, which can be used to inform clinicians and patients to achieve better treatment results.


Subject(s)
Bicuspid , Bisphenol A-Glycidyl Methacrylate , Dental Bonding , Orthodontic Brackets , Resin Cements , Shear Strength , Humans , Dental Bonding/methods , In Vitro Techniques , Resin Cements/chemistry , Color , Coloring Agents , Materials Testing , Dental Enamel/chemistry , Dental Stress Analysis , Phosphoric Acids/chemistry , Surface Properties , Tea/chemistry , Acid Etching, Dental
4.
J Chromatogr A ; 1722: 464843, 2024 May 10.
Article in English | MEDLINE | ID: mdl-38574599

ABSTRACT

Reversed-phase high performance liquid chromatography (RP-HPLC) is the most widely used chromatographic method. In addition to hydrophobic interactions, additional interactions such as electrostatic interactions may participate in the retention behaviour of an analyte. This makes it possible to use RP-HPLC for many types of analyte. We describe a simple method for separating inorganic anions on a C18 column, in which retention of inorganic anions is almost entirely due to electrostatic interactions. This leads to rapid separations as well as higher theoretical plate numbers. We used 2 mM phosphoric acid containing a low concentration of disodium molybdate as the mobile phase, which allows UV detection of non-UV-absorbing anions. With this method, we determined eight inorganic anions including several non-UV-absorbing anions photometrically at 220 nm. The detection limits of the examined eight inorganic anions calculated at a signal-to-noise ratio of 3 were between 0.3 and 10 µM. The detector response was linear over three orders of magnitude of inorganic anion concentration. The proposed RP-HPLC/UV method was successfully applied to determine inorganic anions in some water samples.


Subject(s)
Anions , Chromatography, Reverse-Phase , Molybdenum , Phosphoric Acids , Anions/chemistry , Molybdenum/chemistry , Phosphoric Acids/chemistry , Chromatography, Reverse-Phase/methods , Chromatography, High Pressure Liquid/methods , Limit of Detection
5.
J Esthet Restor Dent ; 36(6): 930-940, 2024 Jun.
Article in English | MEDLINE | ID: mdl-38433719

ABSTRACT

OBJECTIVE: This study aimed to evaluate the effects of different surface treatments on the repair bond strength between a fiber-reinforced dentin composite and a posterior composite. METHODS: Forty fiber-reinforced dentin composite resin blocks (4 mm × 4 mm × 4 mm) were separated into eight groups (n = 5) according to the surface preparation methods: (G1) negative control group, (G2) adhesive application, (G3) 50% dimethylsulfoxide (DMSO) application, (G4) 50% DMSO + adhesive application, (G5) 37% phosphoric acid etch + adhesive application, (G6) air abrasion + adhesive application, (G7) 37% phosphoric acid etch + 50% DMSO application + adhesive application, and (G8) air abrasion +50% DMSO application + adhesive application group. The composite surfaces were repaired in two layers with a posterior composite. Composite sticks were subjected to a micro tensile bond strength (µTBS) test. Fractured surfaces were evaluated using a stereomicroscope (×25). Short fiber-reinforced composite samples' surfaces were investigated by scanning electron microscope (SEM). Shapiro Wilk, one-way ANOVA, and Tukey HSD tests were used for statistical evaluation. RESULTS: The highest average (µTBS) values were observed in G8, whereas the lowest mean µTBS values were evident in the G1 group. Statistically significant µTBS values were found in all adhesive-applied groups when compared with the negative control group. Notably, the application of 50% DMSO without adhesive did not lead to a statistically significant increase in µTBS values. SEM images demonstrated that acid etching partially eliminated residues on the composite surface, while air abrasion had a detrimental effect on the integrity of fiber structures. CONCLUSION: In the repair of fiber-reinforced dentin composite with a posterior composite, adhesive application is an effective approach. The treatment of 50% DMSO without adhesive did not confer a statistically significant advantage, and the supplemental use of acid etch or air abrasion did not show an additional benefit compared to adhesive-only repairs. CLINICAL SIGNIFICANCE: Adhesive application emerges as a potent and effective strategy for the repair of bur-roughened fiber-reinforced dentin composites. With its limitations, the study highlights the efficacy of adhesive-only repairs without the necessity for additional surface treatments.


Subject(s)
Composite Resins , Dental Bonding , Surface Properties , Tensile Strength , Composite Resins/chemistry , Dental Bonding/methods , Humans , Dentin , Acid Etching, Dental , Materials Testing , Phosphoric Acids/chemistry , Dentin-Bonding Agents/chemistry , Dental Stress Analysis , Microscopy, Electron, Scanning
6.
Am J Orthod Dentofacial Orthop ; 165(5): 565-575, 2024 May.
Article in English | MEDLINE | ID: mdl-38372682

ABSTRACT

INTRODUCTION: This study aimed to investigate the surface free energy and surface roughness (SR) of metallic alloys under the influence of acid solutions. METHODS: The experiment involved the use of 270 rectangular wire samples measuring 0.019 × 0.025-in. These samples were sourced from 3 different commercial brands: Dentsply GAC, American Orthodontics, and Orthoclassic. This in vitro study categorized the samples into 3 groups based on the solutions employed: deionized water, citric acid, and phosphoric acid. Each group consisted of 90 samples, with 30 samples representing each type of alloy-stainless steel, nickel-titanium, and titanium molybdenum alloy (TMA). The wire segments were immersed in their respective solutions for 72 hours at a controlled temperature of 37°C, with continuous orbital agitation at 130 rpm. After the immersion period, the study analyzed both surface free energy and SR. The mean values obtained were subjected to an analysis of variance at a significance level of 5%. RESULTS: All alloys displayed hydrophobic behavior, as indicated by interaction free energy values <0. In acidic environments (phosphoric acid and citric acid), significant differences were observed among different brands and alloys, affecting surface energy and interaction free energy. Variations in SR among metallic alloys included steel with the lowest SR variations, followed by nickel-titanium and TMA. Notably, the TMA alloy stood out with significantly higher surface energy compared with that of the other alloys (P <0.001). CONCLUSIONS: In this study, all examined alloys demonstrated a hydrophobic nature, suggesting a limited attraction to water. Notably, TMA exhibited the least hydrophobic behavior among the alloys studied. However, when exposed to citric acid, TMA displayed the most substantial alterations in its surface properties. These results underscored the significance of accounting for the distinctive properties of each alloy and their responses to diverse challenges, such as exposure to acidic solutions, during the selection of orthodontic wires for orthodontics treatment.


Subject(s)
Alloys , Dental Alloys , Materials Testing , Orthodontic Wires , Surface Properties , Corrosion , Dental Alloys/chemistry , Nickel/chemistry , Titanium/chemistry , Citric Acid/chemistry , Stainless Steel/chemistry , Phosphoric Acids/chemistry , Molybdenum/chemistry
7.
J Prosthet Dent ; 131(4): 743.e1-743.e6, 2024 Apr.
Article in English | MEDLINE | ID: mdl-38368144

ABSTRACT

STATEMENT OF PROBLEM: Phosphoric acid is commonly used in dentistry as an etchant but can result in excessive demineralization of dentin, a major contributor to the instability of dentin-bonded restorations. Nevertheless, research on the development of etchants that can reduce acid damage is sparse. PURPOSE: The purpose of this in vitro study was to investigate the effects of polyvinylpyrrolidone-modified phosphoric acid on the dentin bonding of an etch-and-rinse adhesive. MATERIAL AND METHODS: Protective etchants were prepared by adding polyvinylpyrrolidone to 35% phosphoric acid aqueous solutions: the 3 concentrations were 0.5% (P0.5% group), 1% (P1% group), and 2% (P2% group) w/v. The treatment agent of the control group (C) was 35% phosphoric acid gel. Scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), microhardness, microtensile bonding strength (µTBS), nanoleakage, and in situ zymography were used to evaluate the appearance of the protective etchant on dentin bonding. The results were analyzed with a 1-way ANOVA test (α=.05). RESULTS: SEM showed no obviously exposed collagen fiber in the P1% and P2% groups. FTIR showed less demineralization of the dentin surface, and microhardness was higher after treatment with the protective etchant (P<.05). The µTBS of P1% (70 ±9.2 MPa) was the highest, and group C (44 ±5.8 MPa) was the lowest in all groups (P<.05). Moreover, there was weaker MMP activity in the P1% and P2% groups (P<.05). CONCLUSIONS: This study demonstrated that the protective etchant effectively reduced demineralization, enhanced bond strength, and reduced nanoleakage and enzyme activity within the hybrid layer.


Subject(s)
Dental Bonding , Tooth Demineralization , Humans , Povidone , Phosphoric Acids/chemistry , Phosphoric Acids/pharmacology , Microscopy, Electron, Scanning , Dentin , Tensile Strength , Dentin-Bonding Agents/chemistry , Materials Testing , Resin Cements/chemistry
8.
Angew Chem Int Ed Engl ; 63(15): e202319958, 2024 Apr 08.
Article in English | MEDLINE | ID: mdl-38300702

ABSTRACT

Nucleoside monophosphates (NMPs) are the subunits of RNA. They are incorporated into growing complementary strands when sequences are copied in enzyme-free reactions using organic leaving groups at the phosphates. Amino acids are rarely considered as leaving groups, but proline can act as a leaving group when N-linked to NMPs, so that prolinyl NMPs hydrolyze in aqueous buffer at 37 °C, with half-life times as short as 2.4 h, and they act as monomers in enzyme-free primer extension. Still, their level of reactivity is insufficient for practical purposes, requiring months for some extensions. Herein we report the synthesis of eight substituted prolinyl AMPs together with seven related compounds and the results of a study of their reactivity. A δ-carboxy prolinyl NMP was found to be converted with a half-life time of just 11 min in magnesium-free buffer, and a δ-isopropyl prolinyl NMP was shown to react sevenfold faster than its prolinyl counterpart in enzyme-free genetic copying of RNA. Our results indicate that both anchimeric and steric effects can be employed to increase the reactivity of aminoacidyl nucleotides, i.e. compounds that combine two fundamental classes of biomolecules in one functional entity.


Subject(s)
Amides , Nucleotides , Amides/chemistry , Phosphoric Acids/chemistry , RNA/chemistry
9.
J Dent ; 138: 104734, 2023 11.
Article in English | MEDLINE | ID: mdl-37793561

ABSTRACT

OBJECTIVE: To analyze the effect of Katana™ Cleaner (KC) in nanomechanical and triboscopic properties of etched dentin. METHODS: Dentin disks from human third molars were prepared. Two main groups of study were established in function of the etching conditioning, phosphoric acid (PA) and Clearfil SE Bond primer (CSEB). Four subgroups were tested within each group: i) untreated dentin (UD), ii) etched dentin (ED) [(PAED/CSEB)], iii) etched dentin contaminated with saliva (PAED+S)/(CSEB+S), and iv) etched and contaminated dentin treated with KC (PAED+S+KC)/(CSEB+S+KC). Nano-DMA testing and imaging, atomic force microscopy (AFM) analysis and nanoroughness (SRa) measurements were obtained. Field emission scanning electron microscopy (FESEM) images were also acquired. RESULTS: Phosphoric acid etched dentin samples and those specimens contaminated with saliva (PAED+S) attained the highest SRa values, that decreased after Katana™ Cleaner application (PAED+S+KC). In the group of dentin treated with CSEB primer, all subgroups performed similar, except in CSEB+S that attained the highest SRa values. The treatment with KC restored the original values of complex modulus of the untreated dentin. KC application produced the lowest and the highest tan delta values on PAED and CSEB groups, respectively. CONCLUSION: Katana™ Cleaner provided equally mature dentin surfaces after any of the etching methods. Tan delta increased when Katana™ Cleaner was applied on the dentin surface previously etched and contaminated with saliva, regardless the kind of etchant, thus facilitating the dissipation of energy for elastic recoil during loading. CLINICAL SIGNIFICANCE: Katana™ Cleaner application after saliva contamination originated similar low roughness levels, regardless the type of etching method. Both complex and storage moduli were similar, after Katana™ Cleaner application, in any case.


Subject(s)
Dental Bonding , Dentin-Bonding Agents , Humans , Dentin-Bonding Agents/chemistry , Dentin/chemistry , Resin Cements/chemistry , Phosphoric Acids/pharmacology , Phosphoric Acids/chemistry , Saliva , Surface Properties , Microscopy, Electron, Scanning , Dental Bonding/methods , Materials Testing
10.
J Prosthet Dent ; 130(5): 744.e1-744.e9, 2023 Nov.
Article in English | MEDLINE | ID: mdl-37730466

ABSTRACT

STATEMENT OF PROBLEM: Secondary caries is a major factor in the failure of dental restorations. However, studies on the fabrication of acid-resistant and antibacterial dentin to improve dentin bonding are sparse. PURPOSE: The purpose of this in vitro study was to compare the effects of 2 types of fluoride-containing etchants on dentin bonding and explore the feasibility of formulating an altered dentin substrate to improve dentin bonding. MATERIAL AND METHODS: NaF-containing and SnF2-containing etchants were developed by adding sodium fluoride and stannous fluoride to a 35% phosphoric acid aqueous solution. Two groups (N1 and N2) containing NaF, 10 and 30 mg/mL respectively, and 2 groups (S1 and S2) containing SnF2, 18.6 and 55.8 mg/mL respectively, were formulated. The etchant of the control group (C) was 35% phosphoric acid gel. Scanning electron microscopy (SEM), energy dispersive spectrometry (EDS), Fourier transform infrared spectroscopy (FTIR), microhardness, antierosion, and antibacterial tests were performed on the treated dentin. Moreover, the microtensile bond strength (µTBS) of each group was tested, and the fracture mode was determined after testing. Statistical analysis was performed with the 2-way ANOVA test (α=.05). RESULTS: The exposed collagen fiber was observed in group C, and minerals were formed on the dentin in the experimental groups. SEM, FTIR, and the microhardness test indicated more remineralization in the SnF2-containing etchant groups. The µTBS of S1 (77.5 ±10.36 MPa) was the highest in all groups, and group C (38.5 ±9.01 MPa) was the lowest. Moreover, the antierosion and antibacterial properties of the S2 group were the best among all groups (P<.05). CONCLUSIONS: Compared with NaF-containing etchant, SnF2-containing etchant could improve the dentin substrate, increase remineralization, improve bonding strength, and enhance antibacterial ability, especially by increasing resistance to acid erosion.


Subject(s)
Dental Bonding , Dental Caries , Humans , Phosphoric Acids/pharmacology , Phosphoric Acids/analysis , Phosphoric Acids/chemistry , Microscopy, Electron, Scanning , Dentin/chemistry , Anti-Bacterial Agents/pharmacology , Anti-Bacterial Agents/therapeutic use , Tensile Strength , Materials Testing , Dentin-Bonding Agents/pharmacology , Dentin-Bonding Agents/therapeutic use , Resin Cements/chemistry
11.
Nucleic Acid Ther ; 33(5): 319-328, 2023 10.
Article in English | MEDLINE | ID: mdl-37638793

ABSTRACT

We describe here the design, synthesis, physicochemical properties, and hepatitis B antiviral activity of new 2'-O-alkyl ribonucleotide N3'→P5' phosphoramidate (2'-O-alkyl-NPO) and (thio)-phosphoramidite (2'-O-alkyl-NPS) oligonucleotide analogs. Oligonucleotides with different 2'-O-alkyl modifications such as 2'-O-methyl, -O-ethyl, -O-allyl, and -O-methoxyethyl combined with 3'-amino sugar-phosphate backbone were synthesized and evaluated. These molecules form stable duplexes with complementary DNA and RNA strands. They show an increase in duplex melting temperatures of up to 2.5°C and 4°C per linkage, respectively, compared to unmodified DNA. The results agree with predominantly C3'-endo sugar pucker conformation. Moreover, 2'-O-alkyl phosphoramidites demonstrate higher hydrolytic stability at pH 5.5 than 2'-deoxy NPOs. In addition, the relative lipophilicity of the 2'-O-alkyl-NPO and NPS oligonucleotides is higher than that of their 3'-O- counterparts. The 2'-O-alkyl-NPS oligonucleotides were evaluated as antisense (ASO) compounds in vitro and in vivo using Hepatitis B virus as a model system. Subcutaneous delivery of GalNAc conjugated 2'-O-MOE-NPS gapmers demonstrated higher activity than the 3'-O-containing 2'-O-MOE counterpart. The properties of 2'-O-alkyl-NPS constructs make them attractive candidates as ASO suitable for further evaluation and development.


Subject(s)
Oligonucleotides, Antisense , Oligonucleotides , Oligonucleotides/pharmacology , Oligonucleotides/chemistry , Oligonucleotides, Antisense/genetics , Oligonucleotides, Antisense/pharmacology , Phosphoric Acids/pharmacology , Phosphoric Acids/chemistry , Amides/pharmacology , Amides/chemistry
12.
Int J Biol Macromol ; 243: 125119, 2023 Jul 15.
Article in English | MEDLINE | ID: mdl-37263332

ABSTRACT

Phosphoric acid has been utilized as a favorable alternative to strong acids for the production of cellulose nanospheres (CNS) in recent years, partly owing to the reduced reliance on mechanical assistance. In the present study, phosphoric acid hydrolysis was applied to synthesize CNS from natural cotton pulp. Compared to reported long-time hydrolysis over 12 h, reduced time of 4 h is achieved for CNS production. Particle size from 530 nm to 1.3 µm was further controlled by changing the hydrolysis time in 4-11 h. Powdered sample was obtained after freeze-drying. CNS prepared in this work exhibits a cellulose II structure. Crystallinity index of the samples locates in 70-75 % which is higher than the reported 43-60 % for the acid-hydrolyzed medical cotton. Moreover, compared to the sulphuric-acid hydrolyzed CNS with higher crystallinity, thermal stability of the CNS generated from phosphoric-acid hydrolysis is significantly greater. A cooperative dissolution-regeneration and degradation is proposed to induce CNS self-assembly. Initial cellulose microfibrils are completely dissolved as exposed to phosphoric acid. Partial chains aggregate as a result while the remaining chains assemble onto the aggregates in a layer-by-layer manner. Acid degradation to cellulose with time affects length of the molecular chains. CNS size is controlled accordingly.


Subject(s)
Nanoparticles , Nanospheres , Cellulose/chemistry , Solubility , Phosphoric Acids/chemistry , Hydrolysis , Nanoparticles/chemistry
13.
J Adhes Dent ; 25(1): 71-78, 2023 Mar 20.
Article in English | MEDLINE | ID: mdl-36939646

ABSTRACT

PURPOSE: To evaluate the effects of etching mode (self-etch and etch-and-rinse) on acid-base resistant zone (ABRZ) formation at the resin cement/enamel interface and enamel etching pattern, as well as the effects of thermocycling (0, 5000, and 10,000 cycles) on the enamel microshear bond strength (µSBS) mediated by dual-cure resin cements (DCRC). MATERIALS AND METHODS: Two DCRC were used in 4 groups: Panavia V5 in self-etch (V5NE) and etch-and-rinse mode (V5E); and Estecem II in self-etch (ENE) and etch-and-rinse mode (EE). For ABRZ observation, the bonded interface was subjected to a demineralizing solution. The morphological attributes of the interface and etching patterns were observed using FE-SEM. For µ-SBS, cylinders with a 0.79-mm internal diameter and 0.5-mm height were made with DCRC and tested in shear after 0, 5000, and 10,000 thermal cycles (TC) (5°C and 55°C) (n = 10). RESULTS: The formation of an enamel ABRZ was observed in all groups with different morphological features between self-etch and etch-and-rinse groups. A funnel-shaped erosion beneath the interface was present using V5NE and ENE modes where enamel was dissolved, while ABRZ formation was confirmed and no funnel-shaped erosion was noticed using V5E and EE. No significant differences in µSBS were observed between resin cements. However, significantly lower µSBSs were recorded when the self-etching mode was used. Thermocycling resulted in a significant reduction in µSBS for all groups. CONCLUSION: Selective enamel etching should be recommended to improve the interfacial quality when dual-cure resin luting cements are used.


Subject(s)
Dental Bonding , Resin Cements , Resin Cements/chemistry , Acid Etching, Dental/methods , Dental Bonding/methods , Dental Enamel , Phosphoric Acids/chemistry , Materials Testing , Shear Strength , Dentin-Bonding Agents/chemistry
14.
Chemistry ; 29(2): e202202953, 2023 Jan 09.
Article in English | MEDLINE | ID: mdl-36161384

ABSTRACT

The linking of phosphoric acids via covalent or mechanical bonds has proven to be a successful strategy for the design of novel organocatalysts. Here, we present the first systematic investigation of singly-linked and macrocyclic bisphosphoric acids, including their synthesis and their application in phase-transfer and Brønsted acid catalysis. We found that the novel bisphosphoric acids show dramatically increased enantioselectivities in comparison to their monophosphoric acid analogues. However, the nature, length and number of linkers has a profound influence on the enantioselectivities. In the asymmetric dearomative fluorination via phase-transfer catalysis, bisphosphoric acids with a single, rigid bisalkyne-linker give the best results with moderate to good enantiomeric excesses. In contrast, bisphosphoric acids with flexible linkers give excellent enantioselectivities in the transfer-hydrogenation of quinolines via cooperative Brønsted acid catalysis. In the latter case, sufficiently long linkers are needed for high stereoselectivities, as found experimentally and supported by DFT calculations.


Subject(s)
Phosphoric Acids , Phosphoric Acids/chemistry , Hydrogenation , Catalysis , Stereoisomerism
15.
Acc Chem Res ; 55(20): 2920-2937, 2022 10 18.
Article in English | MEDLINE | ID: mdl-36177502

ABSTRACT

The growing importance of axially chiral architectures in different scientific domains has unveiled shortcomings in terms of efficient synthetic access and skeletal variety. This account describes our strategies in answering these challenges within the organocatalytic context where the emergence of bifunctional catalysts such as chiral phosphoric acids (CPAs) has proven invaluable in controlling the sense of axial chirality. The wide occurrence of bi(hetero)aryl skeletons in privileged structures constitutes a strong motivation to devise more effective arylation methods. Our design revolves around modulating the intrinsic nucleophilicity of aromatic amines and alcohols. The first approach involves the design of an electron-withdrawing activating group which could associate with the catalyst for reactivity enhancement and selectivity control. The resonance of arenes offers the unique mechanistic possibility to select between activating sites. C2-Azo- and nitroso-substituted naphthalenes undergo atroposelective ortho C- or N-arylation with (hetero)aromatic nucleophiles. For monocyclic benzenes, programmable charge localization leads to regioselective activation by catalytic control alone or aided by substrate design. For instance, selective addition to nitroso nitrogen enables successive annulation initiated by the amine to yield axially chiral N-arylbenzimidazoles. In a biomimetic manner, a finely tuned catalyst could direct a para-selective nucleophilic approach in the atroposelective arylation of azobenzenes. The second strategy employs electrophilic arene precursors for arylation which occurs via rearomatization with central-to-axial chirality transfer. This enabled the arylation of (imino)quinones with indoles to access phenylindole atropisomers. By adapting this chemistry with an additional oxidation event to liberate the carbonyl functionalities, aryl-o-naphthoquinone and aryl-p-quinone atropisomers were attained. Along with the development of new arylation strategies, deriving new axially chiral structures has been another consistent theme of our research program. The atroposelective functionalization of alkynes provides broad entry to atropisomeric alkenes. The monofunctionalization of alkynes through the interception of an electrophilic vinylidene-quinone-methide (VQM) intermediate with 2-naphthols yielded the new EBINOL scaffolds. By designing an internal directing group, the atroposelective dihalogenation of alkynes was realized using abundant alkali halides despite their weak nucleophilicities and poor solubilities. The atroposelective N-alkylation of alkenes was pursued to prepare multifunctionalized alkene atropisomers that could be converted into 2-arylpyrroles with chirality transfer. The synthesis of B-aryl-1,2-azaborines containing a C-B chiral axis was accomplished where the CPA catalyst effects the desymmetrization and defines the configuration of the distal C-B bond. Inspired by the axially chiral scaffold of allenes, we leveraged the developed arene activation strategy to achieve para-addition and dearomatization of judiciously designed azobenzenes, which led to structurally novel cyclohexadienylidene-based hydrazones. To complement these structures, axially chiral cyclohexadienyl oxime ethers were also attained through CPA-catalyzed condensation between hydroxylamines and spiro[4.5]trienones.


Subject(s)
Naphthalenes , Naphthols , Alkalies , Alkenes , Alkynes , Amines/chemistry , Benzoquinones , Ethers , Hydrazones , Hydroxylamines , Indoles , Naphthalenes/chemistry , Naphthols/chemistry , Nitrogen , Oximes , Phosphoric Acids/chemistry , Quinones/chemistry , Skeleton , Stereoisomerism
16.
Org Lett ; 24(38): 6968-6972, 2022 09 30.
Article in English | MEDLINE | ID: mdl-36107734

ABSTRACT

We report a general and scalable method for the synthesis of all-meta-trisubstituted benzenes from readily available 3,5-disubstituted catechols. Oxidation and [4 + 2] cycloaddition with acetylene dienophiles generate a bicyclo[2.2.2]octane structure that is doubly decarbonylated initiated by blue-light irradiation, leading to a meta,meta-disubstitution pattern on the re-aromatized system. This enables this substitution pattern even with very bulky alkyl groups (deemed excellent dispersion energy donors) to be incorporated into, for example, chiral phosphoric acid catalysts.


Subject(s)
Benzene , Octanes , Acetylene/chemistry , Benzene/chemistry , Catalysis , Catechols/chemistry , Octanes/chemistry , Phosphoric Acids/chemistry
17.
J Am Chem Soc ; 144(33): 15266-15274, 2022 08 24.
Article in English | MEDLINE | ID: mdl-35953065

ABSTRACT

A growing number of out-of-equilibrium systems have been created and investigated in chemical laboratories over the past decade. One way to achieve this is to create a reaction cycle, in which the forward reaction is driven by a chemical fuel and the backward reaction follows a different pathway. Such dissipative reaction networks are still relatively rare, however, and most non-enzymatic examples are based on the carbodiimide-driven generation of carboxylic acid anhydrides. In this work, we describe a dissipative reaction network that comprises the chemically fueled formation of phosphoramidates from natural ribonucleotides (e.g., GMP or AMP) and phosphoramidate hydrolysis as a mild backward reaction. Because the individual reactions are subject to a multitude of interconnected parameters, the software-assisted tool "Design of Experiments" (DoE) was a great asset for optimizing and understanding the network. One notable insight was the stark effect of the nucleophilic catalyst 1-ethylimidazole (EtIm) on the hydrolysis rate, which is reminiscent of the action of the histidine group in phosphoramidase enzymes (e.g., HINT1). We were also able to use the reaction cycle to generate transient self-assemblies, which were characterized by dynamic light scattering (DLS), confocal microscopy (CLSM), and cryogenic transmission electron microscopy (cryo-TEM). Because these compartments are based on prebiotically plausible building blocks, our findings may have relevance for origin-of-life scenarios.


Subject(s)
Phosphoric Acids , Ribonucleotides , Amides/chemistry , Computer-Aided Design , Phosphoric Acids/chemistry
18.
J Contemp Dent Pract ; 23(2): 181-185, 2022 Feb 01.
Article in English | MEDLINE | ID: mdl-35748447

ABSTRACT

AIM: To evaluate the pH and degree of surface roughness caused by five commercially and readily available etchants on tooth enamel. MATERIALS AND METHODS: Five different etchants were chosen. An electric pH meter was utilized to test the pH of the etchants employed. Fifteen maxillary bicuspids that had been extracted were cleansed and stored in thymol solution. The samples were sorted into five groups of three each. A noncontact profilometer was employed to assess the microsurface changes of the pre-etched enamel. The teeth were then etched for 30 seconds with respect to the group to which they belonged before being cleaned and dried. The surface roughness after etching was analyzed, measured and values were tabulated. Descriptive statistics and paired t-test were done. RESULTS: The pH of the etchants and surface roughness of the enamel are varied across the five groups, though they have the same composition of 37% orthophosphoric acid. Etchant from Group C was found to be most acidic while the one manufactured by Group E was least acidic. Ivoclar, DPI, and DTECH showed a statistically significant value in surface roughness parameter post-etching (p <0.05). A statistical difference that was significant was observed with the Kruskal-Wallis test for surface roughness parameter (p <0.05). CONCLUSION: All five etchants had varied pH and the amount of surface roughness was also varied though the composition was the same. Further elemental analysis of these etchants has to be done to validate the results obtained. CLINICAL SIGNIFICANCE: Etchants of the same composition should ideally produce the same effect on the tooth enamel surface, but etchants from different manufacturers produce different levels of surface roughness which could be due to differences in the composition of the prepared etchant. The study was conducted to assist in making an educated selection about the most cost-effective but efficient etchant for clinical application.


Subject(s)
Acid Etching, Dental , Dental Bonding , Acid Etching, Dental/methods , Dental Bonding/methods , Dental Enamel , Hydrogen-Ion Concentration , Phosphoric Acids/chemistry , Surface Properties
19.
J Oleo Sci ; 71(2): 177-185, 2022.
Article in English | MEDLINE | ID: mdl-35110462

ABSTRACT

Phosphoric acid is used in the refining of palm oil for the removal of phosphatides. The high concentration of phosphorus in solvent extracted palm-pressed mesocarp fiber oil hinders palm oil mills to recover this phytonutrients-rich residual oil in pressed fiber which typically contains 0.1 to 0.2% of total oil yield. This study aimed to refine the palm-pressed mesocarp fiber oil and determine the optimum dosage of phosphoric acid for acid-degumming of palm-pressed mesocarp fiber oil while retaining its phytonutrients. The refining process was carried out with combination of wet degumming, acid degumming, neutralisation, bleaching and deodorization. The optimum dose of phosphoric acid was identified as 0.05 wt.% by incorporating the wet degumming process. The refined palm-pressed mesocarp fiber oil showed a reduction in phosphorus content by 97% (from 901 ppm to 20 ppm) and 97% free fatty acid content removal (from 6.36% to 0.17%), while the Deterioration of Bleachability Index increased from 1.76 to 2.48, which showed an increment of 41%. The refined oil retained the key phytonutrients such as carotenoids (1,150 ppm) and vitamin E (1,540 ppm) that can be further developed into high-value products. The oil meets the quality specification of refined, bleached, and deodorized palm oil while preserving the heat-sensitive phytonutrients, which in turn provides a new resource of nutritious oil.


Subject(s)
Food Handling/methods , Liquid-Liquid Extraction/methods , Palm Oil/chemistry , Phospholipids/isolation & purification , Phosphorus/isolation & purification , Phytochemicals/analysis , Carotenoids/analysis , Food Quality , Palm Oil/analysis , Phospholipids/analysis , Phosphoric Acids/chemistry , Phosphorus/analysis , Solvents , Vitamin E/analysis
20.
Molecules ; 27(1)2022 Jan 02.
Article in English | MEDLINE | ID: mdl-35011500

ABSTRACT

Developing an ideal and cheap adsorbent for adsorbing heavy metals from aqueous solution has been urgently need. In this study, a novel, effective and low-cost method was developed to prepare the biochar from lettuce waste with H3PO4 as an acidic activation agent at a low-temperature (circa 200 °C) hydrothermal carbonization process. A batch adsorption experiment demonstrated that the biochar reaches the adsorption equilibrium within 30 min, and the optimal adsorption capacity of Cd(II) is 195.8 mg∙g-1 at solution pH 6.0, which is significantly improved from circa 20.5 mg∙g-1 of the original biochar without activator. The fitting results of the prepared biochar adsorption data conform to the pseudo-second-order kinetic model (PSO) and the Sips isotherm model, and the Cd(II) adsorption is a spontaneous and exothermic process. The hypothetical adsorption mechanism is mainly composed of ion exchange, electrostatic attraction, and surface complexation. This work offers a novel and low-temperature strategy to produce cheap and promising carbon-based adsorbents from organic vegetation wastes for removing heavy metals in aquatic environment efficiently.


Subject(s)
Cadmium/chemistry , Charcoal/chemistry , Lactuca/chemistry , Water Pollutants, Chemical/chemistry , Water Purification , Phosphoric Acids/chemistry
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