A Phosphoramidate Prodrug Platform: One-Pot Amine Functionalization of Kinase Inhibitors with Oligoethylene Glycol for Improved Water-Solubility.

Small molecular kinase inhibitors play a key role in modern cancer therapy. Protein kinases are essential mediators in the growth and progression of cancerous tumors, rendering involved kinases an increasingly important target for therapy. However, kinase inhibitors are almost insoluble in water because of their hydrophobic aromatic nature, often lowering their availability and pharmacological efficacy. Direct drug functionalization with polar groups represents a simple strategy to improve the drug solubility, availability, and performance. Here, we present a strategy to functionalize secondary amines with oligoethylene glycol (OEG) phosphate using a one-pot synthesis in three exemplary kinase inhibiting drugs Ceritinib, Crizotinib, and Palbociclib. These OEG-prodrug conjugates demonstrate superior solubility in water compared to the native drugs, with the solubility increasing up to 190-fold. The kinase inhibition potential is only slightly decreased for the conjugates compared to the native drugs. We further show pH dependent hydrolysis of the OEG-prodrugs which releases the native drug. We observe a slow release at pH 3, while the conjugates remain stable over 96 h under physiological conditions (pH 7.4). Using confocal microscopy, we verify improved cell uptake of the drug-OEG conjugates into the cytoplasm of HeLa cells, further supporting our universal solubility approach.

Aspects of glass and hybridization protocols for bonding of fiber posts to root dentine.

This study evaluated bond strength of glass fiber posts to root dentin using push-out (PO) and diametral compression (DC), testing glycolic acid as a conditioner and varying dentin moisture. An additional aim was to test whether DC can be an alternative test to PO for bond strength assessment. Eighty bovine teeth were divided into eight groups (n = 10) defined by the use of either 37% glycolic acid or 37% phosphoric acid (PA) on moist or wet dentin before bonding with either Adapter SingleBond/RelyX ARC or One Step Plus/Duo-Link Bisco. Each tooth provided discs with an internal diameter of 2 mm, external diameter of 5 mm, and height of 2 mm, which underwent PO and DC. Finite element analysis (FEA) was carried out on 3D models. When analyzing PO results through linear regression, the highest values of bond strength were observed using glycolic acid on wet dentin in the cervical and middle thirds of the teeth. Analyzing DC results, the only statistical influence on values was the dental thirds. The scatterplot of the DC results and the PO bond strength values indicated no relationship between the results of the two tests (r = 0.03; p = 0.64). PO test detected more sensitive changes in bond strength values than DC.

Effects of sodium copper- and sodium iron-chlorophyllin primers on resin bonding to dentin.

This study evaluated the effects of two chlorophyll derivatives, sodium copper chlorophyllin (Cu-Chl) and sodium iron chlorophyllin (Fe-Chl), on the bond strength between a self-curing luting agent (4-META/MMA-TBB resin) and dentin. Five aqueous primers containing 35% 2-hydroxyethylmethacrylate with 0.007% Cu-Chl, 0.07% Cu-Chl, 0.007% Fe-Chl, 0.07% Fe-Chl, or neither Cu-Chl nor Fe-Chl (no-Chl) were prepared. The extracted human dentin surfaces were etched with 10% phosphoric acid (10PA), primed, and bonded to a resin block using the 4-META/MMA-TBB resin. A conventional etching agent (10-3) and 10PA without primer (PA/no-primer) were used as controls. The microtensile bond strength was determined after 48 h. The arithmetic medians for 20 stick specimens were calculated and statistically analyzed using a nonparametric Steel-Dwass test (α = 0.05). The maximum bond strength was achieved in the 0.007% Cu-Chl group, followed by those in the 0.07% Cu-Chl, 0.07% Fe-Chl, 10-3, 0.007% Fe-Chl, no-Chl, and PA/no-primer groups. No significant difference was observed between 0.007% Fe-Chl, 0.07% Fe-Chl, and 10-3. The bond strength to dentin etched with 10PA was influenced by the type and concentration of the chlorophyll derivatives applied. Cu-Chl rather than Fe-Chl should be useful as a component of surface treatment agents for bonding 4-META/MMA-TBB resin to dentin.

Impact of acid and laser etching of enamel on microleakage in different adhesive systems.

This study aimed to evaluate the microleakage of light-cured and self-cured adhesives on enamel surfaces selectively etched with Er, Cr: YSGG laser or 35% phosphoric acid. A total of 60 class V cavities were prepared 1 mm above the cemento-enamel junction (CEJ). The specimens were randomly divided into six groups. Group 1: Clearfil SE Bond with no conditioning, Group 2: Tokuyama Universal Bond with no conditioning, Group 3: Clearfil SE Bond conditioned with 35% phosphoric acid, Group 4: Tokuyama Universal Bond conditioned with 35% phosphoric acid, Group 5: Clearfil SE Bond conditioned with Er, Cr: YSGG laser and Group 6: Tokuyama Universal Bond conditioned with Er, Cr: YSGG laser. Microleakage was evaluated qualitatively (visually) and quantitatively (ImageJ). The data were analyzed using IBM SPSS V23 and submitted to Kruskal-Wallis and Wilcoxon tests. The significance level was set at p < 0.05. In all evaluation methods, the microleakage scores exhibit significant differences (p*<0.001). Group 1 and Group 3 exhibited similar and lower microleakage values than the Group 5. In the occlusal margin, the microleakage values were similar in Group 2, Group 4, and Group 6, whereas in the gingival margin Group 4 showed significantly lower leakage compared to Group 2. Regardless of the etching protocols and adhesive systems used, less microleakage was observed on the occlusal surface than on the gingival surface. Phosphoric acid etching provides better results than laser etching for enamel surface treatment on both occlusal and gingival surfaces.

Effects of different primers and colouring solutions on orthodontic bonding: shear bond strength and colour change.

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.

Effects of different surface treatments on surface topography and bond strength in the repair of fiber-reinforced dentin composite.

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.

Effect of phosphoric acid containing polyvinylpyrrolidone as protective etchant for dentin bonding.

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.

Corrosion-induced changes in surface properties and roughness of orthodontic wires.

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.

EFFECTS OF ACID ETCHING ON COLOR CHANGES AND SURFACE MORPHOLOGY OF ENAMEL TO BE BLEACHED WITH DIFFERENT TECHNIQUES.

Aims - to compare the color changes, the surface roughness and morphology of the enamel bleached with two different bleaching solutions (chemical and laser activated), preceded or not with acid etching. Thirty teeth of bovine prepared and haphazardly assigned to 2 groups (n=15) depending on bleaching technique. Each group subdivided to 3 subgroup (n=5) consistent with acid etching by 37% phosphoric acid. Atomic force microscopy and VITA easy shade spectrophotometer were performed twice for all the specimens before and after bleaching. ANOVA, the Paired sample t-test, and the independent sample t-test used for statistical analysis. As for the color changes, the groups that were bleached by the chemical method, the difference among the three subgroups was statistically significant. This also applies to the groups bleached with the laser method. When comparing the results of the chemical bleaching subgroups with the laser bleaching ones, the difference was not significant. Roughness results showed significant differences between certain subgroups and non-significant differences among others. However, the difference was statistically significant between the chemical and laser groups, laser technique resulted in less surface roughness than the chemical one. Acid etching before bleaching produced better colour change in both the chemical and laser assisted bleaching. In chemical bleaching, surface roughness was higher when acid etching was used. This was also true for laser bleaching technique. In general, laser assisted bleaching produced less surface roughness than chemical bleaching.

Formulating an altered dentin substrate to improve dentin bonding.

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.

Comparative Assessment of pH and Degree of Surface Roughness of Enamel When Etched with Five Commercially Available Etchants: An In Vitro Study.

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.

Poly (N-vinylpyrrolidone) modification mitigates plasma protein corona formation on phosphomolybdate-based nanoparticles.

Phosphomolybdate-based nanoparticles (PMo12-based NPs) have been commonly applied in nanomedicine. However, upon contact with biofluids, proteins are quickly adsorbed onto the NPs surface to form a protein corona, which induces the opsonization and facilitates the rapid clearance of the NPs by macrophage uptake. Herein, we introduce a family of structurally homologous PMo12-based NPs (CDS-PMo12@PVPx(x = 0 ~ 1) NPs) capping diverse content of zwitterionic polymer poly (N-vinylpyrrolidone) (PVP) to regulate the protein corona formation on PMo12-based NPs. The fluorescence quenching data indicate that the introduction of PVP effectively reduces the number of binding sites of proteins on PMo12-based NPs. Molecular docking simulations results show that the contact surface area and binding energy of proteins to CDS-PMo12@PVP1 NPs are smaller than the CDS-PMo12@PVP0 NPs. The liquid chromatography-tandem mass spectrometry (LC-MS/MS) is further applied to analyze and quantify the compositions of the human plasma corona formation on CDS-PMo12@PVPx(x = 0 ~ 1) NPs. The number of plasma protein groups adsorption on CDS-PMo12@PVP1 NPs, compared to CDS-PMo12@PVP0 NPs, decreases from 372 to 271. In addition, 76 differentially adsorption proteins are identified between CDS-PMo12@PVP0 and CDS-PMo12@PVP1 NPs, in which apolipoprotein is up-regulated in CDS-PMo12@PVP1 NPs. The apolipoprotein adsorption onto the NPs is proposed to have dysoponic activity and enhance the circulation time of NPs. Our findings demonstrate that PVP grafting on PMo12-based NPs is a promising strategy to improve the anti-biofouling property for PMo12-based nanodrug design.

Evaluation of bond strength of resin cement to Er:YAG laser-etched enamel and dentin after cementation of ceramic discs.

The purpose of this study was to investigate the shear bond strength (SBS) of ceramic discs luted to differently etched enamel and dentin surfaces. Occlusal surfaces of 64 carious-free human molars and vestibule surfaces of 64 first maxillary incisors were ground to get flat superficial dentin and flattened enamel respectively. After generating 4 groups according to the surface etching method (37% orthophosphoric acid, Er:YAG laser-contact handpiece/scanning handpiece (1 or 2 times of scanning)), ceramic discs were luted to the surfaces with adhesive resin cement (Variolink N, Vivadent Ets., Schaan/Liechtenstein). After etching and cementation, thermocycling of 5000 cycles (Sd Mechatronik Gmbh, Feldkirchen-Westerham, Germany) and SBS test (Servopulser EHFFD1; Shimadzu, Kyoto, Japan) were performed respectively. The surface morphologies of 2 specimens, etched enamel and dentin, prepared for each group were examined with SEM analysis. Failure modes were determined under a USB digital microscope. Data were analyzed with one-way analysis of variance (ANOVA) and Tukey HSD test (α = 0.05). SBS values in dentin surfaces showed statistically significant differences (p < 0.05) among tested groups. The highest SBS among dentin groups was determined in the group which had 2 times etching by Er:YAG laser (11.42 MPa) by a scanning handpiece. No statistical differences were observed in the other dentin or enamel groups. Laser etching seems to be a viable alternative to acid etching on both enamel and dentin surfaces while double etching of dentin with a scanning handpiece can improve the adhesion.

Moisture Resistance, Thermal Stability and Fire Behavior of Unsaturated Polyester Resin Modified with L-histidinium Dihydrogen Phosphate-Phosphoric Acid.

In this paper, the fire behavior of unsaturated polyester resin (UP) modified with L-histidinium dihydrogen phosphate-phosphoric acid (LHP), being a novel intumescent fire retardant (IFR), was investigated. Thermal and thermomechanical properties of the UP with different amounts of LHP (from 10 to 30 wt. %) were determined by thermogravimetric analysis (TG) as well as dynamic mechanical thermal analysis (DMTA). Reaction to small flames was studied by horizontal burning (HB) test, while fire behavior and smoke emission were investigated with the cone calorimeter (CC) and smoke density chamber. Further, the analysis of volatile products was conducted (TGA/FT-IR). It was observed that the addition of LHP resulted in the formation of carbonaceous char inhibiting the thermal decomposition, burning rate and smoke emission. The most promising results were obtained for the UP containing 30 wt. % of LHP, for which the highest reduction in maximum values of heat release rate (200 kW/m2) and total smoke release (3535 m2/m2) compared to unmodified polymer (792 kW/m2 and 6895 m2/m2) were recorded. However, some important disadvantage with respect to water resistance was observed.

A New Approach to Developing Long-Acting Injectable Formulations of Anti-HIV Drugs: Poly(Ethylene Phosphoric Acid) Block Copolymers Increase the Efficiency of Tenofovir against HIV-1 in MT-4 Cells.

Despite the world's combined efforts, human immunodeficiency virus (HIV), the causative agent of AIDS, remains one of the world's most serious public health challenges. High genetic variability of HIV complicates the development of anti-HIV vaccine, and there is an actual clinical need for increasing the efficiency of anti-HIV drugs in terms of targeted delivery and controlled release. Tenofovir (TFV), a nucleotide-analog reverse transcriptase inhibitor, has gained wide acceptance as a drug for pre-exposure prophylaxis or treatment of HIV infection. In our study, we explored the potential of tenofovir disoproxil (TFD) adducts with block copolymers of poly(ethylene glycol) monomethyl ether and poly(ethylene phosphoric acid) (mPEG-b-PEPA) as candidates for developing a long-acting/controlled-release formulation of TFV. Two types of mPEG-b-PEPA with numbers of ethylene phosphoric acid (EPA) fragments of 13 and 49 were synthesized by catalytic ring-opening polymerization, and used for preparing four types of adducts with TFD. Antiviral activity of [mPEG-b-PEPA]TFD or tenofovir disoproxil fumarate (TDF) was evaluated using the model of experimental HIV infection in vitro (MT-4/HIV-1IIIB). Judging by the values of the selectivity index (SI), TFD exhibited an up to 14-fold higher anti-HIV activity in the form of mPEG-b-PEPA adducts, thus demonstrating significant promise for further development of long-acting/controlled-release injectable TFV formulations.

Polymer-Supported Phosphoric, Phosphonic and Phosphinic Acids-From Synthesis to Properties and Applications in Separation Processes.

Efficient separation technologies are crucial to the environment and world economy. The challenge posed to scientists is how to engineer selectivity towards a targeted substrate, especially from multicomponent solutions. Polymer-supported reagents have gained a lot of attention in this context, as they eliminate a lot of inconveniences concerning widely used solvent extraction techniques. Nevertheless, the choice of an appropriate ligand for immobilization may be derived from the behavior of soluble compounds under solvent extraction conditions. Organophosphorus compounds play a significant role in separation science and technology. The features they possess, such as variable oxidation states, multivalence, asymmetry and metal-binding properties, highlight their status as a unique and versatile class of compounds, capable of selective separations proceeding through different mechanisms. This review provides a detailed survey of polymers containing phosphoric, phosphonic and phosphinic acid functionalities in the side chain and covers main advances in the preparation and application of these materials in separation science, including the most relevant synthesis routes (Arbuzov, Perkow, Mannich, Kabachnik-Fields reactions, etc.), as well as the main stages in the development of organophosphorus resins and the most important achievements in the field.

Chemical fixation of toxic metals in stainless steel pickling residue by Na2S∙xH2O, FeSO4∙6H2O and phosphoric acid for beneficial uses.

The leaching concentrations of different metals in stainless steel pickling residue (SSPR) were determined and the toxic metals were treated using Na2S∙xH2O, FeSO4∙6H2O, and phosphoric acid. A modified European Community Bureau of Reference (BCR) sequential extraction was used to identify the speciation of the concerned metals. Results showed that SSPR contains a large amount of Ca (58.41%), Fe (29.44%), Cr (3.83%), Ni (2.94%), Mn (2.82%) and some of Al, Cu, Mg, Zn. Among them, Cr and Ni were the most toxic metals in SSPR, thus the raw SSPR falls into hazardous waste category due to the leaching amount of Cr. In addition, the leached Cr was identified as Cr6+ (MgCrO4) in the waste. BCR test revealed that risk assessment code (RAC) of Cr and Ni were 33.29% and 61.7%, indicating they posed "high" and "very high" risk to the environment, respectively. After fixing by Na2S∙xH2O and FeSO4∙6H2O, the leaching concentrations of Cr and Ni were less than 1.5 and 0.5 mg/L, respectively. After fixing by Na2S∙xH2O and FeSO4∙6H2O the treated SSPR can be safely reused as roadbed materials, concrete and cement aggregates. This study provides a useful implication in treatment and beneficial reuse of heavy metal-containing hazardous wastes.

Effect of laser application on microtensile bond strength of an orthodontic adhesive to water-aged composite.

AIM: This study evaluated the microtensile bond strength (MTBS) of an orthodontic adhesive to water-aged composite surfaces using different surface treatments. SUBJECTS AND METHODS: Twelve composite blocks (10 mm × 10 mm × 5 mm) were fabricated and randomly divided into two groups. Half of the specimens were stored in distilled water for 1 day, and the other specimens were stored for 30 days. The specimens were randomly assigned to six groups according to surface treatments (n = 15): Group 1, control (no treatment); Group 2, phosphoric acid; Group 3, diamond bur; Group 4, diamond bur + phosphoric acid; Group 5, laser; and Group 6, laser + phosphoric acid. One coat of orthodontic adhesive was bonded to one surface of composite blocks, and a microhybrid composite resin was bonded to the surfaces via a Teflon mold. Bond strength was evaluated using an MTBS test. Surface topography was evaluated using scanning electron microscopy (SEM) analysis. The data were analyzed using one-way analysis of variance, Tamhane post-hoc test, and independent sample t-tests (P < 0.05). RESULTS: Bond strength values tended to decrease in all groups (with the exception of Group 2) after storage in water for 30 days (P < 0.05). Laser and diamond bur application (with or without phosphoric acid) enhanced the bond strength. CONCLUSIONS: An Er,Cr:YSGG laser application may be a feasible alternative to diamond bur for enhancing the bond strength of orthodontic adhesive to composite resin.

The Chemical Likelihood of Ribonucleotide-α-Amino acid Copolymers as Players for Early Stages of Evolution.

How ribosomal translation could have evolved remains an open question in most available scenarios for the early developments of life. Rather than considering RNA and peptides as two independent systems, this work is aimed at assessing the possibility of formation and stability of co-polymers or co-oligomers of α-amino acids and nucleotides from which translation might have evolved. Here we show that the linkages required to build such mixed structures have lifetimes of several weeks to months at neutral pH and 20 °C owing to the mutual protecting effect of both neighboring phosphoramidate and ester functional groups increasing their stability by factors of about 1 and 3 orders of magnitude, respectively. This protecting effect is reversible upon hydrolysis allowing the possibility of subsequent reactions. These copolymer models, for which an abiotic synthesis pathway is supported by experiments, form a basis from which both polymerization and translation could have logically evolved. Low temperatures were identified as a critical parameter for the kinetic stability of the aminoacylated nucleotide facilitating the synthesis of the model. This observation independently supports the views that any process involving RNA aminoacyl esters, outstandingly including the emergence of translation, was more probable at 0 °C or below and might be considered a kinetic marker constraining the environment in which translation has evolved.

Phosphoramitoids-A submonomer approach to sequence defined N-substituted phosphoramidate polymers.

There is a growing interest in new methods to generate bio-inspired, chemically diverse, sequence-defined synthetic polymers. Solid-phase submonomer approaches offer facile access to these types of materials, since they take advantage of readily available synthons. Submonomer approaches to date have been applied to peptidomimetics with oligo-amide backbones. Here we extend the approach to a phosphorous-containing backbone, where N-substituted phosphoramidate oligomers are constructed from a set of amine submonomers, diphenyl H-phosphonate, and cyclohexane diol. The key chemical steps in chain elongation are a chain extension reaction based on H-phosphonate (P III) chemistry, and a side chain attachment step based on the Atherton-Todd reaction. Cheap, stable chemical reagents are used without heating, all reaction times are 30 minutes or less and open to air, and no main-chain protecting groups are required. Phosphoramitoid tetramers and pentamers displaying a variety of side chain functionalities were synthesized by a three-step solid-phase submonomer method, typically with >85% crude purities.