Material extrusion of thermoplastic acrylic for intraoral devices: Technical feasibility and evaluation.

With global demand for 3D printed medical devices on the rise, the search for safer, inexpensive, and sustainable methods is timely. Herein, we assessed the practicality of the material extrusion process for acrylic denture bases of which successful outcomes can be extended to implant surgical guides, orthodontic splints, impression trays, record bases and obturators for cleft palates or other maxillary defects. Representative materials comprising denture prototypes and test samples were designed and built with in-house polymethylmethacrylate filaments using varying print directions (PDs), layer heights (LHs) and reinforcements (RFs) with short glass fiber. The study undertook a comprehensive evaluation of the materials to determine their flexural, fracture, and thermal properties. Additional analyses for tensile and compressive properties, chemical composition, residual monomer, and surface roughness (Ra) were completed for parts with optimum parameters. Micrographic analysis of the acrylic composites revealed adequate fiber-matrix compatibility and predictably, their mechanical properties improved simultaneously with RFs and decreased LHs. Fiber reinforcement also improved the overall thermal conductivity of the materials. Ra, on the other hand, improved visibly with decreased RFs and LHs and the prototypes were effortlessly polished and characterized with veneering composites to mimic gingival tissues. In terms of chemical stability, the residual methyl methacrylate monomer contents are well below standards threshold for biological reactions. Notably, 5 vol% acrylic composites built with 0.05 mm LH in 0° on z-axis produced optimum properties that are superior to those of conventional acrylic, milled acrylic and 3D printed photopolymers. Finite element modeling successfully replicated the tensile properties of the prototypes. It may well be argued that the material extrusion process is cost-effective; however, the speed of manufacturing could be longer than that of established methods. Although the mean Ra is within an acceptable range, mandatory manual finishing and aesthetic pigmentation are required for long-term intraoral use. At a proof-of-concept level, it is evident that the material extrusion process can be applied to build inexpensive, safe, and robust thermoplastic acrylic devices. The broad outcomes of this novel study are equally worthy of academic reflection, and further translation to the clinic.

Machine Learning-Based Void Percentage Analysis of Components Fabricated with the Low-Cost Metal Material Extrusion Process.

Additive manufacturing (AM) is a widely used layer-by-layer manufacturing process. Material extrusion (ME) is one of the most popular AM techniques. Lately, low-cost metal material extrusion (LCMME) technology is developed to perform metal ME to produce metallic parts with the ME technology. This technique is used to fabricate metallic parts after sintering the metal infused additively manufactured parts. Both AM and sintering process parameters will affect the quality of the final parts. It is evident that the sintered parts do not have the same mechanical properties as the pure metal parts fabricated by the traditional manufacturing processes. In this research, several machine learning algorithms are used to predict the size of the internal voids of the final parts based on the collected data. Additionally, the results show that the neural network (NN) is more accurate than the support vector regression (SVR) on prediction.

Nitroxide radicals appended to phthalonitriles: synthesis, structural characterization and photophysical properties.

The syntheses of 4-[4-(4,4,5,5-tetramethyl-2-imidazoline-3-oxide-1-oxyl-2-yl)phenoxy]phthalonitrile (3, C21H19N4O3) and 4-[4-(4,4,5,5-tetramethyl-2-imidazoline-1-oxyl-2-yl)phenoxy]phthalonitrile (4) were carried out by microwave-assisted nucleophilic aromatic substitution of 4-nitrophthalonitrile (2) by the pre-formed 2-(4-hydroxyphenyl)-4,4,5,5-tetramethyl-2-imidazoline-3-oxide-1-oxyl (1). Compounds 3 and 4 were characterized unambiguously by a rich array of analyses, such as melting point, FT-IR, MALDI-TOF MS, elemental analysis, UV-Vis, CV, EPR, magnetic measurements and single-crystal X-ray diffraction. Structural studies demonstrate that the C-H...X and C-X...π (X = O and N) interactions in the radical nitronyl nitroxide groups play an important role in the assembly of the crystal structures. Moreover, cyclic voltammetry analyses show that the phthalonitrile substituent retains the redox properties of the Ullman radicals.

Characterization of the Double Bond Conversion of Acrylic Resins for 3D Printing of Dental Prostheses.

Characterization of the double bond conversion of acrylic resins is considered critical in the evaluation of dental materials due to the propensity of end-use devices to accumulate residual monomer and degradation products that can cause local and systemic side effects in high doses. In this study, the authors examine two different acrylic-based photopolymers indicated for 3D printing of dental prostheses using Fourier transform infrared spectroscopy: a denture base material comprising ≥75% ethoxylated bisphenol A dimethacrylate, and a crown-and-bridge material composed of >60% proprietary methacrylic oligomer and 15%-25% 2-hydroxyethyl methacrylate. Infrared spectroscopy data showed a conversion rate (240 s) of 52.37 ± 1.05% for the former material and 45.36 ± 1.41% for the latter. Compared to traditional acrylic resins, both materials exhibited a considerably lower degree of conversion. With limited scientific data available on the clinical performance of 3D printing materials in general, additional evidence is needed to ascertain their in vivo performance in the long-term.

Effect of the Substitution Pattern (Peripheral vs Non-Peripheral) on the Spectroscopic, Electrochemical, and Magnetic Properties of Octahexylsulfanyl Copper Phthalocyanines.

In order to investigate the substitution position effect on the spectroscopic, electrochemical, and magnetic properties of copper phthalocyanines, a detailed structure-property analysis has been performed by examining two copper phthalocyanines that are octasubstituted by hexylsulfanyl chains respectively in the peripheral (Cu-P) and non-peripheral (Cu-NP) positions. Cu-NP showed a marked near-IR maximum absorption compared to Cu-P and, accordingly, a smaller HOMO-LUMO energy gap, calculated via the electrochemical results and simulations in the gas phase, as well as for Cu-NP from its crystallographic data. An electron-spin resonance (ESR) technique is used to extract the g values from the powder spectra that are taken at room temperature. The g values were determined to be g∥ = 2.160 and g⊥ = 2.045 for Cu-P and g∥ = 2.150 and g⊥ = 2.050 for Cu-NP. These values indicate that the paramagnetic copper center in both phthalocyanines has axial symmetry with a planar anisotropy ( g∥ > g⊥). The ESR spectra in solution could be obtained only for Cu-P. Curie law is used to fit the experimental data of the magnetic susceptibility versus temperature graphs, and the Curie constant ( C) and diamagnetic/temperature-independent paramagnetic (α) contributions are deduced as 0.37598 (0.39576) cm3·K/mol and -23 × 10-5 (25 × 10-5) cm3/mol respectively for Cu-P and Cu-NP. The room temperature magnetic moment value (1.70 µB) is close to the spin-only value (1.73 µB) for the peripheral complex, showing that there is no orbital contribution to µeff. In contrast, at room temperature, the value of the magnetic moment (1.77 µB) is above the spin-only value, showing an orbital contribution to the magnetic moment. Cu-NP's room temperature magnetic moment value is larger than the value for Cu-P, demonstrating that the orbital contribution to the magnetic moment depends upon the substituent position. The magnitudes of the effective magnetic moment values also support that both Cu-P and Cu-NP complexes have square-planar coordination. This result is consistent with the determined g values. The spin densities were determined experimentally, and the results suggest that the positions of the substituents affect these values (0.469 for Cu-P and 0.490 for Cu-NP).

Revisiting the Ullman's Radical Chemistry for Phthalocyanine Derivatives.

Phthalocyanine derivatives do not cease to gain attention due to their numerous properties and applications (e.g., sensor, PDT). This makes them a unique scaffold for the design of new material. In this context, we were interested to develop the synthesis of an imino nitroxide-substituted phthalocyanine by Ullman's procedure; a challenge due to the intrinsic low solubility of most phthalocyanine derivative in much solvents. To overcome this solubility problem, we designed a phthalocyanine with bulky neopentyl substituents in peripheral positions as counterpart to the imino nitroxide moieties. The imino nitroxide-substituted phthalocyanine was obtained by condensation of a monoformyl-substituted phthalocyanine with 2,3-bis(hydroxylamino)-2,3-dimethylbutane in refluxing THF-MeOH (2:1) mixture in the presence of p-toluenesulfonic acid monohydrate, follow by oxidation with PbO2 . Characterization was performed by electrochemistry, UV/Vis and EPR spectroscopy in solution as well as SQUID in solid state.

Structure-Photoproperties Relationship Investigation of the Singlet Oxygen Formation in Porphyrin-Fullerene Dyads.

A systematic structure-photoproperties relationship study of the interactions of porphyrin-fullerene dyads with molecular oxygen was conducted on a set of three porphyrin-fullerene dyads, as this approach of related applications - oxygen sensitivity and photo-induced singlet oxygen generation - of such dyads remained to be endeavoured. To promote energy transfers between the porphyrin and fullerene units and limit undesired charge separation, a particular attention was devoted to the choice of the solvents for the photoproperties determination. Toluene, in which in addition the compounds investigated are not aggregated, was selected accordingly. The molecular orbital levels and energy gaps of the dyads were determined by electrochemistry and theoretical calculations. Their ground state absorption, steady-state fluorescence-based oxygen sensitivity and photo-induced singlet oxygen generation were determined. The dyads were designed to benefit from a facilitated synthetic porphyrin-fullerene coupling thanks to an easy access to formyl-functionalized porphyrins. The effect of two structural parameters was investigated: the presence of electron-donating hexyloxy chains at the para position of the meso-phenyl, and the presence of a phenylacetylene spacer. This latest factor appeared to have the most predominant effect on all these properties.

Synthetic Access to a Pure Polyradical Architecture: Nucleophilic Insertion of Nitronyl Nitroxide on a Cyclotriphosphazene Scaffold.

An optimized nucleophilic synthetic approach featuring mild conditions and microwave energy was utilized to circumvent the classical Ullman procedure and access a polynitronyl nitroxide radical easily and in pure form. The simultaneous controlled introduction of preformed nitronyl nitroxide radicals on a cyclotriphosphazene core leads to a novel polyphosphazene monomer which is suitable for both n- and a p-type redox-active material in organic rechargeable batteries as demonstrated by electrochemistry. Additionally, absorption spectra and square-wave voltammetry were utilized to quantify the number of nitronyl nitroxide radical units on the cyclotriphosphazene scaffold.

Synthesis and Straightforward Quantification Methods of Imino Nitroxide-Based Hexaradical Architecture on a Cyclotriphosphazene Scaffold.

The synthesis of a homogeneous neutral hexaradical architecture consisting of six imino nitroxide radical moieties covalently bonded on a cyclotriphosphazene scaffold was reported. The synthesis of hexaradical imino nitroxide compounds follows the Ullman procedure involving the condensation of 2,3-bis(hydroxylamino)-2,3-dimethylbutane with hexa-(4-formylphenoxy)cyclotriphosphazene (3) followed by oxidation of the condensation product hexa-[4-(1-hydroxy-4,4,5,5-tetramethyl-2-imidazoline-2-yl)phenoxy]cyclotriphosphazene (2) by NaIO4. Characterization of hexaradical was performed by X-ray and SQUID in solid state and by EPR, absorption spectroscopy, and electrochemistry in solution. CV of 1 shows an oxidation peak at 1.184 V (vs SCE) and a reduction peak at -0.883 V, both characteristics of the presence of phenyl imino nitroxide (7) moieties, suggesting that the contribution of the cyclotriphosphazene core is negligible. Attention was particularly focused on developing methods, UV-vis spectroscopy and square-wave voltammetry, to quantify the number of radicals in a way to confirm easily and rapidly the polyradicals' structure.

Carbonic anhydrase inhibitors: Design, synthesis, kinetic, docking and molecular dynamics analysis of novel glycine and phenylalanine sulfonamide derivatives.

The inhibition of two human cytosolic carbonic anhydrase isozymes I and II, with some novel glycine and phenylalanine sulfonamide derivatives were investigated. Newly synthesized compounds G1-4 and P1-4 showed effective inhibition profiles with KI values in the range of 14.66-315µM for hCA I and of 18.31-143.8µM against hCA II, respectively. In order to investigate the binding mechanisms of these inhibitors, in silico docking studies were applied. Atomistic molecular dynamic simulations were performed for docking poses which utilize to illustrate the inhibition mechanism of used inhibitors into active site of CAII. These sulfonamide containing compounds generally were competitive inhibitors with 4-nitrophenylacetate as substrate. Some investigated compounds here showed effective hCA II inhibitory effects, in the same range as the clinically used sulfonamide, sulfanilamide or mafenide and might be used as leads for generating enzyme inhibitors possibly targeting other CA isoforms which have not been yet assayed for their interactions with such agents.

Synthesis of 3,4-dihydroxypyrrolidine-2,5-dione and 3,5-dihydroxybenzoic acid derivatives and evaluation of the carbonic anhydrase I and II inhibition.

The inhibition of two human cytosolic carbonic anhydrase (hCA, EC 4.2.1.1) isozymes I and II, with some 3,4-dihydroxypyrrolidine-2,5-dione and 3,5-dihydroxybenzoic acid derivatives, were investigated by using the esterase assay, with 4-nitrophenyl acetate (4-NPA) as substrate. Compounds 10-13 showed KI values in the range of 112.7-441.5 µM for hCA I and of 3.5-10.76 µM against hCA II, respectively. These hydroxyl group containing compounds generally were competitive inhibitors. Some hydroxyl group containing compounds investigated here showed effective hCA II inhibitory effects, in the same range as the clinically used sulfonamide acetazolamide, and might be used as leads for generating enzyme inhibitors possibly targeting other CA isoforms which have not been yet assayed for their interactions with such agents.

Kinetic and in silico analysis of thiazolidin-based inhibitors of α-carbonic anhydrase isoenzymes.

Carbonic anhydrases (CAs, EC 4.2.1.1) are inhibited by sulfonamides, inorganic anions, phenols, salicylic acid derivatives (acting as drug or prodrugs). A novel class of CA inhibitors (CAIs), interacting with the CA isozymes I and II (cytosolic) in a different manner, is reported here. Kinetic measurements allowed us to identify thiazolidin-based compounds as submicromolar-low micromolar inhibitors of these two CA isozymes. Molecular docking studies of a set of such inhibitors within CA I and II active site allowed us to understand the inhibition mechanism. This new class of inhibitors bind differently compared to other classes of inhibitors known to date: they were found between the phenol-binding site, filling thus the middle of the enzyme cavity.

Effect of substituents on spin density in benzimidazole nitronyl nitroxide radicals studied by electron spin resonance.

Several novel benzimidazole-3-oxide-1-oxyl radicals with substituents at 5 and/or 6 position were synthesized. The ESR analysis of nitrogen hyperfine coupling constants (hfccs) revealed that substituents at 5 and 6-position affect the spin density to greater extent than substituents on the phenyl ring at 2-position. Density functional theory calculations of nitrogen hfccs were performed using several different Pople type basis sets, as well as double and triple zeta quality individual gauge for localized orbital (IGLO-II, IGLO-III) and electron paramagnetic resonance (EPR-II, EPR-II) basis sets. Experimental and theoretical hfccs are compared.