Borosilicate glass was developed to enhance the mechanical behavior and smoothness of dental zirconia as an alternative to conventional glaze. This study assessed the mechanical and optical properties of 3 mol% yttria-stabilized tetragonal zirconia polycrystal (3Y-TZP) coated with borosilicate glass or a commercial glaze fired for an extended period of time. Disc-shaped 3Y-TZP zirconia specimens (Zpex, Tosoh) were sintered at 1550°C for 2 hours. The specimens were divided into three groups: as-sintered (control, C); commercial glaze (G); and borosilicate glass (SL). The glaze and borosilicate glass were applied over the zirconia and fired for 20 minutes at 950°C and 1200°C, respectively. Biaxial flexural strength, fractography, X-ray diffraction (XRD), roughness (Ra and Rz), fracture toughness (Vickers indentation method), color difference (∆E00), and translucency (TP00) analyses were conducted. The t-test or the one-way ANOVA and Tukey\'s tests were used to analyze the data (α = 0.05). Flexural strength data were subjected to the Weibull analysis. The SL group exhibited the highest flexural strength (1025.8 MPa), whereas the C (859.41 MPa) and G (816.0 MPa) groups exhibited similar values. The SL group also had the highest characteristic strength. The fracture origin in all groups was on the zirconia surface. XRD analysis revealed that the specimens from the SL group contained tetragonal, cubic, and monoclinic phases. The SL group presented the lowest surface roughness. Fracture toughness in the SL group was lower than in the C group, but similar to that observed in the G group. The translucency and color differences observed in the G and SL groups were similar. Borosilicate glass enhanced the flexural strength of 3Y-TZP, promoted the smoothest surface, and exhibited optical properties similar to those of the glaze.

In this study, biological synthesis of silver nanoparticles (AgNPs) using Senna auriculata flower extract for antibacterial activities was reported. The silver spectra compared to the plant extract show a rightward shift in AgNP peaks, indicating successful nanoparticle formation. The absorption band at 302 nm and the disappearance or shift of other peaks further confirm the synthesis. X-ray diffraction (XRD) analysis reveals that the AgNPs synthesized with S. auriculata extract have an average crystallite size of 25 nm. Transmission electron microscopy (TEM) results exhibited a polydispersed, spherical shape with sizes ranging from 70 nm, in clear contrast to the electron microscope image that showed their spherical shape. When examining the selected area electron diffraction (SAED) image, a specific set of lattice planes was correlated with a specific spot. A histogram of AgNP particle size distribution can be seen. AgNPs were tested against four different strains of bacteria for their antibacterial effectiveness, including gram negative bacteria (Escherichia coli, Klebsiella pneumoniae, and Staphylococcus aureus), as well as gram positive bacteria (S. aureus, d. Bacillus subtilis), at various concentrations of AgNP. The results of in vitro experiments indicate that AgNPs containing S. auriculata flowers inhibit amylase well. At two concentrations, ~16.03% and ~70.99%, AgNPs inhibit the reaction at low and high concentrations, respectively.

Pyrolysis of animal manure at high temperature is necessary to effectively immobilize heavy metals, while the available phosphorus (P) level in biochar is relatively low, rendering it unsuitable for use as fertilizer. In this study, the pretreatment of swine manure with different potassium (K) sources (KOH, K2CO3, CH3COOK and C6H5K3O7) was conducted to produce a biochar with enhanced P availability and heavy metals immobility. The addition of all K compounds lowered the peak temperature of decomposition of cellulose in swine manure. The percentage of ammonium citrate and formic acid extractable P in biochar increased with K addition compared to undoped biochar, with CH3COOK and C6H5K3O7 showing greater effectiveness than KOH and K2CO3, however, water- extractable P did not exhibit significant changes. Additionally, the available and dissolved Si increased due to the doping of K, with KOH and K2CO3 having a stronger effect than CH3COOK and C6H5K3O7. X-Ray Diffraction (XRD) and Fourier Transform Infrared Spectroscopy (FTIR) analysis revealed that K addition led to the formation of soluble CaKPO4 and silicate. In addition, the incorporation of K promoted the transformation of labile copper (Cu) and znic (Zn) into the stable fraction while simultaneously reducing their environmental risk. Our study suggest that the co-pyrolysis of swine manure and organic K represents an effective and valuable method for producing biochar with optimized P availability and heavy metals immobility.

Poly(ADP-ribose) (PAR), a non-canonical nucleic acid, is essential for DNA/RNA metabolism and protein condensation, and its dysregulation is linked to cancer and neurodegeneration. However, key structural insights into PAR\'s functions remain largely uncharacterized, hindered by the challenges in synthesizing and characterizing PAR, which are attributed to its length heterogeneity. A central issue is how PAR, comprised solely of ADP-ribose units, attains specificity in its binding and condensing proteins based on chain length. Here, we integrate molecular dynamics simulations with small-angle X-ray scattering to analyze PAR structures. We identify diverse structural ensembles of PAR that fall into distinct subclasses and reveal distinct compaction of two different lengths of PAR upon the addition of small amounts of Mg2+ ions. Unlike PAR15, PAR22 forms ADP-ribose bundles via local intramolecular coil-to-globule transitions. Understanding these length-dependent structural changes could be central to deciphering the specific biological functions of PAR.

BACKGROUND: Tyrosine-rich amelogenin peptide (TRAP) is the main amelogenin digestion product in the developmental enamel matrix. It has been shown to promote remineralization of demineralized enamel in our previous study. However, direct evidence of the effect of TRAP on the morphology and nanostructure of crystal growth on an enamel surface has not been reported. This study aimed to examine the effect of TRAP on the morphology of calcium phosphate crystals grown on early enamel erosion using a pH-cycling model.
METHODS: Eroded lesions were produced in human premolars by 30-second immersion in 37% phosphoric acid. Forty-five samples of eroded human premolar enamel blocks were selected and randomly divided into 3 groups: deionized water (DDW, negative control); 100 µg/mL TRAP, and 2 ppm sodium fluoride (NaF, positive control group). For 14 days, the specimens were exposed to a pH-cycling model. Using scanning electron microscopy (SEM) and atomic force microscopy (AFM) methods, the surface morphology, calcium-phosphorus ratio, and enamel surface roughness were examined. X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR) were used to assess crystal characteristics.
RESULTS: After pH-cycling, compared to the two control groups, the surface of the eroded enamel of the peptide TRAP group shows a large number of new, densely arranged rod-like crystals, parallel to each other, regularly arranged, forming an ordered structure, with crystal morphology similar to that of natural enamel. The crystals are mostly hydroxyapatite (HA).
CONCLUSIONS: This study demonstrates that the peptide TRAP modulates the formation of hydroxyapatite in eroded enamel and that the newly formed crystals resemble natural enamel crystals and promote the remineralization of enamel, providing a promising biomaterial for remineralization treatment of enamel lesions.

Telomeric G-quadruplexes (G4s) are non-canonical DNA structures composed of TTAGGG repeats. They are extensively studied both as biomolecules key for genome stability and as promising building blocks and functional elements in synthetic biology and nanotechnology. This is why it is extremely important to understand how the interaction between G4s is affected by their topology. We used small-angle x-ray scattering to investigate the end-to-end stacking of antiparallel telomeric G-quadruplexes formed by the sequence AG3(T2AG3)3. To represent the experimental data, we developed a highly efficient coarse-grained fitting tool, which successfully described the samples as an equilibrium mixture of monomeric and dimeric G4 species. Our findings indicate that the antiparallel topology prevents the formation of long multimeric structures under self-crowding conditions, unlike the hybrid/parallel structures formed by the same DNA sequence. This result supports the idea that the stacking of monomeric G-quadruplexes is strongly affected by the presence of diagonal loops.

In this article, we report sterically-controlled iron sites based on non-chelating bulky imidazole ligands. Adding 6 equiv. of 1,2-dimethylimidazole (1,2-Me2Im) to Fe(OTf)2⋅2CH3CN affords the first example of a 5-coordinate imidazole‑iron complex ([Fe(1,2-Me2Im)5](OTf)2, 1). The structure is distorted square pyramidal (τ5 = 0.41). When an iPr group is substituted for the methyl group at the 2-position on the imidazole (2-iPr-1-MeIm), the 14-electron complex ([Fe(2-iPr-1-MeIm)4](OTf)2, 2) is obtained. This complex exhibits slightly distorted tetrahedral geometry (τ\'4 = 0.93) with four N-donors and serves as a 4-His iron structural model complex for carotenoid cleavage dioxygenases (CCD). The electronic structure of 1 and 2 were characterized by Mössbauer spectroscopy. Reactions of 1 and 2 with model olefin substrates (1-R-4-(1-methoxyprop-1-en-2-yl)benzene; R = Me or Br) in the presence of oxygen result in olefin cleavage yielding ketone and aldehyde products, although 2 yields more products than 1. Support for a proposed reaction mechanism for 2 is offered from Density Functional Theory (DFT) calculations.

This work presents a new strategy to achieve the growth of copper sulfide nanoclusters with high nuclearity. Through a phosphine-assisted C-S reductive cleavage approach, an intrinsically chiral [Cu4] cluster passes through a [S-Cu9] cluster and transforms into a higher-nuclearity [S-Cu36] cluster, which features a core-shell structure with a [Cu4]4+ core encapsulated by a chiral [Cu20S12] shell. Interestingly, the spiral arrangement of the bidental ligands on the surface of the [S-Cu36] cluster leads to the L-/R-enantiomeric configurations. Moreover, by utilization of [Na(THF)6]+ as a chiral adaptive counterion, [S-Cu36] can be interlocked separately, thus enabling the isolation of homochiral clusters. Theoretical calculation suggests that the configuration transition between two enantiomeric [Na(THF)6]+ species is favorable at room temperature, thereby promoting the cocrystallization of resulting chiral products. This study introduces a novel perspective on the synthesis of chiral copper sulfide nanoclusters and presents an innovative approach to achieving the chiral separation of nanoclusters.

The focus of the present work was to develop amorphous solid dispersion (ASD) formulation of aprepitant (APT) using sucrose acetate isobutyrate (SAIB) excipient, evaluate for physicochemical attributes, stability, and bioavailability, and compared with hydroxypropyl methylcellulose (HPMC) based formulation. Various formulations of APT were prepared by solvent evaporation method and characterized for physiochemical and in-vivo performance attributes such as dissolution, drug phase, stability, and bioavailability. X-ray powder diffraction indicated crystalline drug conversion into amorphous phase. Dissolution varied as a function of drug:SAIB:excipient proportion. The dissolution was more than 80% in the optimized formulation (F10) and comparable to HPMC based formulation (F13). Stability of F10 and F13 formulations stored at 25 C/60% and 40°C/75% RH for three months were comparable. Both ASD formulations (F10 and F13) were bioequivalent as indicated by the pharmacokinetic parameters Cmax and AUC0-∞. Cmax and AUC0-∞ of F10 and F13 formulations were 2.52 ± 0.39, and 2.74 ± 0.32 μg/ml, and 26.59 ± 0.39, and 24.79 ± 6.02 μg/ml.h, respectively. Furthermore, the bioavailability of ASD formulation was more than twofold of the formulation containing crystalline phase of the drug. In conclusion, stability and oral bioavailability of SAIB based ASD formulation is comparable to HPMC-based formulation of poorly soluble drugs.

Laser lithotripsy mechanisms can cause the chemical decomposition of stone components and the emergence of different end products. However, the potentially toxic end products formed during thulium fiber laser (TFL) lithotripsy of cystine stones have not been sufficiently investigated. The aim of our in vitro study is to analyze the chemical content of the gas products formed during the fragmentation of cystine stone with TFL. Human renal calculi consisting of 100% pure cystine, calcium oxalate monohydrate, or uric acid were fragmented separately with TFL in experimental setups and observed for gas release. After the lithotripsy, only the cystine stones showed gas formation. Gas chromatography-mass spectrometry was used to analyze the gas qualitatively, and scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDX) and X-ray diffraction was used to examine the dried cystine stone fragments. Fragmentation of the cystine stones released free cystine, sulfur, hydrogen sulfide, and carbon disulfide gas. The SEM-EDX and X-ray diffraction analyses revealed that the free cystine in the dried fragments contained 43.1% oxygen, 28.7% sulfur, 16.1% nitrogen, and 12.1% carbon atoms according to atomic weight. The detection of potentially toxic gases after lithotripsy of cystine stones with TFL indicates a risk of in vivo production. Awareness needs to be increased among healthcare professionals to prevent potential inhalation and systemic toxicity for patients and operating room personnel during TFL lithotripsy of cystine stones.