Salivary, acidic and enzymatic degradation of resin composite subjected to different finishing and polishing systems.

PURPOSE: To evaluate the effect of different finishing and polishing systems on the surface roughness of a resin composite subjected to simulated saliva-, acid-, and enzyme-induced degradation. METHODS: 160 specimens (n= 40) were fabricated with Filtek Z350 XT nanofilled composite and analyzed for average surface roughness (Ra). The specimens were finished and polished using: AD - Al2O3-impreginated rubberized discs (medium, fine, and superfine grit, Sof-Lex); SD - silicon carbide and Al2O3-impregnated rubberized discs (coarse, medium and fine grit, Jiffy,); MB - 12- and 30-multiblade burs. The control group (CT) (n= 40) comprised specimens with a Mylar-strip-created surface. Specimens from each group were immersed in 1 mL of one of the degradation methods (n= 10): artificial saliva (ArS: pH 6.75), cariogenic challenge (CaC: pH 4.3), erosive challenge (ErC: 0.05M citric acid, pH 2.3) or enzymatic challenge (EzC: artificial saliva with 700 µg/mL of albumin, pH 6.75). The immersion period simulated a time frame of 180 days. Ra measurements were also performed at the post-polishing and post-degradation time points. The data were evaluated by three-way ANOVA for repeated measures and the Tukey tests. RESULTS: There was significant interaction between the finishing/polishing system and the degradation method (P= 0.001). AD presented the greatest smoothness, followed by SD. After degradation, CT, AD and SD groups became significantly rougher, but not the MB group, which presented no difference in roughness before or after degradation. CT and AD groups showed greater roughness in CaC, ErC and EzC than in ArS. The SD group showed no difference in roughness when the specimens were polished with CaC, EzC or ArS, but those treated with ErC had greater roughness. In the MB group, the lower roughness values were found after using CaC and EzC, while the higher values were found using ErC or ArS. CLINICAL SIGNIFICANCE: As far as degradation resistance of nanofilled composite to hydrolysis, bacterial and dietary acids and enzymatic reactions is concerned, restorations that had been finished and polished with Al2O3-impregnated discs had the smoothest surfaces.

Enhanced efficiencies on purifying acid mine drainage in constructed wetlands based on synergistic adsorption of attapulgite-soda residue composites and microbial sulfate reduction.

Constructed wetlands (CWs) are a promising approach for treating acid mine drainage (AMD). However, the extreme acidity and high loads of heavy metals in AMD can easily lead to the collapse of CWs without proper pre-treatment. Therefore, it is considered essential to maintain efficient and stable performance for AMD treatment in CWs. In this study, pre-prepared attapulgite-soda residue (ASR) composites were used to improve the substrate of CWs. Compared with CWs filled with gravel (CWs-G), the removal efficiencies of sulfate and Fe, Mn, Cu, Zn Cd and Pb in CWs filled with ASR composites (CWs-ASR) were increased by 30% and 10-70%, respectively. These metals were mainly retained in the substrate in stable forms, such as carbonate-, Fe/Mn (oxide)hydroxide-, and sulfide-bound forms. Additionally, higher levels of photosynthetic pigments and antioxidant enzyme activities in plants, along with a richer microbial community, were observed in CWs-ASR than in CWs-G. The application of ASR composites alleviated the adverse effects of AMD stresses on wetland plants and microorganisms. In return, the increased bacteria abundance, particularly SRB genera (e.g., Thermodesulfovibrionia and Desulfobacca), promoted the formation of metal sulfides, enabling the saturated ASR adsorbed with metals to regenerate and continuously capture heavy metals. The synergistic adsorption of ASR composites and microbial sulfate reduction maintained the stable and efficient operation of CWs. This study contributes to the resource utilization of industrial alkaline by-products and promotes the breakthrough of new techniques for low-cost and passive treatment systems such as CWs.

Detection of Biomolecules Using Solid-State Nanopores Fabricated by Controlled Dielectric Breakdown.

Nanopore sensor technology is widely used in biomolecular detection due to its advantages of low cost and easy operation. In a variety of nanopore manufacturing methods, controlled dielectric breakdown has the advantages of a simple manufacturing process and low cost under the premise of ensuring detection performance. In this paper, we have made enhancements to the applied pulses in controlled dielectric breakdown and utilized the improved dielectric breakdown technique to fabricate silicon nitride nanopores with diameters of 5 to 15 nm. Our improved fabrication method offers the advantage of precise control over the nanopore diameter (±0.4 nm) and enhances the symmetry of the nanopore. After fabrication, we performed electrical characterization on the nanopores, and the IV characteristics exhibited high linearity. Subsequently, we conducted detection experiments for DNA and protein using the prepared nanopores to assess the detection performance of the nanopores fabricated using our method. In addition, we also give a physical model of molecule translocation through the nanopores to give a reasonable explanation of the data processing results.

Unravelling performance of honeycomb structures as drug delivery systems for the isoniazid drug using DFT-D3 correction dispersion and molecular dynamic simulations.

In this study, the potential of aluminum nitride (h-AlN), boron nitride (h-BN) and silicon carbide (h-SiC) nanosheets as the drug delivery systems (DDS) of isoniazid (INH) was scrutinized through density functional theory (DFT) and molecular dynamic (MD) simulations. We performed DFT periodic calculations on the geometry and electronic features of nanosheets adsorbed with INH by the DFT functional (DZP/GGA-PBE) employed in the SIESTA code. In the energetically favorable model, an oxygen atom of the C-O group of the INH molecule interacts with a Si atom of the h-SiC at 2.077 Å with an interaction energy of -1.361 eV. Charge transfer (CT) calculation by employing the Mulliken, Hirshfeld and Voronoi approaches reveals that the monolayers and drug molecules act as donors and acceptors, respectively. The density of states (DOS) calculations indicate that the HOMO-LUMO energy gap (HLG) of the h-SiC nanosheet declines significantly from 2.543 to 1.492 eV upon the adsorption of the INH molecule, which causes an electrical conductivity increase and then produces an electrical signal. The signal is linked to the existence of INH, demonstrating that h-SiC may be an appropriate sensor for INH sensing. The decrease in HLG for the interaction of INH and h-SiC is the uppermost (up to 41%) representing the uppermost sensitivity, whereas the sensitivity trend is σ(h-SiC) > σ(h-AlN) > σ(h-BN). Quantum theory of atoms in molecules (QTAIM) investigations is employed to scrutinize the nature of the INH/nanosheet interactions. The QTAIM analysis reveals that the interaction of the INH molecule and h-SiC has a partially covalent nature, while INH/h-AlN model electrostatic interaction occurs in the system and noncovalent and electrostatic interaction for the INH/h-BN model. Finally, the state-of-the-art DFT-MD simulations utilized in this study can mimic ambient conditions. The results obtained from the MD simulation show that it takes more time to bond the INH drug and h-SiC, and the INH/h-SiC system becomes stable. The results of the current research demonstrate the potential of h-SiC as a suitable sensor and drug delivery platform for INH drugs to remedy tuberculosis.

The hemostatic performance and mechanism of palygorskite with structural regulate by oxalic acid gradient leaching.

Palygorskite (Pal) is a naturally available one-dimensional clay mineral, featuring rod-shaped morphology, nanoporous structure, permanent negative charges as well as abundant surface hydroxyl groups, exhibiting promising potential as a natural hemostatic material. In this study, the hemostatic performance and mechanisms of Pal were systematically investigated based on the structural regulate induced by oxalic acid (OA) gradient leaching from perspectives of structure, surface attributes and ion release.In vitroandin vivohemostasis evaluation showed that Pal with OA leaching for 1 h exhibited a superior blood procoagulant effect compared with the raw Pal as well as the others leached for prolonging time. This phenomenon might be ascribed to the synergistic effect of the intact nanorod-like morphology, the increase in the surface negative charge, the release of metal ions (Fe3+and Mg2+), and the improved blood affinity, which promoted the intrinsic coagulation pathway, the fibrinogenesis and the adhesion of blood cells, thereby accelerating the formation of robust blood clots. This work is expected to provide experimental and theoretical basis for the construction of hemostatic biomaterials based on clay minerals.

Planar amorphous silicon carbide microelectrode arrays for chronic recording in rat motor cortex.

Chronic implantation of intracortical microelectrode arrays (MEAs) capable of recording from individual neurons can be used for the development of brain-machine interfaces. However, these devices show reduced recording capabilities under chronic conditions due, at least in part, to the brain's foreign body response (FBR). This creates a need for MEAs that can minimize the FBR to possibly enable long-term recording. A potential approach to reduce the FBR is the use of MEAs with reduced cross-sectional geometries. Here, we fabricated 4-shank amorphous silicon carbide (a-SiC) MEAs and implanted them into the motor cortex of seven female Sprague-Dawley rats. Each a-SiC MEA shank was 8 µm thick by 20 µm wide and had sixteen sputtered iridium oxide film (SIROF) electrodes (4 per shank). A-SiC was chosen as the fabrication base for its high chemical stability, good electrical insulation properties, and amenability to thin film fabrication. Electrochemical analysis and neural recordings were performed weekly for 4 months. MEAs were characterized pre-implantation in buffered saline and in vivo using electrochemical impedance spectroscopy and cyclic voltammetry at 50 mV/s and 50,000 mV/s. Neural recordings were analyzed for single unit activity. At the end of the study, animals were sacrificed for immunohistochemical analysis. We observed statistically significant, but small, increases in 1 and 30 kHz impedance values and 50,000 mV/s charge storage capacity over the 16-week implantation period. Slow sweep 50 mV/s CV and 1 Hz impedance did not significantly change over time. Impedance values increased from 11.6 MΩ to 13.5 MΩ at 1 Hz, 1.2 MΩ-2.9 MΩ at 1 kHz, and 0.11 MΩ-0.13 MΩ at 30 kHz over 16 weeks. The median charge storage capacity of the implanted electrodes at 50 mV/s was 58.1 mC/cm2 on week 1 and 55.9 mC/cm2 on week 16, and at 50,000 mV/s, 4.27 mC/cm2 on week 1 and 5.93 mC/cm2 on week 16. Devices were able to record neural activity from 92% of all active channels at the beginning of the study, At the study endpoint, a-SiC devices were still recording single-unit activity on 51% of electrochemically active electrode channels. In addition, we observed that the signal-to-noise ratio experienced a small decline of -0.19 per week. We also classified observed units as fast and slow repolarizing based on the trough-to-peak time. Although the overall presence of single units declined, fast and slow repolarizing units declined at a similar rate. At recording electrode depth, immunohistochemistry showed minimal tissue response to the a-SiC devices, as indicated by statistically insignificant differences in activated glial cell response between implanted brains slices and contralateral sham slices at 150 µm away from the implant location, as evidenced by GFAP staining. NeuN staining revealed the presence of neuronal cell bodies close to the implantation site, again statistically not different from a contralateral sham slice. These results warrant further investigation of a-SiC MEAs for future long-term implantation neural recording studies.

Highly efficient and selective removal of anionic dyes from aqueous solutions using polyacrylamide/peach gum polysaccharide/attapulgite composite hydrogels with positively charged hybrid network.

To avoid the weakness (lower adsorption rate and selectivity) of peach gum polysaccharide (PGP) and improve the adsorption performance of polyacrylamide (PAAm) hydrogel (lower adsorption capacity), in the present work, the PGP was chemically tailored to afford ammoniated PGP (APGP) and quaternized PGP (QPGP), and attapulgite (ATP) was bi-functionalized with cation groups and carbon­carbon double bond. Then, PAAm/APGP and PAAm/QPGP/ATP hydrogels were synthesized via redox polymerization. The synthesis procedure and properties of hydrogels were traced by FTIR, SEM, XPS, TGA, TEM, and BET methods, and the dye adsorption performance of the hydrogels was evaluated using the new coccine (NC) and tartrazine (TTZ) aqueous solutions as the model anionic dyes. Effects of initial dye concentration, pH, and ionic strength on the adsorption were investigated. Compared with PAAm/APGP hydrogel, PAAm/APGP/ATP hydrogel exhibits higher adsorption rate, superior adsorption capacity, stability, and selectivity towards anionic dye. The adsorption process of PAAm/QPGP/ATP hydrogel reached equilibrium in about 20 min and followed the pseudo-second-order kinetic model and Langmuir isotherm. The adsorption capacities towards NC and TTZ of PAAm/QPGP/ATP hydrogel were calculated as 873.235 and 731.432 mg/g. This hydrogel adsorbent originating from PAAm, PGP, and ATP shows great promise for application in practical water treatment.

Acid modified attapulgite loaded with bacillomycin D for mold inhibition and mycotoxin removal.

Molds and mycotoxins pose severe threats to health. Bacillomycin D (BD) can effectively inhibit mold growth. Attapulgite (ATP) can provide a good carrier for antimicrobial agents. Natural ATP was acid-modified to obtain H-ATP. It was used to load BD to obtain a novel composite material (H-ATP-BD). The results showed H-ATP had better adsorption performance than ATP. BD was adsorbed up to 93.13 % by adding 30 mg H-ATP and stirring at 40 ℃ for 120 min. Fourier transform infrared spectra (FTIR), size and zeta potential, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) results confirmed successful loading of BD onto H-ATP. The composite showed good inhibition of Aspergillus and adding 0.6 % H-ATP-BD composite was effective in removing 89.06 % of aflatoxin B1 (AFB1) at 50 °C. Model fitting indicated that AFB1 removal was a spontaneous exothermic reaction. This research will lay the foundation for the development of efficient and green antimicrobial and toxin-reducing materials.

Chronic toxicity of core-shell SiC/TiO2 (nano)-particles to Daphnia magna under environmentally relevant food rations in the presence of humic acid.

To date, research on the toxicity and potential environmental impacts of nanomaterials has predominantly focused on relatively simple and single-component materials, whilst more complex nanomaterials are currently entering commercial stages. The current study aimed to assess the long-term and size-dependent (60 and 500 nm) toxicity of a novel core-shell nanostructure consisting of a SiC core and TiO2 shell (SiC/TiO2, 5, 25, and 50 mg L-1) to the common model organism Daphnia magna. These novel core-shell nanostructures can be categorized as advanced materials. Experiments were conducted under environmentally realistic feeding rations and in the presence of a range of concentrations of humic acid (0.5, 2, 5, and 10 mg L-1 TOC). The findings show that although effect concentrations of SiC/TiO2 were several orders of magnitude lower than the current reported environmental concentrations of more abundantly used nanomaterials, humic acid can exacerbate the toxicity of SiC/TiO2 by reducing aggregation and sedimentation rates. The EC50 values (mean ± standard error) based on nominal SiC/TiO2 concentrations for the 60 nm particles were 28.0 ± 11.5 mg L-1 (TOC 0.5 mg L-1), 21.1 ± 3.7 mg L-1 (TOC 2 mg L-1), 18.3 ± 5.4 mg L-1 (TOC 5 mg L-1), and 17.8 ± 2.4 mg L-1 (TOC 10 mg L-1). For the 500 nm particles, the EC50 values were 34.9 ± 16.5 mg L-1 (TOC 0.5 mg L-1), 24.8 ± 5.6 mg L-1 (TOC 2 mg L-1), 28.0 ± 10.0 mg L-1 (TOC 5 mg L-1), and 23.2 ± 4.1 mg L-1 (TOC 10 mg L-1). We argue that fate-driven phenomena are often neglected in effect assessments, whilst environmental factors such as the presence of humic acid may significantly influence the toxicity of nanomaterials.

Light-Driven Conversion of Silicon Nitride Nanopore to Nanonet for Single-Protein Trapping Analysis.

The single-molecule technique for investigation of an unlabeled protein in solution is very attractive but with great challenges. Nanopore sensing as a label-free tool can be used for collecting the structural information of individual proteins, but currently offers only limited capabilities due to the fast translocation of the target. Here, a reliable and facile method is developed to convert the silicon nitride nanopore to a stable nanonet platform for single-entity sensing by electrophoretic or electroosmotic trapping. A nanonet is fabricated based on a material reorganization process caused by electron-beam and light-irradiation treatment. Using protein molecules as a model, it is revealed that the solid-state nanonet can produce collision and trapping flipping signals of the protein, which provides more structural information than traditional nanopore sensing. More importantly, thanks to the excellent stability of the solid-state silicon nitride nanonet, it is demonstrated that the ultraviolet-light-irradiation-induced structural-change process of an individual protein can be captured. The developed nanonet supplies a robust platform for single-entity studies but is not limited to proteins.

Morphofunctional reaction of leukocytes and platelets in in vitro contact with a-C:H:SiOx -coated Ti-6Al-4V substrate.

The article deals with the plasma-assisted chemical vapor deposition of 0.3-1.4 µm thick a-C:H:SiOx films in a mixture of argon and polyphenylmethylsiloxane vapor onto the Ti-6Al-4V alloy substrate, which is often used as an implant material. The a-C:H:SiOx film structure is studied by the Fourier-transform infrared and Raman spectroscopies. The pull-off adhesion test assesses the adhesive strength of a-C:H:SiOx films, and the ball-on-disk method is employed to measure their wear rate and friction coefficient. According to these studies, a-C:H:SiOx films are highly adhesive to the Ti-6Al-4V substrate, have low (0.056) friction coefficient and wear rate (9.8 × 10-8  mm3  N-1  m-1 ) in phosphate-buffered saline at 40°C. In vitro studies show neither thrombogenicity nor cytotoxicity of the a-C:H:SiOx film for the human blood mononuclear cells (hBMNCs). The in vitro contact between the hBMNC culture and a-C:H:SiOx films 0.8-1.4 µm thick deposited onto Ti-6Al-4V substrates reduces a 24-hour secretion of pro-inflammatory cytokines and chemokines IL-8, IL-17, TNFα, RANTES, and MCP-1. This reduction is more significant when the film thickness is 1.4 µm and implies its potential anti-inflammatory effect and possible application in cardiovascular surgery. The dependence is suggested for the concentration of anti-inflammatory cytokines and chemokines and the a-C:H:SiOx film thickness, which correlates with the surface wettability and electrostatic potential. The article discusses the possible applications of the anti-inflammatory effect and low thrombogenicity of a-C:H:SiOx films in cardiovascular surgery.

Microfluidic Liquid Cell with Silicon Nitride Super-Thin Membrane for Electron Microscopy of Samples in Liquid.

Microfluidic liquid cells have been developed to visualize nanoscaled biological samples in liquid using a scanning electron microscope (SEM) through an electron-transparent membrane (ETM). However, despite the combination of the high-resolution visualization of SEM and the high experimental capability of microfluidics, the image is unclear because of the scattering of the electron beam in the ETM. Thus, this study developed a microfluidic liquid cell with a super-thin ETM of thickness 10 nm. Because the super-thin ETM is excessively fragile, the bonding of a silicon-nitride-deposited substrate and a polydimethylsiloxane microchannel before silicon anisotropic etching was proposed prevented the super-thin ETM from damage and breakage due to etching. With this protection against etchant using the microchannel, the yield of the fabricated super-thin ETM increased from 0 to 87%. Further, the scattering of the electron beam was suppressed using a microfluidic liquid cell with a super-thin ETM, resulting in high-resolution visualization. In addition, T4 bacteriophages were visualized using a super-thin ETM in vacuum. Furthermore, the cyanobacterium Synechocystis sp. PCC6803 in liquid was visualized using a super-thin ETM, and sub-microscopic structures on the surface were observed.

Silicon Nitride Nanopores Formed by Simple Chemical Etching: DNA Translocations and TEM Imaging.

We demonstrate DNA translocations through silicon nitride pores formed by simple chemical etching on glass substrates using microscopic amounts of hydrofluoric acid. DNA translocations and transmission electron microscopy (TEM) prove the fabrication of nanopores and allow their characterization. From ionic measurements on 318 chips, we report the effective pore diameters ranging from zero (pristine membranes) and sub-nm to over 100 nm, within 50 µm diameter membranes. The combination of ionic conductance, DNA current blockades, TEM imaging, and electron energy loss spectroscopy (EELS) provides comprehensive information about the pore area and number, from single to few pores, and pore structure. We also show the formation of thinned membrane regions as precursors of pores. The average pore density, about 5 × 10-4 pores/µm2, allows pore number adjustment statistically (0, 1, or more). This simple and affordable chemical method for making solid-state nanopores accelerates their adoption for DNA sensing and characterization applications.

Immobilization of EreB on Acid-Modified Palygorskite for Highly Efficient Degradation of Erythromycin.

Erythromycin is one of the most commonly used macrolide antibiotics. However, its pollution of the ecosystem is a significant risk to human health worldwide. Currently, there are no effective and environmentally friendly methods to resolve this issue. Although erythromycin esterase B (EreB) specifically degrades erythromycin, its non-recyclability and fragility limit the large-scale application of this enzyme. In this work, palygorskite was selected as a carrier for enzyme immobilization. The enzyme was attached to palygorskite via a crosslinking reaction to construct an effective erythromycin-degradation material (i.e., EreB@modified palygorskite), which was characterized using FT-IR, SEM, XRD, and Brunauer-Emmett-Teller techniques. The results suggested the successful modification of the material and the loading of the enzyme. The immobilized enzyme had a higher stability over varying temperatures (25-65 °C) and pH values (6.5-10.0) than the free enzyme, and the maximum rate of reaction (Vmax) and the turnover number (kcat) of the enzyme increased to 0.01 mM min-1 and 169 min-1, respectively, according to the enzyme-kinetics measurements. The EreB@modified palygorskite maintained about 45% of its activity after 10 cycles, and degraded erythromycin in polluted water to 20 mg L-1 within 300 min. These results indicate that EreB could serve as an effective immobilizing carrier for erythromycin degradation at the industrial scale.

Wide bandgap semiconductor nanomembranes as a long-term biointerface for flexible, implanted neuromodulator.

Electrical neuron stimulation holds promise for treating chronic neurological disorders, including spinal cord injury, epilepsy, and Parkinson's disease. The implementation of ultrathin, flexible electrodes that can offer noninvasive attachment to soft neural tissues is a breakthrough for timely, continuous, programable, and spatial stimulations. With strict flexibility requirements in neural implanted stimulations, the use of conventional thick and bulky packages is no longer applicable, posing major technical issues such as short device lifetime and long-term stability. We introduce herein a concept of long-lived flexible neural electrodes using silicon carbide (SiC) nanomembranes as a faradic interface and thermal oxide thin films as an electrical barrier layer. The SiC nanomembranes were developed using a chemical vapor deposition (CVD) process at the wafer level, and thermal oxide was grown using a high-quality wet oxidation technique. The proposed material developments are highly scalable and compatible with MEMS technologies, facilitating the mass production of long-lived implanted bioelectrodes. Our experimental results showed excellent stability of the SiC/silicon dioxide (SiO2) bioelectronic system that can potentially last for several decades with well-maintained electronic properties in biofluid environments. We demonstrated the capability of the proposed material system for peripheral nerve stimulation in an animal model, showing muscle contraction responses comparable to those of a standard non-implanted nerve stimulation device. The design concept, scalable fabrication approach, and multimodal functionalities of SiC/SiO2 flexible electronics offer an exciting possibility for fundamental neuroscience studies, as well as for neural stimulation-based therapies.

In vitro antibacterial effect of forsterite nanopowder: synthesis and characterization.

The aims of this study were the preparation, characterization, and in vitro antibacterial activity evaluation of forsterite (FS, Mg2SiO4) nanopowder obtained by two major methods, namely sol-gel (FSsg) and co-precipitation (FSpp). The main aim was to determine the influence of preparation methodologies on physical properties and in vitro antibacterial activity of obtained forsterite nanopowder. To assess the best working temperature for the preparation of FSsg and FSpp, the synthesis and thermal treatment conditions were optimized on the basis of thermal gravimetric (TG) and differential scanning calorimetric (DSC) analysis performed on the dried gel and dried co-precipitated solid, respectively. The FSsg and FSpp powders were characterized by X-ray powder diffraction (XRD), indicating a high purity for both FSsg and FSpp powders. The morphology of FSsg and FSpp nanopowders was explored by scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectroscopy (EDX) and atomic force microscopy (AFM). In vitro antibacterial activity was investigated using a targeted pathogen, namely Staphylococcus aureus (S. aureus) ATCC 6538 P as tested strain by broth dilution technique and inoculations on nutrient agar to highlight the bactericidal inhibitory effect. FSsg nanopowder has no inhibitory capacity, while FSpp produced inhibition, the effect being bactericidal at a concentration of 10 mg/mL. The superior bactericidal activity of FSpp against FSsg is due to variation in the own surface properties, such as specific surface area (SSA) and nano-regime particle size. The FSpp nanoparticles, NPs, obtained by co-precipitation method are reported for the first time as a novel bactericidal nanomaterial against S. aureus.

Anticancer and biological properties of new axially disubstituted silicon phthalocyanines.

This study reports the synthesis of three novel axially disubstituted silicon phthalocyanines (1-3-Si) and their quaternized phthalocyanines (1-3-QSi). The resulting compounds were characterized by applying spectroscopic techniques including 1H NMR, FT-IR, UV-vis, and mass spectroscopy. The biological properties of compounds 1-3-QSi, including DNA cleavage activities, DNA binding modes, and topoisomerase enzyme inhibition activities, were investigated using agarose gel electrophoresis. pBR322 plasmid DNA, CT-DNA, and AL-DNA (isolated from apricot leaf) were used for DNA studies. All the quaternized compounds exhibited acceptable DNA cleavage activities. Human topoisomerase I and E. coli topoisomerase enzymes were used for the topoisomerase I inhibition studies. All the quaternized complexes inhibited topoisomerase I activity. Moreover, these compounds were screened for cytotoxic and apoptotic effects against a human colon cancer cell line (DLD-1) by performing MTT and Annexin V assays. They exhibited toxicity and apoptotic effect on the DLD-1 cell line. The findings reveal that the compounds can be utilized for cancer therapy after further investigations.

Synthesis of ß-Silyl-α-amino Acid Derivatives by Cu-Catalyzed Regio- and Enantioselective Silylamination of α,ß-Unsaturated Esters.

A copper-catalyzed silylamination of α,ß-unsaturated esters with silylboranes and hydroxylamines has been developed to afford the corresponding ß-silyl-α-amino acid derivatives, which are of great interest in medicinal and pharmaceutical chemistry. Additionally, by using a suitable chiral bisphosphine ligand, the asymmetric induction is possible, delivering the optically active ß-silyl-α-amino acids with synthetically acceptable diastereomeric ratios (55:45-82:18 dr) and high enantiomeric ratios (81:19-99:1 er).

Resonator nanophotonic standing-wave array trap for single-molecule manipulation and measurement.

Nanophotonic tweezers represent emerging platforms with significant potential for parallel manipulation and measurements of single biological molecules on-chip. However, trapping force generation represents a substantial obstacle for their broader utility. Here, we present a resonator nanophotonic standing-wave array trap (resonator-nSWAT) that demonstrates significant force enhancement. This platform integrates a critically-coupled resonator design to the nSWAT and incorporates a novel trap reset scheme. The nSWAT can now perform standard single-molecule experiments, including stretching DNA molecules to measure their force-extension relations, unzipping DNA molecules, and disrupting and mapping protein-DNA interactions. These experiments have realized trapping forces on the order of 20 pN while demonstrating base-pair resolution with measurements performed on multiple molecules in parallel. Thus, the resonator-nSWAT platform now meets the benchmarks of a table-top precision optical trapping instrument in terms of force generation and resolution. This represents the first demonstration of a nanophotonic platform for such single-molecule experiments.

Development of Chiral Ligands for the Transition-Metal-Catalyzed Enantioselective Silylation and Borylation of C-H Bonds.

Enantioselective reactions that install functional groups at the positions of unactivated C-H bonds can be envisioned to produce intermediates for the synthesis of the active ingredients in pharmaceuticals and agrochemicals directly from simple feedstocks. Among these C-H bond functionalization reactions, those that form carbon-silicon (C-Si) and carbon-boron (C-B) bonds have been pursued because the products of these reactions can be converted to those containing a wide range of functional groups and because compounds containing silicon and boron possess unique properties that can be valuable for medicinal and materials chemistry. Although the silylation and borylation of C-H bonds have undergone extensive development during the past two decades, enantioselective versions of these reactions were not known until a few years ago. In this Minireview, we present the rapid development of enantioselective silylation and borylation of C-H bonds, with an emphasis on the design and development of the types of chiral ligands needed to achieve these reactions and an intention to inspire an expansion of these types of transformations.