High quantum yield blue- and orange-emitting carbon dots: one-step microwave synthesis and applications as fluorescent films and in fingerprint and cellular imaging.

A high quantum yield (QY) is the key requirement for implementing carbon dots (CDs) in nearly all applications. In this work, blue emissive N-doped CDs with a QY of 83% and orange emissive N-doped CDs with a QY of 47% were successfully prepared using resorcinol and phloroglucin as carbon resources in formamide by one-step microwave synthesis, respectively. Formamide not only plays a role as the solvent but also takes part in the formation of the high QY CDs. It is demonstrated that the as-prepared blue- and orange-emitting N-doped CDs with a high QY can be uniformly dispersed into glue and be fabricated as CD/glue fluorescent composites for fluorescent films and fingerprint imaging. Furthermore, these CDs also show excellent cellular imaging capability.

Removal of phenanthrene in aqueous solution containing photon competitors by TiO2-C-Ag film supported on fiberglass.

Surface interactions with pollutants and photons are key factors that affect the applications of TiO2 in environmental remediation. In this study, the solubilizing agents dimethylsulfoxide and polyoxyethylene sorbitan monooleate, which act as photon competitors, had no effect on the photocatalytic activity of TiO2-C-Ag film in phenanthrene (PHE) removal. Fiberglass with TiO2-C-Ag coating removed 91.1 ± 5.2 and 99.7 ± 0.4% of PHE in treatments using UVA (365-465 nm) and UVC (254 nm) irradiation, respectively. The use of fiberglass as a support increased the superficial area, thus allowing PHE sorption. C and Ag, which are electrically active impurities in TiO2, enhanced its photocatalytic activity and thus the attraction of the pollutant to its surface. The use of high-frequency UV light (UVC) decreased the amount of carbon species deposited on the TiO2CAg film surface. X-ray photoelectron spectroscopy of the TiO2-C-Ag film revealed extensive oxidation of the carbon deposited on the film under UVC light and loss of electrons from Ag clusters by conversion of Ag0 to Ag3+.

Optical property study of FePt-C nanocomposite thin film for heat-assisted magnetic recording.

Optical properties of the FePt-C nanocomposite thin film that was synthesized by sputtering with MgO/NiTa underlayer on glass substrate have been determined by an approach combining spectroscopic ellipsometry and transmission over the wavelength range of 380 - 1700 nm. It was observed that the refractive index is larger than the extinction coefficient, indicating that free electron absorption is not the dominant optical transition in the FePt-C thin film. Compared with FePt thin film, the FePt-C thin film has smaller optical constants, which lead to better optical performance including smaller optical spot on recording media and higher transducer efficiency for heat assisted magnetic recording.

Carbon-centered radicals in γ-irradiated bone substituting biomaterials based on hydroxyapatite.

Gamma irradiated synthetic hydroxyapatite, bone substituting materials NanoBone(®) and HA Biocer were examined using EPR spectroscopy and compared with powdered human compact bone. In every case, radiation-induced carbon centered radicals were recorded, but their molecular structures and concentrations differed. In compact bone and synthetic hydroxyapatite the main signal assigned to the CO(2) (-) anion radical was stable, whereas the signal due to the CO(3) (3-) radical dominated in NanoBone(®) and HA Biocer just after irradiation. However, after a few days of storage of these samples, also a CO(2) (-) signal was recorded. The EPR study of irradiated compact bone and the synthetic graft materials suggest that their microscopic structures are different. In FT-IR spectra of NanoBone(®), HA Biocer and synthetic hydroxyapatite the HPO(4) (2-) and CO(3) (2-) in B-site groups are detected, whereas in compact bone signals due to collagen dominate.

Photodegradation of carbon dots cause cytotoxicity.

Carbon dots (CDs) are photoluminescent nanomaterials with wide-ranging applications. Despite their photoactivity, it remains unknown whether CDs degrade under illumination and whether such photodegradation poses any cytotoxic effects. Here, we show laboratory-synthesized CDs irradiated with light degrade into molecules that are toxic to both normal (HEK-293) and cancerous (HeLa and HepG2) human cells. Eight days of irradiation photolyzes 28.6-59.8% of the CDs to <3 kilo Dalton molecules, 1431 of which are detected by high-throughput, non-target high-performance liquid chromatography-quadrupole time-of-flight mass spectrometry. Molecular network and community analysis further reveal 499 cytotoxicity-related molecules, 212 of which contain polyethylene glycol, glucose, or benzene-related structures. Photo-induced production of hydroxyl and alkyl radicals play important roles in CD degradation as affected by temperature, pH, light intensity and wavelength. Commercial CDs show similar photodegraded products and cytotoxicity profiles, demonstrating that photodegradation-induced cytotoxicity is likely common to CDs regardless of their chemical composition. Our results highlight the importance of light in cytocompatibility studies of CDs.

Influence of curing mode and time on degree of conversion of one conventional and two self-adhesive resin cements.

This study evaluated the effect of curing mode (auto- and dual-polymerizing mode) and time interval (5, 10 and 15 minutes) on the degree of conversion of resin cements. One conventional dual-cured resin cement (Panavia F 2.0 [Kuraray Medical Inc]) and two self-adhesive cements (RelyX Unicem [3M ESPE] and BisCem [BISCO, Inc]) were evaluated. The products (n = 5) were manipulated according to the manufacturer's instructions and applied to the surface of a horizontal attenuated reflectance unit attached to an infrared spectrometer. The materials were either light-cured for 40 seconds (dual-polymerizing mode) or allowed to auto-polymerize. The degree of conversion was calculated according to changes in the aliphatic-to-aromatic peak ratios prior to and 5, 10 and 15 minutes after light-activation or after mixing when the specimens were allowed to auto-polymerize. Data (%) were analyzed by two-way repeated measure ANOVA (curing mode and time interval) and Tukey's post-hoc test (alpha = 0.05%). The light-activating mode led to a higher degree of conversion values than the self-curing mode in self-adhesive cements (RelyX Unicem and BisCem), while there was no difference in the degree of conversion between the self- and light-cured groups of Panavia F 2.0 resin cement. All products showed a higher degree of conversion at 15 minutes postcuring than any other evaluation interval. The self-adhesive cements provide a higher degree of conversion values when light-activated. After 15 minutes of polymerization initiation, the degree of conversion was higher in all resin cements, regardless of the curing mode.

Carbon dot cross-linked polyvinylpyrrolidone hybrid hydrogel for simultaneous dye adsorption, photodegradation and bacterial elimination from waste water.

The creation of a polymeric hydrogel from polyvinylpyrrolidone (PVP) cross-linked by Carbon Quantum Dots (CD) for the adsorption and photocatalytic degradation of both cationic and anionic dyes. PVP, an important biocompatible constituent and often surplus in cosmetic industry, was carboxylated through NaOH refluxing and covalently conjugated to surface amine functionality of CD derived from lemon juice and Cysteamine. The hybrid hydrogel was obtained from PVP-CD covalent conjugate by careful manipulation of pH and found to possess better rheological properties than only carboxylate-PVP. The monolayer physisorption of the dyes on the hydrogel was affected by hydrogen bonding, dispersion or inductive effect, and π-π interaction with the polymer backbone as well as the CD that followed pseudo-second-order kinetics. Degradation of the adsorbed dyes was instated by the unique Reactive Oxygen Species (ROS) generating ability of the CD embedded in the hydrogel matrix upon exposure to sunlight, the mechanism of which is also unveiled. The same CD-induced ROS was found to effectively annihilate both gram-positive and gram-negative bacteria in real polluted water in less than 10 min of photoexcitation of the hydrogel. The hydrogel was restored by mild acid wash that is able to perform dye adsorption and photo-degradation upto four cycles.

Non-thermal desorption/ablation of molecular solids induced by ultra-short soft x-ray pulses.

We report the first observation of single-shot soft x-ray laser induced desorption occurring below the ablation threshold in a thin layer of poly (methyl methacrylate)--PMMA. Irradiated by the focused beam from the Free-electron LASer in Hamburg (FLASH) at 21.7 nm, the samples have been investigated by atomic-force microscope (AFM) enabling the visualization of mild surface modifications caused by the desorption. A model describing non-thermal desorption and ablation has been developed and used to analyze single-shot imprints in PMMA. An intermediate regime of materials removal has been found, confirming model predictions. We also report below-threshold multiple-shot desorption of PMMA induced by high-order harmonics (HOH) at 32 nm. Short-time exposure imprints provide sufficient information about transverse beam profile in HOH's tight focus whereas long-time exposed PMMA exhibits radiation-initiated surface ardening making the beam profile measurement infeasible.

Photo-triggered conversion of hydrophilic fluorescent biomimetic nanostructures for cell imaging.

Fluorescent nanoarchitectures, such as hydrophobic micelles and hydrophilic vesicles decorated with fluorescent carbon nanoparticles, were fabricated from one fatty acid by means of photo-triggering. The biomimetic nanostructures, like cell membrane structures, have applications in fluorescence imaging in both the cell cytoplasm and nucleus. Besides, hydrophobic micelles can be used as very stable fluorescent inks.

Modeling of carbon fiber couch attenuation properties with a commercial treatment planning system.

The purpose of this work is to evaluate the modeling of carbon fiber couch attenuation properties with a commercial treatment planning system (TPS, Pinnacle3, v8.0d). A carbon fiber couch (Brain-Lab) was incorporated into the TPS by automatic contouring of all transverse CT slices. The couch shape and dimensions were set according to the vendor specifications. The couch composition was realized by assigning appropriate densities to the delineated contours. The couch modeling by the TPS was validated by absolute dosimetric measurements. A phantom consisting of several solid water slabs was CT scanned, the CT data set was imported into the TPS, and the carbon fiber couch was auto-contoured. Open (unblocked) field plans for different gantry angles and field sizes were generated. The doses to a point at 3 cm depth, placed at the linac isocenter, were computed. The phantom was irradiated according to the dose calculation setup and doses were measured with an ion chamber. In addition, percent depth dose (PDD) curves were computed as well as measured with radiographic film. The calculated and measured doses, transmissions, and PDDs were cross-compared. Doses for several posterior fields (0 degree, 30 degrees, 50 degrees, 75 degrees, 83 degrees) were calculated for 6 and 18 MV photon beams. For model validation a nominal field size of 10 x 10 cm2 was chosen and 100 MU were delivered for each portal. The largest difference between computed and measured doses for those posterior fields was within 1.7%. A comparison between computed and measured transmissions for the aforementioned fields was performed and the results were found to agree within 1.1%. The differences between computed and measured doses for different field sizes, ranging from 5 x 5 cm2 to 25 x 25 cm2 in 5 cm increments, were within 2%. Measured and computed PDD curves with and without the couch agree from the surface up to 30 cm depth. The PDDs indicate a surface dose increase resulting from the carbon fiber couch field modification. The carbon fiber couch attenuation for individual posterior oblique fields (75 degrees) can be in excess of 8% depending on the beam energy and field size. When the couch is contoured in Pinnacle3 its attenuation properties are modeled to within 1.7% with respect to measurements. These results demonstrate that appropriate contouring together with relevant density information for the contours is sufficient for adequate modeling of carbon fiber supporting devices by modern commercial treatment planning systems.

O3 and UV/O3 oxidation of organic constituents of biotreated municipal wastewater.

Dissolved organic matter (DOM) in the biotreated effluent of a municipal wastewater treatment plant was separated by XAD-8 and XAD-4 resins into four fractions: hydrophobic acids, non-acid hydrophobics, transphilics and hydrophilics. Ozonation with and without ultraviolet (UV) enhancement removed most UV-absorbing substances in the first 30 min achieving 78% and 63% reduction in UV254, respectively; the UV enhancement resulted in a greater reduction in dissolved organic carbon (DOC) (90% vs. 36%). Ozone reacted sequentially with aromatic hydrophobics, transphilics, and then hydrophilics; however, under UV, it reacted with all four organic fractions simultaneously. Low-MW hydrophilics were the most abundant fraction in the ozone-treated effluent.

Effects of the solvent evaporation technique on the degree of conversion of one-bottle adhesive systems.

This study evaluated the effect of four methods of solvent evaporation on the degree of conversion (DC) of seven one-bottle adhesive systems: Excite (EX), ONE-STEP (OS), Optibond Solo Plus (OB), Prime&Bond 2.1 (PB), Prime&Bond NT (NT), Single Bond (SB) and Single Bond Plus (SP) using Fourier Transform Infrared Analysis (FTIR). Adhesive resins were: 1) applied to KBr pellet surfaces and left undisturbed for 30 seconds (condition 1), 2) left undisturbed for 30 seconds and air-dried with an air stream for 10 seconds (condition 2), 3) left undisturbed for 60 seconds (condition 3) and 4) left undisturbed for 60 seconds and air-dried for 10 seconds (condition 4) before curing. FTIR spectra were obtained and the DC was calculated by comparing the ratio of aliphatic/aromatic double carbon bonds before and after light-activation for 10 seconds (XL 3000, 3M). The results of each product were analyzed by one-way repeated measure ANOVA and post-hoc Tukey's test (p<0.05). The DC of PB, NT, OB and SP adhesives was not affected by the four evaporation conditions, while the DC of EX, OS and SB changed according to the evaporation method. The results suggested that the DC of some adhesives was similar regardless of the evaporation method when no water from dentin or rinsing was involved. Other bonding agents showed higher DC after specific conditions of solvent evaporation.

Polymerization eficiency of dual-polymerized resin cements light-irradiated through ceramics and laboratory-processed resin composite.

The purpose of the study was to determine the influence of light-irradiation through two ceramic and one resin composite materials on the degree of remaining double carbon bonds in 3 dual-polymerized resin cements. After mixing, the cement was inserted into a 0.5 mm deep recess in a silicon mold, covered with one ceramic or resin composite rectangular block and exposed through the block with the light from a halogen polymerization unit for 40 s. Infrared spectroscopic analysis was used to record the degree of remaining double carbon bonds. Light irradiation through 2 mm-thick ceramic and resin composite materials increased the degree of remaining double carbon bonds relative to the direct photopolymerization analogues.

Sonochemical preparation of carbon nanosheet from carbon black.

Preparation of carbon nanosheet via ultrasound irradiation of carbon black under ambient conditions was reported for the first time. The structure of resulting carbon nanosheet was characterized by TEM, HRTEM, EDX and AFM. The experimental results showed that the carbon nanosheet is composed of ordered graphite carbon layers with a thickness of several nanometers.

The effect of soft-start polymerization by second generation LEDs on the degree of conversion of resin composite.

Fourier-Transform (FT)--Raman spectroscopy was used to evaluate in vitro the degree of conversion (DC) of Charisma dental composite cured by three different light curing units (LCUs) using soft-start and normal protocols. Eighty circular blocks of resin (7 mm in diameter x 2.5 mm thick) were prepared and cured using the following sources: halogen light (Degulux soft-start, n = 20, G1-G2), low power light emitting diode (LED) with transparent polymer tip (LD13, n = 20, G3-G4) and fiber optic tip (LD13, n = 20, G5-G6) and, finally, high power LED (Radii, n = 20, G7-G8). The top and bottom surfaces of the blocks were analyzed by FT-Raman spectroscopy. The respective DCs were estimated calculating the peak height ratio of the aliphatic C=C (1640 cm(-1)) and aromatic C=C (1610 cm(-1)) Raman modes. The DC at the surfaces ranged between 50% and 60% for the top and 46% and 58% for the bottom. The halogen light and high power LED LCUs with the soft-start and normal protocols produced the highest DC values of dental composite at both surfaces (p < 0.001). Curing by low power LED in the soft-start protocol did not produce adequate DC at the depth of 2.5 mm. The type of LCU light guide tip did not present a significant statistical difference in the final DC of the dental composite (p > 0.05).

Great improvement on tetracycline removal using ZnO rod-activated carbon fiber composite prepared with a facile microwave method.

New composite materials of activated carbon fiber (ACF) coated with zinc oxide (ZnO) were obtained by applying a green, cost-effective and rapid synthetic route using a commercial microwave oven. ZnO rods with a uniform and stable structure and an average diameter of 0.3-0.5µm and length of 1.0-1.5µm were achieved after only 3-min microwave treatment. The properties of ZnO were efficiently transferred to ACF, such that the resulting material, termed ZnO rod-ACF, demonstrated a promising potential as an efficient photocatalyst and simultaneously as an adsorbent. Pharmaceutical tetracycline at a concentration of 40mg/L was used to evaluate the organic pollutant removal capacity of the synthesized materials. At pH 8, ZnO rod-ACF exhibited excellent removal capacity (over 99%) and mineralization (90.7%) of tetracycline in aqueous solution within 1h under UV irradiation. The stability of ZnO rod-ACF was maintained and the mineralization of tetracycline was also maintained at 81.35% after multiple usage cycles. The photodegradation pathways of tetracycline were proposed based on the identified reaction intermediates.

Electron beam transport in heterogeneous slab media from MeV down to eV.

An optimized Monte Carlo method based on the null collision technique and on the treatment of individual interactions is used for the simulation of the electron transport in multilayer materials from high energies (MeV or several hundred of keV) down to low cutoff energies (between 1 and 10 eV). In order to better understand the electron transport and the energy deposition at the interface in the composite application framework, two layer materials are considered (carbon and polystyrene with densities of 1.7 g cm(-3) and 1.06 g cm(-3), respectively) under two slab or three slab configurations as, e.g. a thin layer of carbon sandwiched between two polystyrene layers. The electron-matter cross-sections (electron-carbon and electron-polystyrene) used in the case of pure material (carbon and polystyrene) as well as our Monte-Carlo code have been first validated. The boundary interface layer is considered without any mean free path truncation and with a rigorous treatment of the backscattered and also the forward scattered electrons from one layer to another. The large effect of the choice of a low cutoff energy and the dissociation process consideration are also clearly shown in the heterogeneous multi-layer media more particularly on the secondary electron emission, inelastic collision number and energy spectra.

Degree of remaining C=C bonds, polymerization shrinkage and stresses of dual-cured core build-up resin composites.

This study measured the degree of remaining C=C bonds (RDB), linear polymerization shrinkage (LPS) and polymerization stresses (PS) of dual-cured resin composite build-up materials using a variety of light exposure scenarios. Four commercially available materials were used: Bis-Core, FluoroCore, Build-it! and Permalute. The RDB was measured using FTIR spectroscopy, and custom-made devices were used to measure LPS and PS values. Data were obtained using three different modes of photoactivation: NLC (No Light-Curing); ILC (Immediate Light-Curing, where 60 second light-curing was applied at the start of the observation period); and DLC (Delayed Light-Curing, where 60-second light-curing was applied 10 minutes from the start of the observation period). Statistical evaluation of the data at the end of the 13-minute observation period was performed with two-way analysis of variance (ANOVA), Tukey's Studentized Range (HSD) Test (p=0.05) and simple linear regression. Differences in the development of LPS and PS during the 13 minutes were studied using mathematical calculus. Bis-Core presented the highest RDB and Permalute the lowest when ILC was applied, while no differences were found between Build-it! and FluoroCore and NLC and DLC increased RDB for FluoroCore and Permalute compared to ILC; whereas, no differences were noted for Build-it! and Bis-Core. Using DLC, a decrease in RDB was found only for Build-it! FluoroCore and Permalute exhibited a reduction in LPS and PS using NLC relative to ILC. No differences in LPS and PS values were detected for the materials Bis-Core and Build-it! when subjected to NLC or DLC, compared to ILC. Simple linear regression showed that only the two polymerization shrinkage properties studied were highly correlated (LPS-PS r2=0.85). The RDB rate was not correlated with either polymerization shrinkage properties (RDB-LPS r2=0.40; RDB-PS r2=0.57). A study of the evolution of the real-time curves of percentage values of LPS and PS showed that these properties evolved in a similar exponential mode and that, most often, there was a delay in the development of PS.

Heterogeneous photo-Fenton degradation of acid red B over Fe2O3 supported on activated carbon fiber.

Fe2O3 supported on activated carbon fiber (Fe2O3/ACF) was prepared via an impregnation method and characterized by X-ray diffraction, scanning electron microscopy and BET analysis. The results indicated that Fe2O3 with small particle size was highly dispersed on the surface of the ACF and the introduction of Fe2O3 did not change the ACF pore structure. Fe2O3/ACF exhibited a higher Fenton efficiency for the degradation of acid red B (ARB), especially under simulated solar irradiation. Complete decoloration of the ARB solution and 43% removal of TOC could be achieved within 200 min under optimal conditions. It was verified that more ˙OH radicals were generated in the photo-assisted Fenton process and involved as active species in ARB degradation. FTIR analysis indicated that the degradation of ARB was initiated through the cleavage of -N=N-, followed by hydroxylation and opening of phenyl rings to form aliphatic acids, and further oxidation of aliphatic acids would produce CO2 and H2O. Moreover, Fe2O3/ACF maintained its activity after being reused 4 times and the release of iron from the catalyst was found to be insignificant during the Fenton and photo-Fenton processes, indicating that Fe2O3/ACF had good long-term stability.

Effects of erbium,chromium:YSGG laser irradiation on root canal walls: a scanning electron microscopic and thermographic study.

The present study evaluates the morphological changes in root canal walls and temperature changes at root surfaces as a result of intracanal irradiation by erbium,chromium:YSGG laser under various conditions in vitro. Sixty single-rooted human teeth were examined. Root canals were prepared, and laser irradiation was performed using an optic fiber at output powers ranging from 1 to 6 W with or without water spray cooling. Specimens were evaluated by stereoscopy, scanning electron microscopy, and thermography. Carbonization and cracks were observed in all samples irradiated without cooling, whereas little or no carbonization and no smear layer or debris were observed in samples irradiated with cooling. Maximum temperature rise at irradiation without cooling was above 37 degrees C, whereas that at irradiation with cooling was 8 degrees C. Results of the present study indicate that erbium,chromium:YSGG laser irradiation with water spray cooling is a useful method for removal of smear layer and debris from root canals.