Robustness of hypofractionated breast radiotherapy after breast-conserving surgery with free breathing.

Purpose: This study aimed to evaluate the robustness with respect to the positional variations of five planning strategies in free-breathing breast hypofractionated radiotherapy (HFRT) for patients after breast-conserving surgery. Methods: Twenty patients who received breast HFRT with 42.72 Gy in 16 fractions were retrospectively analyzed. Five treatment planning strategies were utilized for each patient, including 1) intensity-modulated radiation therapy (IMRT) planning (IMRTpure); 2) IMRT planning with skin flash tool extending and filling the fluence outside the skin by 2 cm (IMRTflash); 3) IMRT planning with planning target volume (PTV) extended outside the skin by 2 cm in the computed tomography dataset (IMRTePTV); 4) hybrid planning, i.e., 2 Gy/fraction three-dimensional conformal radiation therapy combined with 0.67 Gy/fraction IMRT (IMRThybrid); and 5) hybrid planning with skin flash (IMRThybrid-flash). All plans were normalized to 95% PTV receiving 100% of the prescription dose. Six additional plans were created with different isocenter shifts for each plan, which were 1 mm, 2 mm, 3 mm, 5 mm, 7 mm, and 10 mm distally in the X (left-right) and Y (anterior-posterior) directions, namely, (X,Y), to assess their robustness, and the corresponding doses were recalculated. Variation of dosimetric parameters with increasing isocenter shift was evaluated. Results: All plans were clinically acceptable. In terms of robustness to isocenter shifts, the five planning strategies followed the pattern IMRTePTV, IMRThybrid-flash, IMRTflash, IMRThybrid, and IMRTpure in descending order. V 95% of IMRTePTV maintained at 99.6% ± 0.3% with a (5,5) shift, which further reduced to 98.2% ± 2.0% with a (10,10) shift. IMRThybrid-flash yielded the robustness second to IMRTePTV with less risk from dose hotspots, and the corresponding V 95% maintained >95% up until (5,5). Conclusion: Considering the dosimetric distribution and robustness in breast radiotherapy, IMRTePTV performed best at maintaining high target coverage with increasing isocenter shift, while IMRThybrid-flash would be adequate with positional uncertainty<5 mm.

Bimetallic Cu-Fe catalysts on MXene for synergistically electrocatalytic conversion of nitrate to ammonia.

NO3- is a common water pollutant that can serve as a potential nitrogen source for electrocatalytic NH3 production. However, an efficient and complete removal of low NO3- concentrations remains a challenge. Fe1Cu2@MXene bimetallic catalysts were constructed on two-dimensional Ti3C2Tx MXene carriers via a simple solution-based synthetic method and used for the electrocatalytic reduction of NO3-. The combination of the rich functional groups, high electronic conductivity on the MXene surface, and the synergistic effect between the Cu and Fe sites enabled the composite to effectively catalyse NH3 synthesis, with a 98% conversion of NO3- in 8 h and a selectivity for NH3 of up to 99.6%. In addition, Fe1Cu2@MXene showed excellent environmental and cyclic stability at various pH values and temperatures over multiple (14) cycles. Semiconductor analysis techniques and electrochemical impedance spectroscopy confirmed that the synergistic effect provided by the dual active sites of the bimetallic catalyst enabled fast electron transport. This study provides new insights into the synergistic promotion of NO3- reduction reactions using bimetals.

Coordination Symmetry Breaking of Single-Atom Catalysts for Robust and Efficient Nitrate Electroreduction to Ammonia.

Nitrate electrocatalytic reduction (NO3 RR) for ammonia production is a promising strategy to close the N-cycle from nitration contamination, as well as an alternative to the Haber-Bosch process with less energy consumption and carbon dioxide release. However, current long-term stability of NO3 RR catalysts is usually tens of hours, far from the requirements for industrialization. Here, symmetry-broken Cusingle-atom catalysts are designed, and the catalytic activity is retained after operation for more than 2000 h, while an average ammonia production rate of 27.84 mg h-1 cm-2 at an industrial level current density of 366 mA cm-2 is achieved, obtaining a good balance between catalytic activity and long-term stability. Coordination symmetry breaking is achieved by embedding one Cu atom in graphene nanosheets with two N and two O atoms in the cis-configuration, effectively lowering the coordination symmetry, rendering the active site more polar, and accumulating more NO3 - near the electrocatalyst surface. Additionally, the cis-coordination splits the Cu 3d orbitals, which generates an orbital-symmetry-matched π-complex of the key intermediate *ONH and reduces the energy barrier, compared with the σ-complex generated with other catalysts. These results reveal the critical role of coordination symmetry in single-atom catalysts, prompting the design of more coordination-symmetry-broken electrocatalysts toward possible industrialization.

Effect of plan complexity on the dosimetry, delivery accuracy, and interplay effect in lung VMAT SBRT with 6 MV FFF beam.

PURPOSE: The purpose of this study is to investigate the effect of plan complexity on the dosimetry, delivery accuracy, and interplay effect in lung stereotactic body radiation therapy (SBRT) using volumetric modulated arc therapy (VMAT) with 6 MV flattening-filter-free (FFF) beam. METHODS: Twenty patients with early stage non-small cell lung cancer were included. For each patient, high-complexity (HC) and low-complexity (LC) three-partial-arc VMAT plans were optimized by adjusting the normal tissue objectives and the maximum monitoring units (MUs) for a Varian TrueBeam linear accelerator (Varian Medical Systems, Palo Alto, CA, USA) using 6 MV FFF beam. The effect of plan complexity was comprehensively evaluated in three aspects: (1) The dosimetric parameters, including CI, D2cm, R50, and dose-volume parameters of organs at risk were compared. (2) The delivery accuracy was assessed by pretreatment quality assurance for two groups of plans. (3) The motion-induced dose deviation was evaluated based on point dose measurements near the tumor center by using a programmable phantom. The standard deviation (SD) and maximum dose difference of five measurements were used to quantify the interplay effect. RESULTS: The dosimetry of HC and LC plans were similar except the CI (1.003 ± 0.032 and 1.026 ± 0.043, p = 0.030) and Dmax to the spinal cord (10.6 ± 3.2 and 9.9 ± 3.0, p = 0.012). The gamma passing rates were significantly higher in LC plans for all arcs (p < 0.001). The SDs of HC and LC plans ranged from 0.5-16.6% and 0.03-2.9%, respectively, under the conditions of one-field, two-field, and three-field delivery for each plan with 0.5, 1, 2, and 3 cm motion amplitudes. The maximum dose differences of HC and LC plans were 34.5% and 9.1%, respectively. CONCLUSION: For lung VMAT SBRT, LC plans have a higher delivery accuracy and a lower motion-induced dose deviation with similar dosimetry compared with HC plans.

Straightforward synthesis of quinazolin-4(3H)-ones via visible light-induced condensation cyclization.

A green, simple and efficient method is developed for the synthesis of quinazolin-4(3H)-ones via visible light-induced condensation cyclization of 2-aminobenzamides and aldehydes under visible light irradiation. The reaction proceeds using fluorescein as a photocatalyst in the presence of TBHP without the need for a metal catalyst. In addition, this reaction tolerates a broad scope of substrates and could afford a variety of desirable products in good to excellent yields. Thus, the present synthetic method provides a straightforward strategy for the synthesis of quinazolin-4(3H)-ones.

Selection Strategy of Jaw Tracking in VMAT Planning for Lung SBRT.

PURPOSE: This study aimed to investigate the dosimetric effect and delivery reliability of jaw tracking (JT) with increasing planning target volume (PTV) for lung stereotactic body radiation therapy (SBRT) plans. A threshold of PTV was proposed as a selection criterion between JT and fixed-jaw (FJ) techniques. METHODS: A total of 28 patients with early-stage non-small-cell lung cancer were retrospectively included. The PTVs ranged from 4.88 cc to 68.74 cc, prescribed with 48 Gy in four fractions. Three-partial-arc volumetric modulated arc therapy (VMAT) plans with FJ and with JT were created for each patient with the same optimization objectives. These two sets of plans were compared using metrics, including conformity index (CI), V50%, R50%, D2cm, dose-volume parameters of organs at risk, and monitor units (MUs). The ratio of small subfields (<3 cm in either dimension), %SS, was acquired as a surrogate for the small-field uncertainty. Statistical analyses were performed to evaluate the correlation between the differences in these parameters and the PTV. RESULTS: The V50%, R50%, D2cm, and V20Gy, D1,500cc, and D1,000cc of the lung showed a statistically significant improvement in JT plans as opposed to FJ plans, while the number of MU in JT plans was higher by an average of 1.9%. Between FJ and JT plans, the PTV was strongly correlated with the differences in V50%, moderately correlated with those in V20Gy of the lung, and weakly correlated with those in D2cm and D1,500cc of the lung. By using JT, %SS was found to be negatively correlated with the PTV, and the PTV should be at least approximately 12.5 cc for an expected %SS <50%, which was 15 cc for a %SS <20% and 20 cc for a %SS <5%. CONCLUSIONS: Considering the dosimetric differences and small-field uncertainties, JT could be selected using a PTV threshold, such as 12.5, 15, or 20 cc, on the basis of the demand of delivery reliability for lung SBRT.

Optimization of collimator angles in dual-arc volumetric modulated arc therapy planning for whole-brain radiotherapy with hippocampus and inner ear sparing.

To optimize the collimator angles in dual-arc volumetric modulated arc therapy (VMAT) plans for whole-brain radiotherapy with hippocampus and inner ear sparing (HIS-WBRT). Two sets of dual-arc VMAT plans were generated for 13 small-cell lung cancer patients: (1) The collimator angles of arcs 1 and 2 (θ1/θ2) were 350°/10°, 350°/30°, 350°/45°, 350°/60°, and 350°/80°, i.e., the intersection angle of θ1 and θ2 (Δθ) increased. (2) θ1/θ2 were 280°/10°, 300°/30°, 315°/45°, 330°/60°, and 350°/80°, i.e., Δθ = 90°. The conformity index (CI), homogeneity index (HI), monitor units (MUs), and dosimetric parameters of organs-at-risk were analyzed. Quality assurance for Δθ = 90° plans was performed. With Δθ increasing towards 90°, a significant improvement was observed for most parameters. In 350°/80° plans compared with 350°/10° ones, CI and HI were improved by 1.1% and 25.2%, respectively; MUs were reduced by 16.2%; minimum, maximum, and mean doses (D100%, Dmax, and Dmean, respectively) to the hippocampus were reduced by 5.5%, 6.3%, and 5.4%, respectively; Dmean to the inner ear and eye were reduced by 0.7% and 5.1%, respectively. With Δθ kept at 90°, the plan quality was not significantly affected by θ1/θ2 combinations. The gamma-index passing rates in 280°/10° and 350°/80° plans were relatively lower compared with the other Δθ = 90° plans. Δθ showed a significant effect on dual-arc VMAT plans for HIS-WBRT. With Δθ approaching 90°, the plan quality exhibited a nearly continuous improvement, whereas with Δθ = 90°, the effect of θ1/θ2 combination was insignificant.

Built-in Electric Field Triggered Interfacial Accumulation Effect for Efficient Nitrate Removal at Ultra-Low Concentration and Electroreduction to Ammonia.

A built-in electric field in electrocatalyst can significantly accumulate higher concentration of NO3 - ions near electrocatalyst surface region, thus facilitating mass transfer for efficient nitrate removal at ultra-low concentration and electroreduction reaction (NO3 RR). A model electrocatalyst is created by stacking CuCl (111) and rutile TiO2 (110) layers together, in which a built-in electric field induced from the electron transfer from TiO2 to CuCl (CuCl_BEF) is successfully formed . This built-in electric field effectively triggers interfacial accumulation of NO3 - ions around the electrocatalyst. The electric field also raises the energy of key reaction intermediate *NO to lower the energy barrier of the rate determining step. A NH3 product selectivity of 98.6 %, a low NO2 - production of <0.6 %, and mass-specific ammonia production rate of 64.4 h-1 is achieved, which are all the best among studies reported at 100 mg L-1 of nitrate concentration to date.

Surfactant-Free, One-Step Synthesis of Lead-Free Perovskite Hollow Nanospheres for Trace CO Detection.

Owing to their special photoelectric properties, halide perovskites have always attracted research attention. Hollow-structured halide perovskites have many practical applications but are challenging to prepare as most template methods violate their poor chemical and thermal stability. In this study, novel halide perovskite Cs2 PdBr6 hollow nanospheres are prepared using a template-free method; specifically, large quantities of highly pure lead-free halide perovskite Cs2 PdBr6 hollow nanospheres are produced at 30 °C without a surfactant. These ultrapure nanospheres exhibit superiority in chemresistive detection of CO with a detection limit of 50 ppb, which is the lowest among all the reported CO sensing materials. Moreover, in situ sum-frequency-generation spectra and density functional theory calculations reveal that the high sensitivity is attributable to the large specific surface area and surfactant-free surface of rich Br- vacancies that favor CO binding. Overall, this work provides insight on regulation of the halide perovskite structure and the use of hollow spheres in gas-sensing applications.

Technical Note: Induced radioactivity in stereotactic body radiation therapy with a flattening-filter-free 10 MV beam model.

PURPOSE: The induced radioactivity in stereotactic body radiation therapy with a flattening-filter-free 10 MV beam model (10 FFF SBRT) was investigated for the risk to therapists. METHODS: This study was performed on a Varian TrueBeam linac. The induced radioisotopes were identified by γ spectroscopy. The dose rate from the induced activity was measured for 12 treatment cycles in 4 h continuously. The impacts of the characteristic factors of 10 FFF SBRT on the dose rate were investigated, including monitor units (MU), beam rate, field size, and flattening filter. The dose rate was compared between the SBRT plans and conventional fractionation plans. A mathematical model was used to analyze the results and estimate the annual dose to therapists. RESULTS: (a) The induced radioisotopes included 24 Na, 28 Al, 38 Cl, 56 Mn, 66 Cu, 187 W, and 196 Au. (b) In 4 h, the total dose contribution ratios were more than 70% for 28 Al, about 20% for 56 Mn, and 10% for all other long-lived radioisotopes, combining doses at the isocenter and end of the treatment couch. (c) The dose rate showed a nonlinear growth with increasing MU and beam rate. The variation of the dose rate was complicated with the jaw field and not sensitive to the MLC field. The removal of the flattening filter reduced the dose rate by about 40%. The dose level of SBRT was two to three times that of conventional fractionation. (d) The estimated annual dose to therapists was up to 0.20 mSv/y. CONCLUSIONS: The induced radioactivity in 10 FFF SBRT was higher compared with that in 10 MV conventional fractionation. More MU and higher beam rate were the primary factors that caused the increase. The therapists should wait longer after beam-off to reduce the occupational dose. In addition, aluminum and manganese should be less used in the treatment room.

Surface Functionalization of Single-Layered Ti3C2Tx MXene and Its Application in Multilevel Resistive Memory.

MXenes are a new type of two-dimensional material, and they have attracted extensive attention because of their outstanding conductivity and rich surface functional groups that make surface engineering easy and possible for adapting to diverse applications. However, there are scarce studies on surface engineering of MXene. Herein, we demonstrate for the first time that octylphosphonic acid-modified Ti3C2Tx MXene can be used as an active layer for memory devices and exhibits stable ternary memory behavior. Low threshold voltage, steady retention time, clearly distinguishable resistance states, high ON/OFF rate, OFF/ON1/ON2 = 1:102.7:104.1, and considerable ternary yield (58%) were obtained. In the proof of the mechanism, in situ conductive atomic force microscopy was conducted and the electrode-area relationship was analyzed to demonstrate that charge trapping and filament conduction are more suitable in the nonvolatile information memory of Ti3C2Tx-OP MXene devices. In addition, a polyethylene-terephthalate-based flexible Ti3C2Tx-OP memory device can maintain its stable ternary memory performance after being bent 5000 times. This work provides an easy method for surface modification of MXene and broadens the field of MXene.

One-Step Fabrication of Bio-Compatible Coordination Complex Film on Diverse Substrates for Ternary Flexible Memory.

Recently, resistance random access memories (RRAMs) have been studied extensively, because the demand for information storage is increasing. However, it remains challenging to obtain a flexible device because the active materials involved need to be nontoxic, nonpolluting, distortion-tolerable, and biodegradable as well adhesive to diverse flexible substrates. In this paper, tannic acid (TA) and an iron ion (FeIII ) coordination complex were employed as the active layer in a sandwich-like (Al/active layer/substrate) device to achieve memory performance. A nontoxic, biocompatible TA-FeIII coordination complex was synthesized by a one-step self-assembly solution method. The retention time of the TA-FeIII memory performance was up to 15 000 s, the yield up to 53 %. Furthermore, the TA-FeIII coordination complex can form a high-quality film and shows stable ternary memory behavior on various flexible substrates, such as polyethylene terephthalate (PET), polyimide (PI), printer paper, and leaf. The device can be degraded by immersing it in vinegar solution. Our work will broaden the application of organic coordination complexes in flexible memory devices with diverse substrates.

Visible-Light-Induced C-C Coupling Reaction to Synthesize Bipyridine From 3-Cyano-1,4-Dihydropyridines.

A concise and efficient photocatalytic C-C coupling of 1-benzyl-3-cyano-1, 4-dihydropyridine for synthesis of 1,1'-dibenzyl-3, 3'-dicyano-1,1',4,4'-tetrahydro-4, 4'-bipyridine is described. The reporter system provides a novel technique that facilitates synthesis of C-C coupling derivatives without addition of transition metals and oxidants or other additives. A plausible synthetic pathway is proposed, and the coupling product was characterized via nuclear magnetic resonance spectroscopy (1H and 13C NMR), high-resolution electrospray ionization mass spectrometry (ESI-HRMS) and X-ray analyses.

Discovery of novel picolinamide-based derivatives as novel VEGFR-2 kinase inhibitors: synthesis, in vitro biological evaluation and molecular docking.

Vascular endothelial growth factor receptor-2 (VEGFR-2) plays a crucial role in tumor angiogenesis, and inhibition of the VEGFR-2 signaling pathway has emerged as an attractive target for cancer therapy. In our effort, a novel series of picolinamide-based derivatives were designed and synthesized as potent and effective VEGFR-2 inhibitors. All the newly prepared compounds were evaluated in vitro for their antiproliferative activity against A549 and HepG2 cell lines. Among the new compounds, 8j and 8l exhibited better activity against both A549 and HepG2 cell lines. Molecular docking was performed to investigate the binding capacity and binding mode with VEGFR-2 (PDB code: ; 4ASD).

Mussel-Inspired Polydopamine Coating for Flexible Ternary Resistive Memory.

In recent years, numerous organic molecules and polymers carrying various functional groups were synthesized and used in fabrication of wearable electronic devices. Compared to previous materials that suffer from poisonousness, stiffness and complex film fabrication, we circumvent above matters by taking advantage of mussel-inspired polydopamine as our active material to realize resistive random access memories (RRAMs). Polydopamine thin films were grown on indium tin oxide glass catalyzed by Cu2 SO4 /H2 O2 and characterized by Fourier infrared spectroscopy (FT-IR), UV/Vis spectroscopy and scanning electron microscopy. The Al/Polydopamine film/ITO devices possess ternary memory behavior with good ternary device yield with two threshold voltages around 1.50 V and 3.50 V, long data retention over 104  s of continuous reading or 104 pulse reading. The two resistance switchings are attributed to defects functioning as charge traps and the formation of conductive filaments. A flexible device based on Al/polydopamine film/ITO/polyethylene terephthalate retains its ternary memory behavior after being bent with a bending radius of 1.54 cm and bending cycles up to 5000, demonstrating good compatibility and flexibility of polydopamine.

Design, synthesis and biological evaluation of pyrimidine-based derivatives as VEGFR-2 tyrosine kinase inhibitors.

Vascular endothelial growth factor receptor-2 (VEGFR-2) plays a crucial role in tumor angiogenesis, and inhibition of the VEGFR-2 signaling pathway has already become an attractive approach for cancer therapy. In this study, a novel pyrimidine-based derivative 7j was designed as lead compound, and three series of potent VEGFR-2 inhibitors were synthesized and biologically evaluated against A549 and HepG2 cell lines. Compounds 7d, 9s and 13n exhibited superior inhibitory activities against A549 cell with IC50 ranged from 9.19 to 13.17 µM and HepG2 cell with IC50 ranged from 11.94 to 18.21 µM compared to those of Pazopanib (IC50 = 21.18 and 36.66 µM). In addition, molecular docking study was performed to investigate the binding capacity and binding mode between target compounds and VEGFR-2.

Synthesis and evaluation of pyridinium polyoxometalates as anti-HIV-1 agents.

The unique properties of polyoxometalates, such as molecular polarity, redox potential, surface charge distribution, shape and acidity, influence their response of recognition to targeted biological macromolecules. By using PM-19 (K7PTi2W10O40) as a lead-compound, a series of novel pyridinium polyoxometalates (A7PTi2W10O40), which hadn't been reported in literatures, were designed and synthesized. The evaluation was conducted using the single-cycle pseudovirus infection assay (TZM-bl assay), CCK-8 method was used for determining the cytotoxicity. The results indicated that the designed pyridinium polyoxometalates had a lower toxicity to TZM-bl cells, and showed higher inhibitory activity against HIV-1 virus.