An investigation of the corrosion behavior of zinc-coated stainless steel orthodontic wires: the effect of physical vapor deposition method.

BACKGROUND: Releasing of metal ions might implicate in allergic reaction as a negative subsequent of the corrosion of Stainless Steel (SS304) orthodontic wires. The aim of this study was to evaluate the corrosion resistance of zinc-coated (Zn-coated) SS orthodontic wires. METHODS: Zinc coating was applied on SS wires by PVD method. Electrochemical impedance spectroscopy (EIS), Potentiodynamic polarization tests and Tafel analysis methods were used to predict the corrosion behavior of Zn-coated and uncoated SS wires in both neutral and acidic environments. RESULTS: The values of Ecorr ,icorr and Rct ,which were the electrochemical corrosion characteristics, reported better corrosion behavior of Zn-coated SS wires against uncoated ones in both artificial saliva and fluoride-containing environments. Experimental results of the Tafel plot analyses were consistent with that of electrochemical impedance spectroscopy analyses for both biological solutions. CONCLUSION: Applying Zn coating on bare SS orthodontic wire by PVD method might increase the corrosion resistance of the underlying stainless-steel substrate.

Lanthanide Inorganic Nanoparticles Enhance Semiconducting Polymer Nanoparticles Afterglow Luminescence for In Vivo Afterglow/Magnetic Resonance Imaging.

Dual/multimodal imaging strategies are increasingly recognized for their potential to provide comprehensive diagnostic insights in cancer imaging by harnessing complementary data. This study presents an innovative probe that capitalizes on the synergistic benefits of afterglow luminescence and magnetic resonance imaging (MRI), effectively eliminating autofluorescence interference and delivering a superior signal-to-noise ratio. Additionally, it facilitates deep tissue penetration and enables noninvasive imaging. Despite the advantages, only a limited number of probes have demonstrated the capability to simultaneously enhance afterglow luminescence and achieve high-resolution MRI and afterglow imaging. Herein, we introduce a cutting-edge imaging platform based on semiconducting polymer nanoparticles (PFODBT) integrated with NaYF4@NaGdF4 (Y@Gd@PFO-SPNs), which can directly amplify afterglow luminescence and generate MRI and afterglow signals in tumor tissues. The proposed mechanism involves lanthanide nanoparticles producing singlet oxygen (1O2) upon white light irradiation, which subsequently oxidizes PFODBT, thereby intensifying afterglow luminescence. This innovative platform paves the way for the development of high signal-to-background ratio imaging modalities, promising noninvasive diagnostics for cancer.

Legumain-Triggered Macrocyclization of Radiofluorinated Tracer for Enhanced PET Imaging.

Enhancing the accumulation and retention of small-molecule probes in tumors is an important way to achieve accurate cancer diagnosis and therapy. Enzyme-stimulated macrocyclization of small molecules possesses great potential for enhanced positron emission tomography (PET) imaging of tumors. Herein, we reported an 18F-labeled radiotracer [18F]AlF-RSM for legumain detection in vivo. The tracer was prepared by a one-step aluminum-fluoride-restrained complexing agent ([18F]AlF-RESCA) method with high radiochemical yield (RCY) (88.35 ± 3.93%) and radiochemical purity (RCP) (>95%). More notably, the tracer can be transformed into a hydrophobic macrocyclic molecule under the joint action of legumain and reductant. Simultaneously, the tracer could target legumain-positive tumors and enhance accumulation and retention in tumors, resulting in the amplification of PET imaging signals. The enhancement of radioactivity enables PET imaging of legumain activity with high specificity. We envision that, by combining this highly efficient 18F-labeled strategy with our intramolecular macrocyclization reaction, a range of radiofluorinated tracers can be designed for tumor PET imaging and early cancer diagnosis in the future.

Recovery of aluminum oxide and iron oxide from aluminum electrolysis iron-rich cover material and preparation of aluminum fluoride.

In aluminum electrolysis, the iron-rich cover material is formed on the cover material and the steel rod connecting the carbon anode. Due to the high iron content in the iron-rich cover material, it differs from traditional cover material and thus requires harmless recycling and treatment. A process was proposed and used in this study to recovery F, Al, and Fe elements from the iron-rich cover material. This process involved aluminum sulfate solution leaching for fluorine recovery and alkali-acid synergistic leaching for α-Al2O3 and Fe2O3 recovery were obtained. The optimal leaching rates for F, Na, Ca, Fe, and Si were 93.92, 96.25, 94.53, 4.48, and 28.87%, respectively. The leaching solution and leaching residue were obtained. The leaching solution was neutralized to obtain the aluminum hydroxide fluoride hydrate (AHFH, AlF1.5(OH)1.5·(H2O)0.375). AHFH was calcined to form a mixture of AlF3 and Al2O3 with a purity of 96.14%. The overall recovery rate of F in the entire process was 92.36%. Additionally, the leaching residue was sequentially leached with alkali and acid to obtain the acid leach residue α-Al2O3. The pH of the acid-leached solution was adjusted to produce a black-brown precipitate, which was converted to Fe2O3 under a high-temperature calcination, and the recovery rate of Fe in the whole process was 94.54%. Therefore, this study provides a new method for recovering F, Al, and Fe in iron-rich cover material, enabling the utilization of aluminum hazardous waste sources.

Enzyme Engineering Renders Chlorinase the Activity of Fluorinase.

Organofluorine compounds have attracted substantial attention owing to their wide application in agrochemistry. Fluorinase (FlA) is a unique enzyme in nature that can incorporate fluorine into an organic molecule. Chlorinase (SalL) has a similar mechanism as fluorinase and can use chloride but not fluoride as a substrate to generate 5'-chloro-deoxyadenosine (5'-ClDA) from S-adenosyl-l-methionine (SAM). Therefore, identifying the features that lead to this selectivity for halide ions is highly important. Here, we engineered SalL to gain the function of FlA. We found that residue Tyr70 plays a key role in this conversion through alanine scanning. Site-saturation mutagenesis experiments demonstrated that Y70A/C/S/T/G all exhibited obvious fluorinase activity. The G131S mutant of SalL, in which the previously thought crucial residue Ser158 for fluoride binding in FlA was introduced, did not exhibit fluorination activity. Compared with the Y70T single mutant, the double mutant Y70T/W129F increased 5'-fluoro-5-deoxyadenosine (5'-FDA) production by 76%. The quantum mechanics (QM)/molecular mechanics (MM) calculations suggested that the lower energy barriers and shorter nucleophilic distance from F- to SAM in the mutants than in the SalL wild-type may contribute to the activity. Therefore, our study not only renders SalL the activity of FlA but also sheds light on the enzyme selectivity between fluoride versus chloride.

Synthesis and Evaluation of Glycosyl Luciferins.

Measuring glycosidase activity is important to monitor any aberrations in carbohydrate hydrolase activity, but also for the screening of potential glycosidase inhibitors. To this end, synthetic substrates are needed which provide an enzyme-dependent read-out upon hydrolysis by the glycosidase. Herein, we present two new routes for the synthesis of caged luminescent carbohydrates, which can be used for determining glycosidase activity with a luminescent reporter molecule. The substrates were validated with glycosidase and revealed a clear linear range and enzyme-dependent signal upon the in situ generation of the luciferin moiety from the corresponding nitrile precursors. Besides, we showed that these compounds could directly be synthesized from unprotected glycosyl-α-fluorides in a two-step procedure with yields up to 75 %. The intermediate methyl imidate appeared a key intermediate which also reacted with d-cysteine to give the corresponding d-luciferin substrate rendering this a highly attractive method for synthesizing glycosyl luciferins in good yields.

Effect of Toothpaste Fluoride Concentration on Color Stability of Resin Composites: An In Vitro Study

ABSTRACT Objective: To investigate the effects of two different dentifrice fluoride concentrations on the color stability of the composite. Material and Methods: Twenty-seven specimens (2×4×5 mm) each of microfilled (Gradia, GC, Japan) and nanohybrid (Grandio, VOCO, Germany) composites were prepared. The specimens were randomly divided into six groups (control, Fluoflor caries protection toothpaste with 1450ppm Fluoride (EXW, France), and Fluoflor kids toothpaste with 500ppm Fluoride (EXW, France) (n = 9). The specimens were immersed in a mixture of artificial saliva and toothpaste in a ratio of 1:3 and applied for 60 seconds every 12 hours for 42 days. The control samples were incubated in artificial saliva at 37°C. Primary and secondary color measurements were performed using color parameters (L∗a∗b) with a spectrophotoshade (MHT Optic Research AG, Niederhasli, Switzerland). Data were analyzed using a two-way analysis of variance at a significance level of 0.05. Results: According to the two-way ANOVA analysis, there was no significant difference in color change between the composites and no difference in the level of discoloration between different fluoride concentrations(p>0.05). Also, None of the dentifrices caused clinically significant color changes(∆E˂3.3). Conclusion: No clinically unacceptable color changes were observed in the microfilled and nanofilled composites with different concentrations of fluoride toothpaste.

Covalent drug discovery using sulfur(VI) fluoride exchange warheads.

INTRODUCTION: Covalent drug discovery has traditionally focused on targeting cysteine, but the amino acid is often absent in protein binding sites. This review makes the case to move beyond cysteine labeling using sulfur (VI) fluoride exchange (SuFEx) chemistry to expand the druggable proteome. AREAS COVERED: Recent advances in SuFEx medicinal chemistry and chemical biology are described, which have enabled the development of covalent chemical probes that site-selectively engage amino acid residues (including tyrosine, lysine, histidine, serine, and threonine) in binding pockets. Areas covered include chemoproteomic mapping of the targetable proteome, structure-based design of covalent inhibitors and molecular glues, metabolic stability profiling, and synthetic methodologies that have expedited the delivery of SuFEx modulators. EXPERT OPINION: Despite recent innovations in SuFEx medicinal chemistry, focused preclinical research is required to ensure the field moves from early chemical probe discovery to the delivery of transformational covalent drug candidates. The authors believe that covalent drug candidates designed to engage residues beyond cysteine using sulfonyl exchange warheads will likely enter clinical trials in the coming years.

Efficient removal of fluoride on aluminum modified activated carbon: an adsorption behavioral study and application to remediation of ground water.

In recent times, ground water contamination by toxic elements is of great concern and it is to be addressed for consumption of human, animal, and plant growth. In this context, we have synthesized an adsorbent by modifying commercially available activated carbon with aluminum and tested for de-fluoridation studies. The activity results suggested that the optimized adsorbent is highly efficient in removing the fluoride from ground water. Adsorption maxima are obtained over a wide pH range from 4 to 9, with a contact time of 15 minutes at a dosage of 4 g/L. The results also revealed that the synthesized adsorbent is suitable for application in ground water without any pH adjustment and has exhibited 85%-95% tolerance for common anions in the range of 100-500 mg/L. Equilibrium adsorption isotherm models as well as kinetics of adsorption were applied for the system. An adsorption capacity of 20.4 mg/g and fast kinetics observed are most favorable for defluoridation. Reuse of adsorbent over repeated cycles was investigated. Residual amount of aluminum in treated water is found to be negligible. The removal of toxic elements like Pb, Cd, Cr, Cu, Ni, Zn, As, and Se under the optimized experimental conditions has also been investigated. Al-AC found to be a highly promising material for removal of fluoride and toxic metals from drinking water.

Development and Validation of an Educational Comic Book for Guidance on the Safe Use of Fluoride Toothpaste by Children

ABSTRACT Objective: To describe the elaboration and content validation of a comic book for guidance on the safe use of fluoride toothpaste by children. Material and Methods: Study on the development of educational technology carried out in four phases: 1 - literature review and script; 2 - elaboration of the material (illustrations, layout and design), 3 - validation (Content Validity Index = CVI and Flesch Readability Index = FI), 4 - pilot test to legitimize the material with the target population. Thirty-one individuals participated in the validation, being 07 expert judges and 24 representatives of the lay population, responsible for the daily care of preschool and school-age children. Results: In the validation, CVI= 0.97 (97%), indicating high agreement of the judges' answers; and FI = 92%, which corresponds to "very easy to understand" reading. In the pilot test carried out with the lay population, the 3 assessment blocks had CVI=1.0 (100%). Conclusion: The comic book proved to be valid regarding appearance and content and can be used for health education activities for adults on the use of fluoride toothpaste for oral hygiene in children.

Are inert glasses really inert?

OBJECTIVES: The aim of this study was to investigate the degradation of inert glass fillers which are commonly used in conventional resin-based composites to provide radiopacity, reduce the polymerization shrinkage and improve the mechanical properties. METHODS: 75 mg of five different glass powders (1 µm) was immersed separately into 50 mL of acetic acid (pH 4) and tris buffer (pH 7.4) for up to 4 weeks. At each time point the glass powder was filtered and dried for characterization using ATR-FTIR and XRD to assess the degradation behavior and crystallization. ICP-OES, ISE and pH measurements were performed on the supernatant solutions to monitor the pH and ion release. RESULTS: Although FTIR and XRD analysis showed no significant glass degradation or crystallization upon immersion, there was a substantial release of ions from the inert fillers, especially from BABFG and CDL. Barium release for these fillers were 270 and 165 ppm respectively. G018-373 glass presented the lowest ion release followed by GM27884 and BABG. The ion release was more pronounced in acidic conditions compared to neutral conditions apart from the fluoride release. SIGNIFICANCE: Inert glasses are not as inert as previously thought. This may result in leaching of ions, potentially causing toxicity, reduction in mechanical properties, increased wear and subsequent failure of the composite material. The ions released from the inert glass may interfere with other glass fillers such as bioactive glass fillers, inhibiting degradation of the bioactive glass, beneficial ion release from the bioactive glass, pH neutralization and apatite formation.

The Na+,K+-ATPase in complex with beryllium fluoride mimics an ATPase phosphorylated state.

The Na+,K+-ATPase generates electrochemical gradients of Na+ and K+ across the plasma membrane via a functional cycle that includes various phosphoenzyme intermediates. However, the structure and function of these intermediates and how metal fluorides mimick them require further investigation. Here, we describe a 4.0 Å resolution crystal structure and functional properties of the pig kidney Na+,K+-ATPase stabilized by the inhibitor beryllium fluoride (denoted E2-BeFx). E2-BeFx is expected to mimic properties of the E2P phosphoenzyme, yet with unknown characteristics of ion and ligand binding. The structure resembles the E2P form obtained by phosphorylation from inorganic phosphate (Pi) and stabilized by cardiotonic steroids, including a low-affinity Mg2+ site near ion binding site II. Our anomalous Fourier analysis of the crystals soaked in Rb+ (a K+ congener) followed by a low-resolution rigid-body refinement (6.9-7.5 Å) revealed preocclusion transitions leading to activation of the dephosphorylation reaction. We show that the Mg2+ location indicates a site of initial K+ recognition and acceptance upon binding to the outward-open E2P state after Na+ release. Furthermore, using binding and activity studies, we find that the BeFx-inhibited enzyme is also able to bind ADP/ATP and Na+. These results relate the E2-BeFx complex to a transient K+- and ADP-sensitive E∗P intermediate of the functional cycle of the Na+,K+-ATPase, prior to E2P.

New Cysteine-Containing PEG-Glycerolipid Increases the Bloodstream Circulation Time of Upconverting Nanoparticles.

Upconverting nanoparticles have unique spectral and photophysical properties that make them suitable for development of theranostics for imaging and treating large and deep-seated tumors. Nanoparticles based on NaYF4 crystals doped with lanthanides Yb3+ and Er3+ were obtained by the high-temperature decomposition of trifluoroacetates in oleic acid and 1-octadecene. Such particles have pronounced hydrophobic properties. Therefore, to obtain stable dispersions in aqueous media for the study of their properties in vivo and in vitro, the polyethylene glycol (PEG)-glycerolipids of various structures were obtained. To increase the circulation time of PEG-lipid coated nanoparticles in the bloodstream, long-chain substituents are needed to be attached to the glycerol backbone using ether bonds. To prevent nanoparticle aggregation, an L-cysteine-derived negatively charged carboxy group should be included in the lipid molecule.

Synchrotron radiation analysis of root dentin: the roles of fluoride and calcium ions in hydroxyapatite remineralization.

Although the use of fluoride for root caries control is reported to be effective, the mechanism of maintaining hydroxyapatite is still unclear. This study elucidates the roles of fluoride in the recrystallization of hydroxyapatite, and the impact of calcium to maintain the abundance of hydroxyapatite on acid-challenged root dentin with a novel approach - using synchrotron radiation. Root dentin samples obtained from 40 extracted human premolars were subjected to pH challenge in combination with fluoride treatment. The effect of fluoride on hydroxyapatite regeneration on the root was investigated by using a range of fluoride concentrations (1000-5000 p.p.m.) and the EDTA-chelation technique in vitro. Synchrotron radiation X-ray micro-computed tomography and X-ray absorption spectroscopy were utilized to characterize the chemical composition of calcium species on the surface of prepared samples. The percentage of hydroxyapatite and the relative abundance of calcium species were subsequently compared between groups. The absence of calcium or fluoride prevented the complete remineralization of hydroxyapatite on the surface of early root caries. Different concentrations of fluoride exposure did not affect the relative abundance of hydroxyapatite. Sufficient potency of 1000 p.p.m. fluoride solution in promoting hydroxyapatite structural recrystallization on the root was demonstrated. Both calcium and fluoride ions are prerequisites in a caries-prone environment. Orchestration of F- and Ca2+ is required for structural homeostasis of root dentin during acid attack. Sustainable levels of F- and Ca2+ might thus be a strict requirement in the saliva of the population prone to root caries. Fluoride and calcium contribute to structural homeostasis of tooth root, highlighting that routine fluoride use in combination with calcium replenishment is recommended for maintaining dental health. This study also demonstrates that utilization of synchrotron radiation could provide a promising experimental platform for laboratory investigation especially in the dental material research field.

Quantification of Casein in Baked Food Products by Selective Analysis of Phosphorylated Peptides Using Fluorous Derivatization with Liquid Chromatography-Tandem Mass Spectrometry Method.

Casein is one of the allergen proteins present in milk. Therefore, a quantification method for the selective analysis of casein using fluorous derivatization with LC-tandem mass spectrometry (LC-MS/MS) was developed. After two allergen proteins (αS1-casein and ß-casein) extracted from baked sugar cookies were tryptic digested, the obtained phosphorylated peptides were selectively derivatized by ß-elimination with Ba(NO3)2 under basic condition and Michael addition with perfluoroalkylthiol (1H,1H,2H,2H-perfluorooctanethiol, PFOT). In this study, YKVPQLEIVPN(pSer)AQQR (104-119 fragment from αS1-casein) and FQ(pSer)EEQQQTEDELQDK (33-48 fragment from ß-casein) obtained by tryptic digestion were selected as target peptides. The phosphorylated serine residue in each peptide was converted to a perfluoroalkyl group by derivatization. The obtained fluorous-derivatized peptides were analyzed by LC-MS/MS, to which a fluorous LC column was connected. Therefore, it was possible to analyze casein without being affected by the matrix components in the baked food sample. When the present method was applied to cookies with arbitrary amounts of αS1-casein and ß-casein, the obtained quantification values were in good agreement with the arbitrary amounts spiked. The quantification limits of αS1- and ß-casein in cookie analysis were 246 and 152 ng/g, respectively. Hence, this method can be used to analyze trace amounts of allergen proteins present in the baked food.

Dual-Responsive and ROS-Augmented Nanoplatform for Chemo/Photodynamic/Chemodynamic Combination Therapy of Triple Negative Breast Cancer.

Integrating chemodynamic therapy (CDT) and photodynamic therapy (PDT) into one nanoplatform can produce much more reactive oxygen species (ROS) for tumor therapy. Nevertheless, it is still a great challenge to selectively generate sufficient ROS in tumor regions. Meanwhile, CDT and PDT are restricted by insufficient H2O2 content in the tumor as well as by the limited tumor tissue penetration of the light source. In this study, a smart pH/ROS-responsive nanoplatform, Fe2+@UCM-BBD, is rationally designed for tumor combination therapy. The acidic microenvironment can induce the pH-responsive release of doxorubicin (DOX), which can induce tumor apoptosis through DNA damage. Beyond that, DOX can promote the production of H2O2, providing sufficient materials for CDT. Of note, upconversion nanoparticles at the core can convert the 980 nm light to red and green light, which are used to activate Ce6 to produce singlet oxygen (1O2) and achieve upconversion luminescence imaging, respectively. Then, the ROS-responsive linker bis-(alkylthio)alkene is cleaved by 1O2, resulting in the release of Fenton reagent (Fe2+) to realize CDT. Taken together, Fe2+@UCM-BBD exhibits on-demand therapeutic reagent release capability, excellent biocompatibility, and remarkable tumor inhibition ability via synergistic chemo/photodynamic/chemodynamic combination therapy.

Efficacy of 30% and 38% Silver Diamine Fluoride in Arresting Caries Lesions After Different Application Times: An in Vitro Study

Abstract Objective: To evaluate the efficacy of silver diamine fluoride (SDF) in arresting dentin caries lesions when applied under different concentrations and times. Material and Methods: Forty-two bovine blocks were selected and fixed in 24-well plates. Each well received a mixed bacterial inoculum added to the culture medium with 5% sucrose. The plates were incubated in microaerophilia (7 days) for caries formation, confirmed by micro-CT (M1). SDF was applied over the carious lesions for different times and concentrations (n=6): SDF 30% - immediate removal, 1 minute and 3 minutes; SDF 38%, - immediate removal, 1 minute and 3 minutes. The group without treatment was the control. Then, the samples were again scanned by micro-CT (M2) and submitted to a second cariogenic challenge for 21 days. Then, a final scan was performed (M3). Results: Mean pH at the culture medium and lesion depth were compared using Kruskal-Wallis and Wilcoxon tests. 38% SDF showed the lowest metabolic activity of the biofilm. All 38% groups and 30% 1 and 3 minutes did not show an increase in mean lesion depth comparing M3 with M1. However, only 30% 3 minutes and 38% 1 and 3 minutes showed a significant reduction of lesion depth. Conclusion: The minimum application time of 30% SDF to arrest dentin caries lesion was 1 minute, while 38% SDF arrested with application and immediate removal.

Poly(N,N-dimethylacrylamide)-coated upconverting NaYF4:Yb,Er@NaYF4:Nd core-shell nanoparticles for fluorescent labeling of carcinoma cells.

Upconverting luminescent lanthanide-doped nanoparticles (UCNP) belong to promising new materials that absorb infrared light able to penetrate in the deep tissue level, while emitting photons in the visible or ultraviolet region, which makes them favorable for bioimaging and cell labeling. Here, we have prepared upconverting NaYF4:Yb,Er@NaYF4:Nd core-shell nanoparticles, which were coated with copolymers of N,N-dimethylacrylamide (DMA) and 2-(acryloylamino)-2-methylpropane-1-sulfonic acid (AMPS) or tert-butyl [2-(acryloylamino)ethyl]carbamate (AEC-Boc) with negative or positive charges, respectively. The copolymers were synthesized by a reversible addition-fragmentation chain transfer (RAFT) polymerization, reaching Mn ~ 11 kDa and containing ~ 5 mol% of reactive groups. All copolymers contained bisphosphonate end-groups to be firmly anchored on the surface of NaYF4:Yb,Er@NaYF4:Nd core-shell nanoparticles. To compare properties of polymer coatings, poly(ethylene glycol)-coated and neat UCNP were used as a control. UCNP with various charges were then studied as labels of carcinoma cells, including human hepatocellular carcinoma HepG2, human cervical cancer HeLa, and rat insulinoma INS-1E cells. All the particles proved to be biocompatible (nontoxic); depending on their ξ-potential, the ability to penetrate the cells differed. This ability together with the upconversion luminescence are basic prerequisites for application of particles in photodynamic therapy (PDT) of various tumors, where emission of nanoparticles in visible light range at ~ 650 nm excites photosensitizer.

A CORM loaded nanoplatform for single NIR light-activated bioimaging, gas therapy, and photothermal therapy in vitro.

Carbon monoxide (CO) can cause mitochondrial dysfunction, inducing apoptosis of cancer cells, which sheds light on a potential alternative for cancer treatment. However, the existing CO-based compounds are inherently limited by their chemical nature, such as high biological toxicity and uncontrolled CO release. Therefore, a nanoplatform - UmPF - that addresses such pain points is urgently in demand. In this study, we have proposed a nanoplatform irradiated by near-infrared (NIR) light to release CO. Iron pentacarbonyl (Fe(CO)5) was loaded in the mesoporous polydopamine layer that was coated on rare-earth upconverting nanoparticles (UCNPs). The absorption wavelength of Fe(CO)5 overlaps with the emission bands of the UCNPs in the UV-visible light range, and therefore the emissions from the UCNPs can be used to incite Fe(CO)5 to control the release of CO. Besides, the catechol groups, which are abundant in the polydopamine structure, serve as an ideal locating spot to chelate with Fe(CO)5; in the meantime, the mesoporous structure of the polydopamine layer improves the loading efficiency of Fe(CO)5 and reduces its biological toxicity. The photothermal effect (PTT) of the polydopamine layer is highly controllable by adjusting the external laser intensity, irradiation time and the thickness of the polydopamine layer. The results illustrate that the combination of CO gas therapy (GT) and polydopamine PTT brought by the final nanoplatform can be synergistic in killing cancer cells in vitro. More importantly, the possible toxic side effects can be effectively prevented from affecting the organism, since CO will not be released in this system without near-infrared light radiation.

Spectroscopic glimpses of the transition state of ATP hydrolysis trapped in a bacterial DnaB helicase.

The ATP hydrolysis transition state of motor proteins is a weakly populated protein state that can be stabilized and investigated by replacing ATP with chemical mimics. We present atomic-level structural and dynamic insights on a state created by ADP aluminum fluoride binding to the bacterial DnaB helicase from Helicobacter pylori. We determined the positioning of the metal ion cofactor within the active site using electron paramagnetic resonance, and identified the protein protons coordinating to the phosphate groups of ADP and DNA using proton-detected 31P,1H solid-state nuclear magnetic resonance spectroscopy at fast magic-angle spinning > 100 kHz, as well as temperature-dependent proton chemical-shift values to prove their engagements in hydrogen bonds. 19F and 27Al MAS NMR spectra reveal a highly mobile, fast-rotating aluminum fluoride unit pointing to the capture of a late ATP hydrolysis transition state in which the phosphoryl unit is already detached from the arginine and lysine fingers.