Interaction Of Boron Research Articles

Synthesis and mucin binding to silicone boronic acid elastomers

Event Abstract Back to Event Synthesis and mucin binding to silicone boronic acid elastomers Benjamin Macphail1, Laura Zepeda-Velazquez1 and Michael A. Brook1 1 McMaster University, Chemistry and Chemical Biology, Canada Boronic acids form weak to strong complexes with saccharides[1]: the degree of binding depends upon the structure of both partners. One important consequence of this is the affinity that boronic acids have for mucosal surfaces. Synthetic structures containing boronic acids ranging from polymers to nanoparticles[2] can be delivered to mucosal surfaces, e.g., by binding to mucin[3], as a preface to drug delivery, for example[4]. The same strategy has been used to stabilize tear film with guar in the presence of boric acid to treat dry eye[5]. Silicone elastomers are widely used in biomedical devices that may encounter mucosal surfaces. Perhaps the most common examples of such devices are the silicone hydrogel contact lenses that dominate the market. As part of a study to improve the biocompatibility of silicone, particularly in the eye, we report the development of boronic acid-modified silicones and their physical properties: surprisingly, the materials can be induced to form elastomeric structures without chemical crosslinks. Both telechelic and pendant silicone boronates were readily prepared by hydrosilylation of protected boronates[6]. In the former case (Figure 1A), the molecular weight (MW) between boronates varied between 1000-7000 g/mol. In the latter case (Figure B), more important than MW was the content of pendant boronic acids, which ranged from 7-50% (average spacing between boronic acids of 14, 7 or 2 monomer units, respectively). When protected, the compounds were transparent, water clear oils. Figure 1. Preparation of protected A: telechelic and B: pendant silicone boronic acids and models for their associative behaviour after hydrolysis. C: Model of mucin binding to the exposed surface of a silicone boronate. Exposure to water immediately converted the materials to elastomers. Pendant molecules should only undergo chain extension via boronic acid dimers[7] to give viscous oils. However, the interaction of the trivalent boron with adjacent oxygen atoms provides secondary crosslinking through Lewis acid/base complexes (as with Silly Putty, Figure 2A). As a consequence, it is possible tune the modulus within a fairly narrow range. By contrast, the crosslink density is much higher with pendant boronic acids, which exhibit moduli that span an order of magnitude (Figure 2B). Figure 2. Moduli after hydrolysis of A: telechelic and B: pendant silicone boronic acids. These elastomers clearly present a surface of boronic acids, the concentration of which can be readily tuned. We will report the ability of mucin to bind to surface-bound boronic acids (Figure 1C) and describe the optimization of surface density of boronic acids on the silicone layer to facilitate monolayer coverage. We thank the Natural Sciences and Engineering Council of Canada and 20/20 NSERC Ophthalmic Materials Network for financial support of this work.

Electrical properties and hyperfine interactions of boron doped Fe3O4 nanoparticles

The single spinel phase nano-structured particles of FeBxFe2−xO4 (x = 0.1, 0.2, 0.3, 0.4 and 0.5) were synthesized by the glycothermal method and the effect of B3+ substitution on structural and dielectric properties of Fe3O4 were studied. From 57Fe Mössbauer spectroscopy data, the variation in line width, isomer shift, quadrupole splitting and hyperfine magnetic field values on B3+ substitution have been determined. The hyperfine field values at B- and A-sites gradually decrease with increasing B3+ ion concentration (x). The cation distributions obtained from Bertaut method are in line with Mössbauer results. Complex impedance analysis of boron-substituted spinel ferrites have been made extensively in order to investigate the significant changes in ac and dc conductivity as well as complex permittivity when the boron composition ratio varies from 0.1 to 0.5. It is found that both ac and dc conductivity are also dependent on the boron content in addition to both temperature and applied frequency. The dc conductivity tendency does not purely obey the Arrhenius plots. The dielectric constant and loss of complex permittivity, in general, show similar attitudes as seen in some nanocomposites containing spinel ferrites except for some fluctuations and shifts along the characteristics of the curves. Furthermore, their imaginary components of both permittivity and modulus are almost found to obey the power law with any exponent values varying between 0.5 and 2 in accordance with the level of boron concentrations.

SU‐E‐T‐656: Quantitative Analysis of Proton Boron Fusion Therapy (PBFT) in Various Conditions

Purpose:Three alpha particles are concomitant of proton boron interaction, which can be used in radiotherapy applications. We performed simulation studies to determine the effectiveness of proton boron fusion therapy (PBFT) under various conditions.Methods:Boron uptake regions (BURs) of various widths and densities were implemented in Monte Carlo n‐particle extended (MCNPX) simulation code. The effect of proton beam energy was considered for different BURs. Four simulation scenarios were designed to verify the effectiveness of integrated boost that was observed in the proton boron reaction. In these simulations, the effect of proton beam energy was determined for different physical conditions, such as size, location, and boron concentration.Results:Proton dose amplification was confirmed for all proton beam energies considered (< 96.62%). Based on the simulation results for different physical conditions, the threshold for the range in which proton dose amplification occurred was estimated as 0.3 cm. Effective proton boron reaction requires the boron concentration to be equal to or greater than 14.4 mg/g.Conclusion:We established the effects of the PBFT with various conditions by using Monte Carlo simulation. The results of our research can be used for providing a PBFT dose database.

A Theoretical Study on the Functionalisation Process of C18NB Fullerene Through its Open [5,5] Cycloaddition with 4-Pyridine Nitrile Oxide

C20 nanofullerene and its derivatives, as the smallest carbon cages, are amongthe most important compounds in the field of nanoscience. As a result, it is very important to find a procedure to functionalise these precious compounds to exploit their numerous benefits. So, in this study, the process was investigated of adding a functional group to one of the C20 fullerene derivatives, via its open [5,5] cycloaddition reaction with 4-pyridine nitrile oxide. This showed that the open [5,5] cycloaddition reaction between 4-pyridine nitrile oxide and C18NB fullerene takes place with sufficient speed that would need no catalyst. According to the calculations, a highly asynchronous concerted mechanism operates in this reaction. It seems that oxygen–boron interaction causes the mechanism to be asynchronous. All calculations were performed at the B3LYP/6-311G(d,p) level of theory.

Assessing the suitability of saline wastewaters for irrigation of Citrus spp.: Emphasis on boron and specific-ion interactions

Many ground waters and recycled municipal wastewaters contain elevated concentrations of boron (B) and salts but are nonetheless potential irrigation water sources for agricultural production. Unlike most agricultural crops, Citrus spp. is among the most sensitive to B and salinity. Here, an extensive review of the literature from 1928 to present on Citrus spp. tolerance to B and specific ions has been conducted. The overall suitability of such water supplies largely depends upon the salt and B concentration in the irrigation water, irrigation management, rainfall, soil and climatic conditions and orange rootstock. Since salinity and B stresses often occur together, the overall suitability may depend on interactive abiotic stresses as well. The combination and potential interaction of these constituents, combined with the soil and climatic conditions, can affect the overall suitability of B in irrigation water over the long-term. And there is evidence of internal tolerance mechanisms (i.e. B transport/compartmentation; B complexation) present allowing leaves to tolerate higher B concentrations than they would otherwise and that certain amendments can reduce uptake and transport from rootstock to scion. Regardless, new research does not provide any more information to suggest that the existing B tolerance guidelines for orange (0.50–0.75mg/L in the soil solution, Bss) should be adjusted upwards or downwards. The challenge comes in determining the maximum B concentration in the irrigation water (Bw) that would result in these Bss tolerance values. Two steady-state approaches that were used here suggest that the maximum Bw for the protection of orange falls between 0.3 and 0.5mg/L over the long term provided good water management, adequate leaching and no additional stresses are affecting the tree. For lemon, maximum Bw concentrations would be less. The presence of specific ions and ion interactions makes water quality assessment difficult.

The interaction of boron with glycolipids is required to increase tolerance to stresses in Anabaena PCC 7120

Boron (B) is an essential nutrient for heterocystous cyanobacteria growing under diazotrophic conditions. Under B-deficient conditions, the heterocyst envelope is highly disorganized, and the glycolipid layer is predominantly lost. Therefore, we examined whether B is implicated in the regulation of synthesis or processing and/or stability of glycolipids in Anabaena PCC 7120. RT-PCR analysis indicated that the expression of hglE was not significantly changed under B deficiency, suggesting that the synthesis of glycolipids during heterocyst formation was not compromised. In contrast, the overexpression of devB and hepA, encoding a glycolipid and a carbohydrate transporter, respectively, results in the instability of the envelope under B-deficient conditions. The capacity of borate to bind and stabilize molecules is considered the basis of any B biological function. Using a borate-binding-specific resin and thin layer chromatography, we detected the glycolipids that interact with B. Several heterocyst-specific glycolipids were detected as putative B ligands, suggesting a role for B in stabilizing the heterocyst envelope. Moreover, the glycolipids of Anabaena growing in non-diazotrophic conditions were also detected as putative B ligands. Although B is not essential for Anabaena under non-N2-fixing conditions, the presence of this micronutrient increased the tolerance of Anabaena to detergent treatment, salinity and hyperosmotic conditions. Taken together, the results of the present experiment suggest a beneficial role for B in environmental adaptation. Furthermore, we discuss the nutrient requirement for living organisms growing in nature and not under laboratory conditions.

Preparation of a new sorbent based on boronate affinity monolith and evaluation of its extraction performance for nitrogen-containing pollutants

In this study, a new boronate affinity sorbent based on poly(4-vinylphenylboronic acid-divinylbenzene) monolith (VPB–DB) was prepared and used as extractive medium of stir cake sorptive extraction (SCSE). The effect of the preparation parameters in the polymerization mixture on extraction performance was investigated thoroughly. The sorbent was characterized by infrared spectroscopy, elemental analysis, scanning electron microscopy and mercury intrusion porosimetry. The determination of 8 sulfonamides in environmental water samples with the combination of SCSE and high performance liquid chromatography tandem mass spectrometry detection was selected as a paradigm for the evaluation of extraction performance of poly(VPB–DB) monolith for nitrogen-containing pollutants. Under the optimal extraction conditions, the limits of detection (S/N=3) and limits of quantification (S/N=10) for the target analytes were 0.0012–0.010 and 0.0040–0.033μg/L, respectively. The method also showed good linearity, repeatability, recoveries and high feasibility. At the same time, aromatic amines, nitrophenols, amide herbicides and sudan dyes were also used to evaluate the extractive performance of the sorbent for nitrogen-containing compounds. Results well indicate that the interaction of boron–nitrogen coordination between sorbent and analytes plays a key role in the extraction of nitrogen-containing compounds.

On the kinetics and reaction mechanisms of boronic acid in interaction with diols for non-enzymatic glucose monitoring applications: a hybrid DFT study

Boronic acids are well-known for their ability to complex with saccharides and to form cyclic boronic esters or cyclic boronate ions. Increasing the reactivity of boronic acids would lead towards the design of a highly responsive sensor for non-enzymatic glucose monitoring applications. Many studies have been carried out to investigate the reactivity of boronic acids towards diols in different environmental effects. The symmetry around boron in their reactive species, however, is still an open question. In this study, we used computational quantum chemistry calculations to propose a model in which boronic acid is highly reactive towards diols. B3LYP/6-31+G(d,p) model chemistry was used in water to calculate the transition states of several proposed reaction mechanisms and the rates of the reactions were calculated using the transition state theory. The reaction takes place in two steps with the first step known as the rate determining step. The model we proposed in this study includes two different electronegative R-groups attached to boronic acid (i.e. CF3 and CH3) which highly influence the interaction of boron with diols. The kinetic results in our study show that boronate ion with a low electronegative R-group is a better sensor in alkaline medium and boronic acid with a high electronegative R-group is a better sensor in acidic medium. Using the latter in alkaline medium results in a very poor sensor since it is highly reactive and promptly forms a tetrahedral boronate ion. The high electronegative R-group on boronate ion decreases its basic characteristics and results in a low reactive sensor. The same scenario goes for the former i.e. boronate ion attached to a low electronegative R-group in acidic medium. As a result, we can conclude that boronic acid's reactivity is not mainly due to the symmetry around boron, it is due to the characteristics of boron itself which can be affected by both the R-group and the medium.

Interaction of Boron and Phosphorus Impurities in Silicon Nanowires during Low-Temperature Ozone Oxidation

In doped Si nanowires (SiNWs) boron (B) atoms segregate to the surface oxide layers during thermal oxidation, while phosphorus (P) atoms preferentially pile up in Si crystalline regions close to the Si/SiO2 interface. Here we report on micro-Raman scattering and electron spin resonance (ESR) measurements showing that B atoms can be stabilized at the crystalline Si core region in codped SiNWs with average diameters of 20–30 nm because of the strong interaction between B and P atoms during thermal oxidation below 800 °C. Theoretical calculation clearly demonstrated the effect of B–P pairing, which can stabilize the B atoms in the Si side. In the B–P pairing configuration, dopant passivation—beyond simple compensation—occurs, making the impurities electrically inactive.

Investigation of the characteristic features of interface interaction and corrosion resistance of boron–aluminum composites by the method of simultaneous thermal analysis

We study the influence of temperature, aggressiveness of the media, and interface interaction on the corrosion characteristics of boron-aluminum composites with the help of simultaneous thermal analysis that combines two methods of investigation, namely, thermogravimetry and differential scanning calorimetry. By using the simultaneous thermal analysis, we establish the mass fraction of reinforcing components (boron fibers), the amount of inhibitors on the surfaces of composite materials, their thermal resistance, and the comparative intensities of corrosion in various corrosive media.

A new diketopyrrolopyrrole (DPP) derivative bearing boronate group as fluorescent probe for fluoride ion

Abstract A new diketopyrrolopyrrole (DPP) derivative bearing pinacol boronate group has been synthesized via Suzuki–Miyaura reaction under mild conditions in good yield. The product could act as a colorimetric and ratiometric fluorescent probe for fluoride ion with high sensitivity and selectivity. The recognition mechanism was attributed to unique fluoride–boron interaction, which blocked the charge transfer (CT) between DPP chromophore and the empty p orbitals of boron atoms, and proved by the fluorescence spectra, 19F NMR spectra and 1H NMR spectra titration experiments.

PH dependent salinity-boron interactions impact yield, biomass, evapotranspiration and boron uptake in broccoli (Brassica oleracea L.)

Soil pH is known to influence many important biochemical processes in plants and soils, however its role in salinity—boron interactions affecting plant growth and ion relations has not been examined. The purpose of this research was to evaluate the interactive effects of salinity, boron and soil solution pH on broccoli (Brassica oleracea L.) growth, yield, consumptive water use and shoot-boron accumulation. A greenhouse experiment was conducted using a sand tank system where salinity-B-pH treatment solutions were supplemented with a complete nutrient solution. Sulfate-dominated irrigation waters, characteristic of groundwater in California’s San Joaquin valley (SJV), were tested at EC levels of 2, 5, 8, 11 and 14 dS m−1. Each salinity treatment consisted of two boron treatments (0.5 and 21 mg L−1) and each of those treatments was tested under slightly basic (pH 8.0) and slightly acidic (pH 6.0) conditions. Results included multiple salinity-boron-pH interactions affecting shoot biomass, head yield and consumptive water use. Broccoli fresh head yields were significantly reduced by salinity and boron, but the degree of yield reductions was influenced by pH. Relative head yields were substantially reduced in treatments with high pH and high B, particularly under low and high salinity where head yields were decreased by 89 % and 96 %, respectively, relative to those at low salinity and low boron. Intermediate levels of salinity were far less damaging. Increased salinity and boron reduced evapotranspiration (ET) and there were no salinity-boron associated interactions on ET. However, increased salinity and boron concentrations increased water use efficiency (shoot biomass/cumulative volume ET). Shoot B concentration increased with increased boron and was greater at pH 6 as compared to pH 8. Shoot boron concentration decreased with increasing salinity at both pH levels but particularly at the high substrate boron concentration. It is likely that different mechanisms, yet unknown, are responsible for severe head-yield reductions at low and high salinity in the presence of high boron under alkaline conditions. We found that boron in the shoot did not accumulate by a simple passive process. Rather as boron increased from 0.5 to 21 mg L−1, there was a restrictive mechanism where total shoot boron (mg plant−1) was reduced by 10 to 40 times the amount potentially supplied to the shoot by passive transport via mass flow perhaps involving complex interactions with membrane channels and B exporters. Total shoot boron concentration was a poor indicator of plant growth response.

V1+xNb1–xIrB2 (x ≈ 0.1), The First Quaternary Metal‐Rich ­Boride Adopting The Mo2IrB2‐Type Structure: Synthesis, Crystal and Electronic Structure and Bonding Analysis

AbstractPolycrystalline samples and single crystals of the new metal‐rich boride V1+xNb1–xIrB2 (x ≈ 0.1), were synthesized by arc‐melting the elements in a water‐cooled copper crucible under an argon atmosphere and characterized by X‐ray diffraction and EDX measurements. The crystal structure was refined on the basis of single crystal data. The new phase adopts the Mo2IrB2‐type structure (space group Pnnm, no. 58) with the lattice parameters a = 7.301(7) Å, b = 9.388(9) Å and c = 3.206(5) Å. It is the first quaternary representative of Mo2IrB2‐type structure. The structure contains zigzag B4‐fragments with boron–boron distances of 1.83–1.85 Å. The electronic density of states and crystal orbital Hamilton population (for bonding analysis) were calculated, using the linear muffin‐tin orbital atomic sphere approximation (LMTO‐ASA) method. According to these calculations, this metal‐rich compound should be metallic, as expected. Furthermore, very strong boron–boron interactions are observed in the zigzag B4‐fragment and two significantly different Ir–B interactions are observed in the new phase and the prototype Mo2IrB2.

Boron incorporation into calcite during growth: Implications for the use of boron in carbonates as a pH proxy

Current interest in boron incorporation into carbonates arises from the observation that the isotopic composition of carbonates depends on the pH of the fluid from which they precipitated. This finding opened the possibility of using boron isotopic composition of natural carbonates as a paleo-pH proxy. In this study, coprecipitation of boron by calcite was investigated using Atomic Force Microscopy (AFM), as a function of pH, supersaturation and boron concentration. In situ AFM observations reported here provide experimental evidence of boron incorporation into calcite, which takes place to a greater extent at high pH (9.5) and under close to equilibrium conditions. Moreover, we report nanoscale observations that give indirect evidence of the incorporation of boron in non-lattice sites. Step-specific interactions of tetrahedrally-coordinated boron with calcite obtuse steps during growth are revealed as a reduction in the obtuse-step spreading rate as well as rounding and roughening of such steps. Our results suggest that, together with changes in pH, variations in the calcification rate or the calcite crystallographic form in which boron is incorporated are important factors to consider when using boron in carbonates as a pH proxy, as these factors could also influence the amount of boron incorporated during growth and possibly the boron isotopic signature.

Electron density shift description of non-bonding intramolecular interactions

A new methodology is described for the study of the electron density shift in intramolecular interactions. The methodology has been tested in an intermolecular complex and compared to the electron density shift obtained as the difference between the complex and the isolated monomers. The molecular fragmentation procedures and its application to hydrogen bonds, chalcogen–chalcogen interactions, nitrogen–boron interactions, dihydrogen interactions and silicon–nitrogen interactions are described. A careful selection of the fragmentation scheme is necessary in order to describe correctly the electron density shift in the intramolecular interactions. For this reason, different orders of fragmentation have been studied and analyzed pointing out the problems and limitations which are inherent to the methodology. It has been found that this methodology is a new tool which provides a good qualitative description of the electron density shift within the interacting region between two or more contacts, in both inter and intramolecular contacts with a reasonable low computational cost.

The complex metal-rich boride Ti1+xRh2−x+yIr3−yB3 (x=0.68, y=1.06) with a new structure type containing B4 zigzag fragments: Synthesis, crystal chemistry and theoretical calculations

Polycrystalline samples and single crystals of the new complex boride Ti1+xRh2−x+yIr3−yB3 (x=0.68; y=1.06) were synthesized by arc-melting the elements in a water-cooled copper crucible under an argon atmosphere and characterized by X-Ray diffraction as well as EDX measurements. The crystal structure was refined on the basis of single crystal data. The new phase, which represents a new structure type containing trans zigzag B4 fragments as well as isolated boron atoms crystallizes in the orthorhombic space group Pbam (Nr. 55) with the lattice parameters a=8.620(1)Å, b=14.995(2)Å and c=3.234(1)Å. First-principles density functional theory calculations using the Vienna ab-initio simulation package (VASP) were performed on an appropriate structural model (using a supercell approach) and the experimental crystallographic data could be reproduced accurately. Based on this model, the density of states and crystal orbital Hamilton population (for bonding analysis) were calculated, using the linear muffin-tin orbital atomic sphere approximation (LMTO-ASA) method. According to these calculations, this metal-rich compound should be metallic, as expected. Furthermore, very strong boron–boron interactions are observed in the trans zigzag B4 fragment, which induce a clear differentiation of two types of metal–boron contacts with different strength. The observed three-dimensional metal–metal interaction is in good agreement with the predicted metallic behavior.

The bonding in hexagonal Ba2/3Pt3B2 and CeCo3B2 type ternary metal borides

Tight-binding calculations with an extended Huckel Hamiltonian were performed on Ba2/3Pt3B2 and LuOs3B2. Hypothetical linear metal boride chains present in these materials are analyzed with a three-dimensional model that contains a trigonal bipyramidal T3B2 (T = transition metal) building unit for the compounds. The geometrical structure for the T3B2 trigonal bipyramids depends on the number of electrons. For systems that have greater than 36 electrons in its trigonal bipyramidal building unit, a structural distortion is expected. Electron back donation from the electron-rich M3 fragment to the empty e′ set on B2 creates boron–boron interaction along the z-axis. Boron–boron pairing then participates as an electron sink and causes a trigonal distortion of the platinum Kagome net. On the other hand, a system with <35 electrons should have an undistorted, CeCo3B2 type structure. The electronic factors that create the breathing motion are discussed and analyzed with the aid of molecular and solid-state models. The metal–metal bonding associated with the structural properties also has been examined.

Further investigation on boric acid catalytic graphitization of polyacrylonitrile carbon fibers: Mechanism and mechanical properties

Catalytic graphitization of polyacrylonitrile based carbon fibers by boric acid doping was studied and the dependence of fiber tensile strength on the boron content and temperature was discussed. It was found that there existed a key temperature point for the boron to take effect. When the fibers were modified with 7.0wt.% boric acid solution, with increasing temperature, the tensile strength was lower than that of the unmodified ones below 2300°C, but a reverse thing happened above 2300°C. Moreover, when being heated at 2500°C, the modified fibers showed an increasing tensile modulus and strength with increasing boron content till maximums of 404GPa and 2.46GPa, 26% and 16% higher than those of unmodified ones. The mechanical properties of the fibers were affected by the interaction of carbon and boron, and also related with boron states. The decomposition of boron acid and its interaction with carbon brought defects on fiber surface, degrading the mechanical properties below 1300°C. With further heat treatment, the boron diffused into the fibers and divided into two states: substitutional and interstitial. At a temperature over 2300°C with an appreciate boron content, the substitutional would be formed predominantly, which removed the structural defects and relaxed the distortions, so as to benefit the mechanical properties.

Lewis Acids and Lewis Acid-Functionalized Ligands in Rhodium-Catalyzed Methyl Acetate Carbonylation

The application of Lewis acids and Lewis acid-functionalized ligands as activators for methyl acetate in the rhodium-catalyzed carbonylation of methyl acetate to acetic anhydride has been investigated. The reaction of methyl acetate with B(C6F5)3 results in the formation of the adduct [MeOAc·B(C6F5)3]. The combination of this adduct with [Rh(OAc)(CO)2]2 results in a transfer of the Lewis acid to the rhodium complex, rather than an anticipated oxidative addition reaction. In a second approach, novel Lewis acid-functionalized rhodium(I) complexes [Rh(CO)Cl(BPP)], [Rh(CO)2(BPP)]SbF6, and [Rh(MeCN)2(BPP)]SbF6 (BPP = PhB(C6H4PPh2)2) have been prepared. The lack of reactivity of [Rh(CO)2(BPP)]SbF6 toward MeOAc has shown that the rhodium–boron interaction is too strong for activation of methyl acetate, and no carbonylation activity was observed under the conditions used.

Impact of carbon coimplantation on boron behavior in silicon: Carbon–boron coclustering and suppression of boron diffusion

Coimplantation of heterogeneous dopants in materials can be used to control the principal dopant distribution. We used atom probe tomography (APT) and secondary ion mass spectrometry (SIMS) to investigate the impact of coimplanted carbon on boron diffusion in silicon. After annealing, three-dimensional APT analysis of dopant distributions revealed the presence of carbon–boron coclusters around the projection range of boron. In addition, SIMS depth profiles revealed enhanced boron concentration around the projection range of carbon. These results suggest that the carbon–boron interaction suppresses boron diffusion in silicon.