Boron Research Articles

Dissolution behavior and kinetic investigation of in solution in the reaction of colemanite ore with propionic acid

Colemanite ore, which is one of the most significant commercially substantial boron minerals, is used to produce various boron compounds in the industry with its rich B_2 O_3 content. Calcium propionate, used in the food industry, is formed as a by-product in its production. In the production of boric acid from colemanite, the use of different solvent reagents is at the forefront to prevent the formation of Mg^(2+), Ca^(2+) and SO_4^(2-) impurities and borogypsum by-products. For this reason, in our study, the dissolution kinetics of colemanite ore in propionic acid solution in an aqueous medium were carried out in a batch reactor system. As dissolution parameters; reaction temperature, solid/liquid ratio, propionic acid (CH_3 CH_2 COOH) concentration, stirring speed and particle size were selected as. According to the experimental results, the amount of Mg^(2+) passed to the solution; was observed that the solution increased with the increase in reaction temperature with the decrease in solid-liquid ratio, grain size, and acid concentration. In addition, it was determined that the mixing speed was not effective. Obtained experimental data were analyzed according to homogeneous and heterogeneous reaction models using the Statistica 10.0 package program. It was determined that the dissolution kinetic of Mg^(2+) passing to solution conformed to the "Avrami model" and activation energy (E) was calculated as 8.18 kJ⁄mol.

New technologies for beam spectrometry, quality assurance, real-time monitoring and microdosimetry in BNCT

Boron neutron capture therapy (BNCT) is a next-generation radiotherapy that combines neutron beams with boron compounds that selectively accumulate in cancer cells. Because this therapy requires neutrons for irradiation, compact accelerator-based neutron source devices that can be installed in hospitals are being developed around the world. Clinical trials of several devices have been conducted in Japan, China, and South Korea. The most advanced device was approved by the Japanese regulatory authorities in 2020. As a result, BNCT with the device is being implemented as an insured therapy for recurrent head and neck cancer at two hospitals in Japan. Thus, the development of accelerator-based neutron generators is proceeding in the field of BNCT. However, much remains to be done to establish this therapy as a common cancer treatment and to make it available worldwide. Dosimetry methods in BNCT are one of the issues. In the treatment, the dose given to a patient by neutron irradiation has to be estimated accurately. However, it is difficult to measure neutrons accurately and in real time. Currently, the neutron dose delivered to patients during treatment is not measured. Instead, the current of the charged particles that irradiate the neutron target material is measured to indirectly evaluate the neutron fluence and dose. In addition, accurate dose estimation based on reactions with neutrons and various elements in a human body uses the Monte Carlo method, which is computationally time-consuming. To address these dosimetry issues, several neutron fluence and dose measurement methods are being developed. This review briefly describes the current dosimetry methods and then presents several methods under development that allow real-time neutron measurements applicable to BNCT.

An automated positive selection screen in yeast provides support for boron-containing compounds as inhibitors of SARS-CoV-2 main protease.

The severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) virus continues to cause severe disease and deaths in many parts of the world, despite massive vaccination efforts. Antiviral drugs to curb an ongoing infection remain a priority. The virus-encoded 3C-like main protease (MPro; nsp5) is seen as a promising target. Here, with a positive selection genetic system engineered in Saccharomyces cerevisiae using cleavage and release of MazF toxin as an indicator, we screened in a robotized setup small molecule libraries comprising ~2,500 compounds for MPro inhibitors. We detected eight compounds as effective against MPro expressed in yeast, five of which are characterized proteasome inhibitors. Molecular docking indicates that most of these bind covalently to the MPro catalytically active cysteine. Compounds were confirmed as MPro inhibitors in an in vitro enzymatic assay. Among those were three previously only predicted in silico; the boron-containing proteasome inhibitors bortezomib, delanzomib, and ixazomib. Importantly, we establish reaction conditions in vitro preserving the MPro-inhibitory activity of the boron-containing drugs. These differ from the standard conditions, which may explain why boron compounds have gone undetected in screens based on enzymatic in vitro assays. Our screening system is robust and can find inhibitors of a specific protease that are biostable, able to penetrate a cell membrane, and are not generally toxic. As a cellular assay, it can detect inhibitors that fail in a screen based on an in vitro enzymatic assay using standardized conditions, and now give support for boron compounds as MPro inhibitors. This method can also be adapted for other viral proteases.IMPORTANCEThe coronavirus disease 2019 (COVID-19) pandemic triggered the realization that we need flexible approaches to find treatments for emerging viral threats. We implemented a genetically engineered platform in yeast to detect inhibitors of the virus's main protease (MPro), a promising target to curb severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) infections. Screening molecule libraries, we identified candidate inhibitors and verified them in a biochemical assay. Moreover, the system detected boron-containing molecules as MPro inhibitors. Those were previously predicted computationally but never shown effective in a biochemical assay. Here, we demonstrate that they require a non-standard reaction buffer to function as MPro inhibitors. Hence, our cell-based method detects protease inhibitors missed by other approaches and provides support for the boron-containing molecules. We have thus demonstrated that our platform can screen large numbers of chemicals to find potential inhibitors of a viral protease. Importantly, the platform can be modified to detect protease targets from other emerging viruses.

Platinum-Catalyzed Regio- and Enantioselective Diboration of Unactivated Alkenes with (pin)B-B(dan).

Asymmetric diboration of terminal alkenes is well established, and subsequent selective functionalization of the less hindered primary boronic ester is commonly achieved. Conversely, selective functionalization of the sterically less accessible secondary boronic ester remains challenging. An alternative way to control chemoselective functionalization of bis(boron) compounds is by engendering different Lewis acidity to the two boryl moieties, since reactivity would then be dictated by Lewis acidity instead of sterics. We report herein the regio- and enantioselective Pt-catalyzed diboration of unactivated alkenes with (pin)B-B(dan). A broad range of terminal and cyclic alkenes undergo diboration to furnish the differentiable 1,2-bis(boron) compounds with high levels of regio- and enantiocontrol, giving access to a wide variety of novel building blocks from a common intermediate. The reaction places the less Lewis acidic B(dan) group at the less hindered position and the resulting 1,2-bisboryl alkanes undergo selective transformations of the B(pin) group located at the more hindered position. The regioselectivity of the diboration has been studied by DFT calculations and is believed to originate from the trans influence, which lowers the activation barrier for formation of the regioisomer that places the weaker electron donor [B(pin) vs B(dan)] opposite the strong electron donor (alkyl group) in the platinum complex.

Isolable Si=B Analogue of a Vinyl Halide: A Building Block for Facile Access toward Silicon-Boron Multiple Bonded Species.

Compared to the outstanding development in the synthesis of Si-B single bonded species, borylsilanes and their application to organic synthesis, the chemistry of Si=B double bonded species, borasilenes and boratasilenes have only made little progress, first of all, due to the difficulties in accessing such double bonds. Herein we report the synthesis of the first Si=B analogue of a vinyl halide, a bromoboratasilene, via formal borylene insertion to the coordination sphere of a monoatomic Si(0) complex, using a dihaloborane as the borylene source.The treatment of bromoboratasilene toward neutral or anionic Lewis bases gives access to new boratasilenes, all of which were proved to possess significant Si=B double bond character by XRD analysis and DFT calculations. These results demonstrate exciting strategies to synthesize new types of Si=B double bonded species which should further progress the chemistry of boron, silicon-containing molecules.

Electroless Deposition of Ni Nanoparticles on Boron Particles: Physicochemical and Oxidation Properties

Elemental boron also has a high volumetric heat of combustion (136 kJ/cm3), the third highest gravimetric heat of combustion (58.5 MJ/kg) and its oxidation is a highly exothermic process. All these features make boron an attractive constituent of propellants, explosives, and high energy density solid fuels for air-breathing propulsion as an energetic material. Given these uses, researchers have worked on the ignition and combustion processes of boron. However, boron has several serious issues that limit its practical use, including large ignition delay, inefficient combustion, and a complex burning process in solid propellants due to the formation of a defensive boron oxide (B2O3) layer on the boron surface. Previous studies have found that the ignition and combustion performance of boron can be improved by coating it with metal particles, metal oxides, or organic materials, as well as by removing the boron oxide layer.In the literature, there are limited studies on metal particle coating of a boron surface using the electroless Ni plating method. The electroless coating has several impressive advantages over conventional electrolytic coating. The prime advantage is that electroless plating does not require any electricity to operate and is a low-cost process. Among other advantages, it provides a uniform coating and can be used with all kinds of substrates with complex shapes. Conductive and non-conductive materials/powders can be coated with constant thickness with good adhesion.The present work investigated Ni nanoparticle coating on irregularly shaped/non-spherical boron particles using the electroless Ni-plating method at room temperature to prevent the oxidation of boron particles. This is preferable since it is very difficult to coat large quantities at relatively high temperatures. The four different simple paths were chosen during the electroless Ni plating to coat Ni on boron particles: no rinsing and no drying (Path A), only drying (Path B), both rinsing and drying (Path C) and only rinsing (Path D). Previous studies have explored the effect of bath concentration, pH, and temperature on the Ni coating. However, the influence of the four different paths mentioned above on Ni coating with boron particles or any other materials has rarely been investigated. Surface morphology confirmed the Ni nanoparticles coating on the surface of boron particles. The size of the Ni nanoparticles varied between 10 and 120 nm concerning the chosen paths used for preparation using TEM. XRD characterization results of the Ni coated boron particles showed the formation of crystalline Ni nanoparticles. EDAX and XPS results showed the presence of the primary B and Ni elements in samples synthesized in the present study. Thermogravimetric analysis conducted in air atmosphere found the boron particles coated with Ni nanoparticles had enhanced oxidation resistance compared to bare boron particles. Also, the Ni coated boron particles showed a shift in exothermic peak to a lower temperature and higher heat evolution than the bare boron particles.Acknowledgements:This work was supported by the National Research Foundation (NRF) of Korea grant funded by the Korea government (MSIT) No. 2019R1A2C1010862, 2022R1A2C2013508

Ultrasound Combination to Improve the Efficacy of Current Boron Neutron Capture Therapy for Head and Neck Cancer.

Boron neutron capture therapy (BNCT) is radiotherapy in which a nuclear reaction between boron-10 (10B) in tumor cells and neutrons produces alpha particles and recoiling 7Li nuclei with an extremely short range, leading to the destruction of the tumor cells. Although the neutron source has traditionally been a nuclear reactor, accelerators to generate neutron beams have been developed and commercialized. Therefore, this treatment will become more widespread. Recurrent head and neck cancer (HNC) close to the body surface is considered a candidate for BNCT using the boron compound boronophenylalanine (BPA) and has been found to be highly responsive to this treatment. However, some cases recur early after the completion of the treatment, which needs to be addressed. Ultrasound is a highly safe diagnostic method. Ultrasound with microbubbles is expected to promote the uptake of BPA into tumor cells. Ultrasound also has the ability to improve the sensitivity of tumor cells to radiotherapy. In addition, high-intensity focused ultrasound may improve the efficacy of BNCT via its thermal and mechanical effects. This review is not systematic but outlines the current status of BPA-based BNCT and proposes plans to reduce the recurrence rate of HNC after BNCT in combination with ultrasound.

Two-Dimensional M-Chalcogene Family with Tunable Superconducting, Topological, and Magnetic Properties.

An interesting question is whether chalcogen atoms can emulate the role of carbon or boron elements stabilized between two transition metal layers, as observed in MXenes or MBenes. Here, we predict a new family of two-dimensional ternary compounds M4XY2 (where M = Pd, Y, Zr, etc.; X = S, Se, Te; and Y = Cl, Br, I), named M-chalcogene. Through first-principles calculations, we reveal diverse physical properties in these compounds, including superconducting, topological, and magnetic characteristics, where the bilayer transition metals play crucial roles. Moreover, the expected helical edge states and superconducting transition temperatures in Pd4SCl2 can be finely tuned by strains. Additionally, the Ti4SCl2 is predicted to be a topological insulator and shows promise as a gas sensor candidate for certain exotic gases. Our findings expand two-dimensional material families and provide promising platforms for diverse physical phenomena with efficient tunability by external stimuli for various applications.

Simultaneous Bulk‐Rock Elemental and Boron Isotope Ratio Measurement Using LA‐ICP‐MS on Silicate Micro‐Particulate Pellets

We have established a method for the simultaneous measurement of element abundances and boron isotopic compositions of bulk‐rock silicate samples by laser ablation coupled to two different ICP‐MS instruments. Fifteen silicate reference materials were prepared as micro‐particulate pressed powder pellets (MP) for analysis. Approximately 1/5th of the ablated material was transported to a single‐collector ICP‐MS for elemental measurement, while 4/5ths were sent to a multi‐collector ICP‐MS for boron isotope ratio measurement. Compositions of different milling materials (agate, zirconium oxide, tungsten carbide, sintered corundum and silicon nitride) were measured for the evaluation of potential contamination during sample preparation. Determined element mass fractions are in agreement with literature values within ±20%. For boron isotope ratios, the matrix‐dependent background elevation across the m/z from 9.9 to 11, and the effect of ablation mass was quantified. Measured δ11B values of most reference materials are consistent with literature values within ±1‰. The intermediate measurement precision is ±0.3‰ for JB‐2 with 30 μg g−1 B and ±0.4‰ for JA‐2 with 21 μg g−1 B. A publically available, web‐based streamlit app was developed for data processing (https://zenodo.org/doi/10.5281/zenodo.11150471). This paves the way for combined, accurate and precise elemental and boron isotope ratio measurements of geological materials.

The Impact of Boron Compounds on the Structure and Ionic Conductivity of LATP Solid Electrolytes.

The increasing demand for safe and high-energy-density battery systems has led to intense research into solid electrolytes for rechargeable batteries. One of these solid electrolytes is the NASICON-type Li1+xAlxTi2-x(PO4)3 (LATP) material. In this study, different boron compounds (10% B2O3 doped, 10% H3BO3 doped, and 5% B2O3 + 5% H3BO3 doped) were doped at total 10 wt.% into the Ti4+ sites of an LATP solid electrolyte to investigate the structural properties and ionic conductivity of solid electrolytes using the solid-state synthesis method. Characterization of the synthesized samples was conducted using X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), and electrochemical impedance spectroscopy (EIS). The XRD patterns of the boron-doped LATP (LABTP) samples show that the samples have a rhombohedral phase with space group R3¯c together and low amounts of impurity phases. While all the LABTP samples exhibited similar ionic conductivity values of around 10-4 S cm-1, the LABTP2 sample doped with 10 wt.% H3BO3 demonstrated the highest ionic conductivity. These findings suggest that varying B3+ ion doping strategies in LATP can significantly advance the development of solid electrolytes for all-solid-state lithium-ion batteries.

Enabling α-Functionalization of Carboxylic Acids by Boron Compounds

Enabling α-Functionalization of Carboxylic Acids by Boron Compounds

Ultrathin Boron Growth onto Nanodiamond Surfaces via Electrophilic Boron Precursors.

Diamond as a templating substrate is largely unexplored, and the unique properties of diamond, including its large bandgap, thermal conductance, and lack of cytotoxicity, makes it versatile in emergent technologies in medicine and quantum sensing. Surface termination of an inert diamond substrate and its chemical reactivity are key in generating new bonds for nucleation and growth of an overlayer material. Oxidized high-pressure high temperature (HPHT) nanodiamonds (NDs) are largely terminated by alcohols that act as nucleophiles to initiate covalent bond formation when an electrophilic reactant is available. In this work, we demonstrate a templated synthesis of ultrathin boron on ND surfaces using trigonal boron compounds. Boron trichloride (BCl3), boron tribromide (BBr3), and borane (BH3) were found to react with ND substrates at room temperature in inert conditions. BBr3 and BCl3 were highly reactive with the diamond surface, and sheet-like structures were produced and verified with electron microscopy. Surface-sensitive spectroscopies were used to probe the molecular and atomic structure of the ND constructs' surface, and quantification showed the boron shell was less than 1 nm thick after 1-24 h reactions. Observation of the reaction supports a self-terminating mechanism, similar to atomic layer deposition growth, and is likely due to the quenching of alcohols on the diamond surface. X-ray absorption spectroscopy revealed that boron-termination generated midgap electronic states that were originally predicted by density functional theory (DFT) several years ago. DFT also predicted a negative electron surface, which has yet to be confirmed experimentally here. The boron-diamond nanostructures were found to aggregate in dichloromethane and were dispersed in various solvents and characterized with dynamic light scattering for future cell imaging or cancer therapy applications using boron neutron capture therapy (BNCT). The unique templating mechanism based on nucleophilic alcohols and electrophilic trigonal precursors allows for covalent bond formation and will be of interest to researchers using diamond for quantum sensing, additive manufacturing, BNCT, and potentially as an electron emitter.

Synthesis of monofluoroalkenes via photocatalyzed decarboxylative and deboronative coupling of α-fluoroacrylic acids with organotrifluoroborates

A novel approach for the synthesis of monofluoroalkenes through photocatalyzed decarboxylative/deboronative coupling has been established, utilizing α-fluoroacrylic acids and alkyl trifluoroborates. This methodology provides an efficient strategy to forge C (sp2)–C (sp3) bonds, enabling the transformation of alkyl boron compounds into valuable monofluoroalkenes. The method demonstrates broad substrate scope, accepting a variety of α-fluoroacrylic acids, and yields the sought-after monofluoroalkene products with outstanding Z-selectivity under mild conditions.

Biomimetic Exploration and Reflection on Switchable Coordination and Narrow-Band Electrofluorochromic Devices.

Electrofluorochromic (EFC) materials and devices with controllable fluorescence properties show great application potential in advanced anticounterfeiting, information storage and display. However, the low color purity caused by the broad emission spectra and underperforming switching time of the existing EFC materials limit their application. Through biomimetic exploration and the study of reversible electrochemical responsive coordination reactions, boron-nitrogen embedded polyaromatics (B,N-PAHs) with narrow-band emission and high color purity have been successfully integrated into EFC systems, which also help to better understand the role of boron in biological activity. The EFC device achieve good performance containing quenching efficiency greater than 90% within short switching time (ton: 0.6s, toff: 2.4s), and nearly no performance change after 200 cycles test. Three primary color (red, green, and blue) EFC devices are successfully prepared. In addition, new phenomena are obtained and discussed in this biomimetic exploration of related boron reactions. The success and harvest of this exploration are expected to provide new ideas for optimizing properties and broadening applications of EFC materials. Moreover, it may provide ideas and reference significance for further exploring and understanding the function of boron compounds in biological systems.

Cell-cycle dependence on the biological effects of boron neutron capture therapy and its modification by polyvinyl alcohol

Boron neutron capture therapy (BNCT) is a unique radiotherapy of selectively eradicating tumor cells using boron compounds (e.g., 4-borono-l-phenylalanine [BPA]) that are heterogeneously taken up at the cellular level. Such heterogenicity potentially reduces the curative efficiency. However, the effects of temporospatial heterogenicity on cell killing remain unclear. With the technical combination of radiation track detector and biophysical simulations, this study revealed the cell cycle-dependent heterogenicity of BPA uptake and subsequent biological effects of BNCT on HeLa cells expressing fluorescent ubiquitination-based cell cycle indicators, as well as the modification effects of polyvinyl alcohol (PVA). The results showed that the BPA concentration in the S/G2/M phase was higher than that in the G1/S phase and that PVA enhances the biological effects both by improving the uptake and by canceling the heterogenicity. These findings might contribute to a maximization of therapeutic efficacy when BNCT is combined with PVA and/or cell cycle-specific anticancer agents.

A Coppoborylene Stabilized by Multicenter Covalent Bonding and Its Amphoteric Reactivity to CO.

A cationic copper-stabilized coppoborylene was prepared and structurally characterized via infrared photodissociation spectroscopy and density functional theory calculations. This structure exemplifies a new class of borylenes stabilized by three-center-two-electron metal-boron-metal covalent bonding interaction, displaying exceptional σ-acidity and unparalleled π-donor capability for CO activation that outperforms all of the known transition metal cations and is comparable or even superior to the documented base-trapped borylenes. Its neutral form represents a monovalent boron compound with a strongly reactive amphoteric boron center built on transition-metal-boron bonds, which inspires the design and synthesis of new members of the borylene family.

A Coppoborylene Stabilized by Multicenter Covalent Bonding and Its Amphoteric Reactivity to CO

AbstractA cationic copper‐stabilized coppoborylene was prepared and structurally characterized via infrared photodissociation spectroscopy and density functional theory calculations. This structure exemplifies a new class of borylenes stabilized by three‐center‐two‐electron metal‐boron‐metal covalent bonding interaction, displaying exceptional σ‐acidity and unparalleled π‐donor capability for CO activation that outperforms all of the known transition metal cations and is comparable or even superior to the documented base‐trapped borylenes. Its neutral form represents a monovalent boron compound with a strongly reactive amphoteric boron center built on transition‐metal‐boron bonds, which inspires the design and synthesis of new members of the borylene family.

Computing Molecular Descriptors of Boron Icosahedral sheet

AbstractBoron, the element which is in close proximity with carbon in the periodic table has been hypothesized to produce diverse two‐dimensional structures that differ from well‐studied 2D materials. Icosahedron , the monomers of which form the crystalline boron structure, appears as a recurring pattern in the chemistry of boron compounds, elemental boron and boron‐rich materials, functions as a building block in a majority of boron allotropes. The topological study of the icosahedral sheets is a necessary field to be investigated for the effective analysis and characterization of its physico‐chemical attributes without undertaking time‐consuming experimental research. The topological descriptors being expressed as numerical values enable scientists to compare and correlate data, which can be applied to quantitative structure‐activity relationships and quantitative structure‐property relationships modeling. In this study, various degree based molecular descriptors of the crystal boron icosahedral sheet has been formulated from a two‐dimensional lattice perspective using the ‐polynomial approach. To establish the significance of these descriptors in the study of chemical attributes, an efficient linear regression modeling has also been performed, enabling the prediction of properties of several other boron sheets.

Enhancement of structural, optical, electrical, optoelectronic and thermoelectric properties of ZnO thin film via Ni doping and Ni-B co-doping

In this study, the effects of nickel (Ni) and boron (B) elements on the structural, optical, electrical, optoelectronic, and thermoelectric properties of zinc oxide (ZnO) material were investigated. Therefore, undoped ZnO, 3% Ni-doped ZnO (Zn0.97Ni0.03O), and 3% Ni-1% B co-doped ZnO (Zn0.96Ni0.03B0.01O) solutions were prepared by the sol gel method. The produced solutions were coated on glass and p-type Si substrates via dip coating and spraying methods in the form of thin films. We produce pure and n-type semiconductors in the form of nanodots which have wurtzite ZnO polycrystalline structure for all samples. Ni and B co-doped sample is morphologically, electrically and optically enhanced the ZnO material with 3.08 eV band gap, homogenous surface and the highest electrical conductivity. In addition, the best material among the three samples that can be used as a visible light-sensitive sensor is Zn0.96Ni0.03B0.01O under feedback voltage. Technologically, this material can be turned into a photodiode device in the form of Au/Zn0.96Ni0.03B0.01O/p-Si. While the obtained ideality factor of ZnO from the forward bias region decreases from 5.7 to 3.4, its barrier height increases from 0.636 eV to 0.667 eV and serial resistance of contact decreases from 121.6 × 103 Ω to 5.6 × 103 Ω with Ni and B co-doping. Ni doping thin film improves the photovoltaic, and thermoelectric properties of ZnO. Ni-doped ZnO sample can be studied in form of the thin films as a thermoelectric material due to its ZT value is nearly 1.73 × 10–4 at 650 K. Its thermoelectric performance is 13 times better than the that of pure ZnO for the same temperature values. The efficiency of Ni-doped ZnO sample as solar cell increases 10 times compared to pure ZnO. In addition to the production of materials with improved energy efficiency, economical products suitable for use in large areas have been obtained in this study.

Determination of the properties of medium-density fiberboards produced using urea-formaldehyde resins modified with boron compounds

Effects of adding different boron compounds to the urea-formaldehyde resin were evaluated relative to the physical, mechanical, and other properties of medium-density fiberboard (MDF). While the chemical addition of boric acid to the urea-formaldehyde resin increased the modulus of rupture and modulus of elasticity values of MDF boards, the physical and chemical additions of other boron compounds decreased those values. While there were no significant decreases in internal bond values, the chemical addition of boric acid and borax decahydrate to urea-formaldehyde resin increased the internal bond values of MDF boards. It was observed that in both types of addition, borax pentahydrate reduced the formaldehyde emission values of MDF boards the most and also reduced the burnt area by up to 30%. When the type of addition of boron compounds to urea-formaldehyde was compared, the addition of boron compounds at the resin formation stage showed better results in the properties of MDF boards than physical addition.