Geology and geochemistry of the Paleoproterozoic borate deposits in Liaoning-Jilin,northeastern China: evidence of metaevaporites

The borate deposits in Liaoning, Jilin province, China, are hosted in the Paleoproterozoic meta-volcanic-sedimentary sequence which comprises magnetite-microcline rocks, K- and Na-rich leptynites and leptites, magnesium marbles and amphibolites. The borates are exclusively hosted in the magnesium carbonates and Mg-silicate rocks. The association of these rocks, their sedimentary structures and unusual chemical composition suggest that their protolithes were sediments deposited in evaporite basins: red beds, zeolitized tuffs and evaporites. Therefore, the borate deposits are metamorphosed evaporites. The initial precipitates were magnesium carbonates and hydrous magnesium borates, reflecting a MgSO_4 brine stage in a playa lake environment. During the subsequent metamorphism, these borates were dehydrated to form anhydrous borates, e.g. suanite and ludwigite. These deposits are analogous to many modern evaporite sequences in rift systems. Mineralogically, these borates are comparable to the borates in the saline lakes in the Qinghai-Xizang (Tibet) plateau. This revised version was published online in July 2006 with corrections to the Cover Date.     

Comparative toxicology of borates

Inorganic borates, including boric acid, Na, ammonium, K, and Zn borates generally display low acute toxicity orally, dermally, and by inhalation. They are either not irritant or mild skin and eye irritants. Exceptions owing to physiochemical properties do occur. Longer-term toxicological studies have been reported mainly on boric acid or borax where the properties are generally similar on an equivalent boron (B) basis. The critical effects in several species are male reproductive toxicity and developmental toxicity. The doses that cause these effects are far higher than any levels to which the human population could be exposed. Humans would need to consume daily some 3.3 g of boric acid (or 5.0 g borax) to ingest the same dose level as the lowest animal NOAEL. No effects on fertility were seen in a population of workers exposed to borates or to a population exposed to high environmental borate levels. There is remarkable similarity in the toxicological effects of boric acid and borax across different species. Other inorganic borates that simply dissociate to boric acid are expected to display similar toxicity, whereas those that do not dissociate simply to boric acid may display a different toxicological profile.     

Borate Minerals and Origin of the RNA World

The RNA World is generally thought to have been an important link between purely prebiotic (>3.7 Ga) chemistry and modern DNA/protein biochemistry. One concern about the RNA World hypothesis is the geochemical stability of ribose, the sugar moiety of RNA. Prebiotic stabilization of ribose by solutions associated with borate minerals, notably colemanite, ulexite, and kernite, has been proposed as one resolution to this difficulty. However, a critical unresolved issue is whether borate minerals existed in sufficient quantities on the primitive Earth, especially in the period when prebiotic synthesis processes leading to RNA took place. Although the oldest reported colemanite and ulexite are 330 Ma, and the oldest reported kernite, 19 Ma, boron isotope data and geologic context are consistent with an evaporitic borate precursor to 2400-2100 Ma borate deposits in the Liaoning and Jilin Provinces, China, as well as to tourmaline-group minerals at 3300–3450 Ma in the Barberton belt, South Africa. The oldest boron minerals for which the age of crystallization could be determined are the metamorphic tourmaline species schorl and dravite in the Isua complex (metamorphism between ca. 3650 and ca. 3600 Ma). Whether borates such as colemanite, ulexite and kernite were present in the Hadean (>4000 Ma) at the critical juncture when prebiotic molecules such as ribose required stabilization depends on whether a granitic continental crust had yet differentiated, because in its absence we see no means for boron to be sufficiently concentrated for borates to be precipitated.     

Inactivation of tobacco ribulosebisphosphate carboxylase by 2,3-butanedione.

Treatment of crystalline tobacco ribulosebisphosphate carboxylase (EC 4.1.1.39) with the arginine-selective α-dicarbonyl, 2,3-butanedione, results in a time- and concentration-dependent loss of activity. Inactivation is markedly enhanced by borate buffer and alkaline pH and is partially reversed upon removal of excess reagent and borate by gel filtration. Of the various ligands examined, only the phosphorylated substrate, ribulosebisphosphate, protects against inactivation. These results suggest an essential role for arginyl residues in the enzymic mechanism of ribulosebisphosphate carboxylase, probably as binding sites for the negatively charged phosphate groups of the non-gaseous substrate.     

The synthesis and use of thionphospholipids in 31P-NMR studies of lipid polymorphism

(1) Dipalmitoyl- and dioleoylthionphosphatidylcholine, which are phosphatidylcholine analogues in which the double bonded oxygen of the phosphate group is replaced by a sulfur atom, have been synthesized in 50–60% yields by condensation of diacylglycerol with phosphorus thionchloride in the presence of choline toluene-sulfonate. Dioleoylthionphosphatidylethanolamine has been prepared by the phospholipase D-catalyzed base exchange reaction. (2) Freeze-fracturing of aqueous dispersions of the thionphospholipids reveals that the thionphosphatidylcholines are organized in extended bilayers whereas dioleoylthionphosphatidylethanolamine above 0°C forms the hexagonal H_II phase similar to dioleoylphosphatidylethanolamine. The gel → liquid crystalline phase transition of the dipalmitoylthionphosphatidylcholine occurs at 44°C which is only slightly higher than the transition temperature of dipalmitoylphosphatidylcholine which together with other data demonstrates that the thionphospholipids closely resemble the natural phospholipids in physicochemical behaviour. (3) Proton decoupled ³¹P-NMR spectra of aqueous dispersions of thionphosphatidylcholines have the characteristic asymmetrical line-shape with a low-field shoulder and a high-field peak typical of phospholipids organized in extended bilayers in which the phosphate group can undergo fast axial rotation. The ³¹P-NMR spectrum of the thionphosphatidylethanolamine in the hexagonal H_II phase has a line-shape with a reversed asymmetry and an effective chemical shift anisotropy half of that of thionphospholipids organized in bilayers which is caused by fast lateral diffusion of the lipids around the cylinders of the hexagonal H_II phase as has been observed for the corresponding phosphatidylethanolamines. (4) Since the ³¹P-NMR resonance of the thionphospholipids is completely separated from that of natural phospholipids, these lipids can be used to study by ³¹P-NMR the motional and structural properties of individual lipids in mixed systems. This is demonstrated for various lipid mixtures in which non-bilayer lipid structures have been induced by variations in composition, temperature and presence of divalent cations. It is shown that bilayer → non-bilayer transitions can be modulated by gel → liquid crystalline phase transitions and that typical bilayer forming lipids can be incorporated into non-bilayer structures such as the hexagonal H_II phase.     

Is Boron a Prebiotic Element? A Mini-review of the Essentiality of Boron for the Appearance of Life on Earth

Boron is probably a prebiotic element with special importance in the so-called "sugars world". Boron is not present on Earth in its elemental form. It is found only in compounds, e.g., borax, boric acid, kernite, ulexite, colemanite and other borates. Volcanic spring waters sometimes contain boron-based acids (e.g., boric, metaboric, tetraboric and pyroboric acid). Borates influence the formation of ribofuranose from formaldehyde that feeds the "prebiotic metabolic cycle". The importance of boron in the living world is strongly related to its implications in the prebiotic origins of genetic material; consequently, we believe that throughout the evolution of life, the primary role of boron has been to provide thermal and chemical stability in hostile environments. The complexation of boric acid and borates with organic cis-diols remains the most probable chemical mechanism for the role of this element in the evolution of the living world. Because borates can stabilize ribose and form borate ester nucleotides, boron may have provided an essential contribution to the "pre-RNA world".     

Reducing leaching of boron-based wood preservatives - a review of research

Inorganic borates offer good protection to timber in most non-ground contact applications. The effective use of low solubility borates has not yet been achieved in the treatment of solid lumber. Interest in reducing the leaching of borates stems from their favorable environmental characteristics and broad spectrum efficacy. The key to extending the use of borates to cover the entire spectrum of wood preservation is improving their permanence in wood while retaining efficacy by retaining limited mobility of the borate. We review research over the last two decades in laboratories around the world and classify all strategies employed into fifteen categories. For each strategy, resistance of the treated wood to wood destroying organisms, resistance to leaching, and potential applications are discussed.     

Luminescent inorganic mixed borate phosphors materials for lighting

The need of new materials with desirable optical properties has become important in recent years. In particular, a need has emerged for compounds having better luminescence properties in various practical applications. The introduction of rare earth ions as activators improves the luminescence properties of the compounds considerably. Boron is one of the most abundant elements in nature. It readily combines with almost all other elements. In combination with oxygen; it forms borates comprised of various anions such as BO₃³⁻, B₂O₅⁴⁻, etc. Apart from these simple borates, several complex compositions exist involving mixed anions as well as double metal borates, due to the three-fold, or four-fold coordination of borate atoms. Borates intrinsically possesses characteristics that are advantageous for optical materials, which include a wide transparency range, large electronic band gap, good thermal and chemical stability, low preparative temperature, optical stability with good nonlinear characteristics, and an exceptionally high optical damage threshold. The unique crystal structure of borates determines their enhanced ultraviolet light transparency, good nonlinearity, and relatively high resistance against laser-induced damage. Some of these complex borates have interesting luminescence properties that are covered in this review. These include double borates containing rare earths RM₃(BO₃)₄, pentaborates LaMgB₅O₁₀, M₃R₂(BO₃)₄, where M is an alkaline earth, mixed anion borates such as aluminoborate SrAl₂B₂O₇, silicate-borates such as pekovite, SrB₂Si₂O₈, haloborates, M₂B₅O₉X, where M is an alkaline earth and X is a halogen, phosphate borates, and MBPO₅, where M is an alkaline earth. Phosphors based on these compositions find use in various applications such as fluorescence lamps, colour TVs, plasma display panels, high-intensity discharge lamps based on xenon, optically pumped solid-state lasers, eye-safe lasers, and X-ray imaging.     

Limited rotational motion of amphiphilic flavins in dipalmitoylphosphatidylcholine vesicles

The rotational motion of amphiphilic flavins in dipalmitoyl phospholipid bilayers was investigated with fluorescence anisotropy decay measurements. At temperatures between 10 and 50°C the rotation proved to be anisotropic, which indicated composite motion of both the aliphatic side-chain and the isoalloxazine moiety of the octadecyllumiflavin derivatives. Above the phase transition temperature (crystalline→liquid-crystalline state) the depolarization is complete within the average flavin fluorescence lifetime, implicating unrestricted motion and resulting in a non-ordered microenvironment. In the gel or crystalline state the flavin motion can best be characterized as a limited rotation or librational motion. The fluorescence decay of the flavins is heterogeneous at temperatures between 10 and 50°C, which is explained by assuming nanosecond relaxation of the polar phosphatidyl head-groups around the excited flavin. The lack of a significant cholesterol effect suggests that the isoalloxazine is located at the interphase of the bilayer and not in the hydrocarbon region. The microstructure is fluid-like, not in agreement with a preferred static localization of the flavins in the bilayer.     

Synthesis and spectroscopic investigations of four-coordinate nickel complexes supported by a strongly donating scorpionate ligand

Two four-coordinate nickel complexes, HB(^tBuIm)₃NiBr and HB(^tBuIm)₃NiNO, were prepared by reaction of a bulky tris(carbene)borate ligand with NiBr₂(PPh₃)₂ and NiBr(NO)(PPh₃)₂, respectively, and structurally and spectroscopically characterized. In addition to standard techniques, high-frequency and -field electron paramagnetic resonance (HFEPR) was employed to understand the spin triplet (S = 1) ground state of the bromo complex. HFEPR, combined with electronic absorption spectroscopy allows comparison of this novel complex with other paramagnetic four-coordinate Ni(II) species. The tris(carbene)borate ligand is a stronger σ-donor than corresponding tris(pyrazolyl)borates (traditional “scorpionate” ligands). The tris(carbene)borate ligand may also act as a π-acceptor, in contrast to tris(pyrazolyl)borates, which show relatively little π-bonding interactions. The influence of tris(carbene)borate substituents on the donor strength of the ligand have been elucidated from IR spectroscopic investigations of {NiNO}¹⁰ derivatives. HFEPR spectra of HB(^tBuIm)₃NiBr exhibit hyperfine coupling from Br, which indicates the strong electronic interaction between Ni(II) and this halide ligand, consistent with studies on tris(pyrazolyl)borate Ni(II) complexes.     

Amount of leachant and water absorption levels of wood treated with borates and water repellents

Wood protection efficacy of borates against biological agents, flame retardancy, and suitability to the environment is well known. Since borates can be applied to timber as water based solutions, they are preferred economically as well. Even though they are highly mobile in wood, boron compounds are widely used in timber preservation. Borates migrate in liquid and increase the hygroscopicity of wood in damp conditions. This study deals with the physical restriction of water access in wood by impregnating water repellent agents into wood to limit amount of leachant and water absorption levels of wood after boron treatment. Borates were incorporated with polyethylene glycol-400 (PEG-400) their bulking effect in wood was considered. Results indicated that the amount of leachates from wood treated with borates in PEG-400 was remarkably higher compared to those of wood treated with the aqueous solutions of borates. Water absorption (WA) levels of wood treated with aqueous solutions of borates were higher than those of their treated samples with the solutions in PEG-400. Secondary treatments of wood with the water repellent (WR) chemicals following borate impregnation reduced the leaching of chemicals from wood in water and also WA of the specimens were less than those of the wood treated with only borates from aqueous and PEG solutions. Styrene (St) was the most effective monomer among the other agents used in terms of immobility effect on borates and WA.     

Immobilization of lipoxygenase in an alginate-silicate solgel matrix: formation of fatty acid hydroperoxides

A method for the immobilization of lipoxygenase (LOX) in an alginate-silicate gel matrix was developed. In this method, a mixture of calcium alginate beads and LOX in borate buffer are dispersed into a hexane solution of tetramethoxy-ortho-silicate (TMOS). Hydrolysis of the TMOS gives products that permeate and co-polymerize with the alginate gel to form a colloid within the beads that entraps the LOX. Optimum reaction conditions for sol-gel entrapment of LOX are at pH 9.0 in 0.2M borate buffer. The composite gel, after isolation and vacuum drying, had excellent protein retention that has good enzyme activity and stability at room temperature. The activity of the entrapped LOX was less than the activity of the free enzyme. However, the activity of the immobilized LOX can be restored by the addition of borate buffer and glycerol, or borate buffer saturated with an organic solvent. In contrast to the free enzyme in solution, which loses its activity in less than one day, sol-gel entrapped LOX retains its activity at ambient temperature for at least 25 days and can be recycled. This report demonstrates that the sol-gel entrapment method for immobilizing LOX can be useful in developing a process for the oxidation of polyunsaturated fatty acids.     

A comparison of worker exposure to inhalable and total dust, inorganic arsenic, and borates using two types of particulate sampling assemblies in a borate mining and processing facility

This study describes a comparison of worker exposure to total and inhalable dust, inorganic As, and borates using two types of particulate sampling assemblies as part of a comprehensive industrial hygiene evaluation in a borate mining and processing facility. Employees were segmented into similar exposure groups (SEG) based on work location within the facility, job classification, and type of chemical agent. Approximately 10% of the employees from each SEG wore two personal sampling devices simultaneously for the purpose of collecting total and inhalable particulate fractions using a closed face, 37-mm mixed cellulose ester matched-weight filters (MMW), and Institute of Occupational Medicine (IOM) sampling assembly. Sample results indicated that the IOM concentrations were consistently higher than the corresponding MMW concentrations for all three agents. An analysis was performed to investigate a relationship between MMW and IOM. The data revealed correlation coefficient values of 0.72, 0.82, and 0.84 for total dust (n = 197), inorganic As (n = 137), and borates (n = 194), respectively. These positive correlation coefficients indicate that the IOM and MMW measurements are consistent with each other, and can be used for predicting exposure levels. The total dust and borate large mean ratios should be considered in developing inhalable fraction-based regulatory standards.     

Cross-polarization/magic-angle spinning 13C-nmr of (1 → 6)-β-D-glucan (pustulan): Mechanism of gelation

¹³C-nmr has been employed to probe the molecular conformation and crystal structure of (1 → 6)-β-D -glucan (pustulan) in the solution, gel, and solid states. CP/MAS ¹³C-nmr spectra recorded for partially crystalline solid pustulan display a resonance near 82 ppm that is absent in solution spectra. The intensity and peak width of this resonance were found to depend on relative crystallinity as determined by x-ray diffraction. CP/MAS spectra of aqueous pustulan gels also exhibit the 82-ppm resonance, suggesting that the gelation mechanism may involve microcrystalline junction zones. Since the 82-ppm resonance is absent in the CP/MAS spectrum of the (1 → 6)-β-linked dimer gentiobiose, we tentatively conclude the crystal structure of this dimer does not adequately model the yet undetermined structure of pustulan.     

Senescence-Related Changes in the Lipid Transition Temperature of Microsomal Membranes from Algae

The phase behaviour of smooth microsomal membranes from senescing cultures of Scenedesmus quadricauda has been examined by wide-angle x-ray diffraction. The algae were grown in Bristol's medium at 22°C under continuous illumination. The transition temperature, taken to be the highest temperature at which crystalline (gel) phase lipid can be detected, increased with culture age from a low of 0°C for young cultures to a high of about 70°C for 140-day-old cultures. This indicates that for young cultures the membrane lipid is entirely liquid-crystalline (fluid) at physiological temperatures, but as the cultures age portions of the lipid become crystalline. The increase in transition temperature showed a close temporal correlation with loss of chlorophyll and loss of protein per g dry weight, and can thus be construed as an index of senescence. The unsaturated to saturated fatty acid ratio of the membrane lipid, while fluctuating with culture age, did not show any consistent trend that could be related to the change in transition temperature. Thus the formation of gel phase lipid does not appear to be due to a change in fatty acid saturation.     

A Composite Gel Polymer Electrolyte with High Performance Based on Poly(Vinylidene Fluoride) and Polyborate for Lithium Ion Batteries

A composite membrane based on electrospun poly(vinylidene fluoride) (PVDF) and lithium polyvinyl alcohol oxalate borate (LiPVAOB) exhibiting high safety (self‐extinguishing) and good mechanical property is prepared. The ionic conductivity of the as‐prepared gel polymer electrolyte from this composite membrane saturated with 1 mol L^?1 LiPF₆ electrolyte at ambient temperature can be up to 0.26 mS cm^?1, higher than that of the corresponding well‐used commercial separator (Celgard 2730), 0.21 mS cm^?1. Moreover, the lithium ion transference in the gel polymer electrolyte at room temperature is 0.58, twice as that in the commercial separator (0.27). Furthermore, the absorbed electrolyte solvent is difficult to evaporate at elevated temperature. Its electrochemical performance is evaluated by using LiFePO₄ cathode. The obtained results suggest that this gel‐type composite membrane shows great possibilities for use in large‐capacity lithium ion batteries that require high safety.     

The size effect to O2−–Ce4+ charge transfer emission and band gap structure of Sr2CeO4

Sr₂CeO₄ phosphors with different crystalline sizes were synthesized by the sol–gel method or the solid‐state reaction. Their crystalline size, luminescence intensity of O^2??Ce⁴⁺ charge transfer and energy gaps were obtained through the characterization by X‐ray diffraction, photoluminescence spectra, as well as UV–visible diffuse reflectance measurements. An inverse relationship between photoluminescence (PL) spectra and crystalline size was observed when the heating temperature was from 1000°C to 1300°C. In addition, band energy calculated for all samples showed that a reaction temperature of 1200°C for the solid‐state method and 1100°C for sol–gel method gave the largest values, which corresponded with the smallest crystalline size. Correlation between PL intensity and crystalline size showed an inverse relationship. Band structure, density of states and partial density of states of the crystal were calculated to analyze the mechanism using the cambrige sequential total energy package (CASTEP) module integrated with Materials Studio software.     

Mechanical stresses in erythrocyte membranes (theoretical models)

The type of mechanical stresses that arise in erythrocyte membranes on exposure to catecholamines and steroid hormones is considered. Tensors of mechanical stresses and displacements were obtained for a membrane interacting with hormones. A possible mechanism of membrane rupture under mechanical stresses is discussed. Catecholamines and androgens increase the microviscosity of membranes, and alternating kink and stretching sites occur in the lipid membrane bilayer to produce a checker-wise pattern. The membrane becomes thinner in a stretching site (smectic A → smectic C transition). When tensile stresses increase further and exceed a certain critical value the membrane may rupture. It is possible that a gel phase L_β? → liquid crystalline phase L_α transition takes place in the stretching site of the lipid bilayer prior to disruption. The density of the lipid bilayer decreases in the process, pores form, and then cracks occur.     

Analysis of glycopeptides as borate complexes by polyacrylamide gel electrophoresis

A new method using polyacrylamide gel electrophoresis in a Tris-borate buffer to analyze Pronase-derived glycopeptides is described. Examination of immunoglobulin, Sindbis virus, and ovalbumin-radiolabeled glycopeptides by this system demonstrates a pattern similar to that seen after Bio-Gel-P-6 chromatography and, in addition, exposes a heterogeneity in the immunoglobulin and Sindbis virus glycopeptides not apparent after gel filtration. The resolution of glycopeptides by gel electrophoresis depends on the inclusion of borate ions in the sample, the gel, and the electrophoresis buffer. The borate ions react with neutral sugars, converting them to charged complexes which migrate during electrophoresis. The number of borate ions bound to a glycopeptide is a function of the composition, sequence, and linkages of the carbohydrates. Gel electrophoresis of glycopeptides in a borate buffer has several advantages: (1) The method requires no new equipment or special skills beyond those necessary for conventional polyacrylamide gel electrophoresis; (2) when performed on a slab gel, up to 24 samples can be analyzed simultaneously; and (3) since detection is by radio-autography, small amounts of radiolabeled glycopeptides can be visualized by prolonging the exposure time. These characteristics are advantageous for studies of glycopeptides based on digestion products resulting from incubations with specific exo- and endo-glycosidases. Untreated glycopeptides have been compared on the same gel with glycopeptides sequentially treated with different glycosidases to gain structural information.     

Catalysis of three sequential dioxygenase reactions by thymine 7-hydroxylase

A purification scheme has been developed for an enzyme, thymine 7-hydroxylase, which appears to catalyze three sequential dioxygenase reactions, i.e., thymine → 5-hydroxymethyluracil → formyluracil → uracil-5-carboxylic acid. The enzyme was purified 1,300-fold from Neurospora crassa and had specific activities of approximately 1200, 600, and 250 U/mg for the respective reactions. Evidence that a single protein catalyzes the three reactions includes: the parallel purification of the three activities throughout the purification scheme, the inhibition of each reaction by the substrates of the other two, the inhibition of the three reactions by uracil, the parallel loss of the three activities upon heat denaturation, and considerations of a mechanism which suggest that a single active site may be involved.