Adsorption and biotransformation of 17β-estradiol in biological activated carbon adsorbers

As the first systematic study dealing with the adsorption of estrogens by granular activated carbon (GAC), the removal behavior of 17β-estradiol (E2) and its biotransformation product of estrone (E1) in fixed GAC columns was examined using four biological activated carbon (BAC) columns (BAC-1～BAC-4) generated by coating four GAC columns with detached microorganisms from the riverbed sediment of a representative drinking river water source containing lower content of natural organic matter (NOM). For comparison, parallel adsorption experiments were also performed using another four GAC columns (GAC-1～ GAC-4) packed by strictly following the configurations of four BAC columns. Adsorption experimental results obtained by intermittently spiking E2 over a total running period about 350 days into the river water mixed with or without a peaty water containing higher content of NOM showed that E2 was readily removed by adsorption and the combined adsorption/biodegradation. The vertical profiles of E2 and E1, which have great significance for better understanding and optimization of the adsorption process for removal of human estrogens, were also obtained.     

Synthesis and structure revision of litseaone A

Litseaone A, isolated from the stem barks of Litsea rubescens and Litsea pedunculata, is a chalcone derivative with a novel spiro-epoxide moiety. The structural revision of litseaone A was achieved by the racemic synthesis of the proposed structure and the asymmetric synthesis of the revised structure. The major tautomeric structure of litseaone A and the relative stereochemistry at the epoxide carbon center were also clarified.     

Conformational transition of the core chain in radiation-modified polysilane micelles formed in selective solvents

Poly(methyl acrylate)-grafted poly(methyl-n-propylsilane) (PMPrS-g-PMA) and poly(acrylic acid)-grafted PMPrS (PMPrS-g-PAA) were synthesized by gamma-ray-induced graft polymerization, and the association behavior of these graft copolymers was investigated in selective solvents composed of good and poor solvents for the PMPrS main chain. Fluorescence spectroscopy with perylene as a fluorescent probe revealed that PMPrS-g-PAA in a water/THF mixed solvent self-assembles into micelles with a swollen core of PMPrS chains in the water content range of 50-95%. UV spectroscopy demonstrated that a further increase of the water content gives rise to the conformational transition of the PMPrS chains in the micelle core from the random conformation to the conformation that corresponds to that in the solid state at a water content of ca. 95%, independent of the grafting yield. Similar behavior was also observed in DMSO/THF solutions of PMPrS-g-PMA, for which the conformational transition occurred at the constant DMSO content of ca. 95%. These results indicate that solvatochromic behavior of polysilane, which is a characteristic feature of polysilane, proved to provide information on the inner structure of those micelles: PMPrS chains in the core undergo conformational transition as the content of the poor solvents for PMPrS increases, while maintaining the micelle structure.     

Pretreatment with High Mobility Group Box-1 Monoclonal Antibody Prevents the Onset of Trigeminal Neuropathy in Mice with a Distal Infraorbital Nerve Chronic Constriction Injury

Persistent pain following orofacial surgery is not uncommon. High mobility group box 1 (HMGB1), an alarmin, is released by peripheral immune cells following nerve injury and could be related to pain associated with trigeminal nerve injury. Distal infraorbital nerve chronic constriction injury (dIoN-CCI) evokes pain-related behaviors including increased facial grooming and hyper-responsiveness to acetone (cutaneous cooling) after dIoN-CCI surgery in mice. In addition, dIoN-CCI mice developed conditioned place preference to mirogabalin, suggesting increased neuropathic pain-related aversion. Treatment of the infraorbital nerve with neutralizing antibody HMGB1 (anti-HMGB1 nAb) before dIoN-CCI prevented both facial grooming and hyper-responsiveness to cooling. Pretreatment with anti-HMGB1 nAb also blocked immune cell activation associated with trigeminal nerve injury including the accumulation of macrophage around the injured IoN and increased microglia activation in the ipsilateral spinal trigeminal nucleus caudalis. The current findings demonstrated that blocking of HMGB1 prior to nerve injury prevents the onset of pain-related behaviors, possibly through blocking the activation of immune cells associated with the nerve injury, both within the CNS and on peripheral nerves. The current findings further suggest that blocking HMGB1 before tissue injury could be a novel strategy to prevent the induction of chronic pain following orofacial surgeries.     

Spontaneous and Widespread Electricity Generation in Natural Deep-Sea Hydrothermal Fields

Deep-sea hydrothermal vents discharge abundant reductive energy into oxidative seawater. Herein, we demonstrated that in situ measurements of redox potentials on the surfaces of active hydrothermal mineral deposits were more negative than the surrounding seawater potential, driving electrical current generation. We also demonstrated that negative potentials in the surface of minerals were widespread in the hydrothermal fields, regardless of the proximity to hydrothermal fluid discharges. Lab experiments verified that the negative potential of the mineral surface was induced by a distant electron transfer from the hydrothermal fluid through the metallic and catalytic properties of minerals. These results indicate that electric current is spontaneously and widely generated in natural mineral deposits in deep-sea hydrothermal fields. Our discovery provides important insights into the microbial communities that are supported by extracellular electron transfer and the prebiotic chemical and metabolic evolution of the ocean hydrothermal systems.     

Direct observation of unstable intermediate species in the reaction of trans-2-butene on ferrierite zeolite by picosecond infrared laser spectroscopy

The reaction dynamics of trans-2-butene adsorbed to acidic hydroxyl groups on the surface of ferrierite zeolite is examined by time-resolved spectroscopy using a tunable infrared picosecond pulse laser system. The transient absorption spectra measured by a two-color pump-probe technique at 188-243 K reveal bleaching and hot bands of the OD stretching mode 2 ps after excitation. This vibrationally excited state relaxes within 20 ps at 188 K, while the bleaching band includes a long-lifetime component that lasts for more than 100 ps at 243 K. Thus, the OD (isotope-exchanged hydroxy groups) stretching band does not entirely recover in this period and is mirrored by an analogous weakening of the CH bending band of the adsorbed trans-2-butene. Simultaneously, three new bands in CH stretching region were observed at 3045, 3095, and 3130 cm(-1). This result suggests the presence of a short-lived intermediate formed by reaction between the acidic hydroxyl groups and adsorbed trans-2-butene.     

Mechanical properties and structure of the zone‐drawn poly(L‐lactic acid) fibers

The zone‐drawing (ZD) method was applied three times to the melt‐spun poly(L ‐lactic acid) (PLLA) fibers of low molecular weight (M_v = 13,100) at different temperatures under various tensions. The mechanical properties and superstructure of the ZD fibers were investigated. The resulting ZD‐3 fiber had a draw ratio of 10.5, birefringence of 37.31 × 10⁻³, and crystallinity of 37%, while an orientation factor of crystallites remarkably increased to 0.985 by the ZD‐1. The Young's modulus and tensile strength of the ZD‐3 fiber respectively attained 9.1 GPa and 275 MPa, and the dynamic storage modulus was 10.4 GPa at room temperature. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 991–996, 1999     

Noncanonical RNA Nucleosides as Molecular Fossils of an Early Earth—Generation by Prebiotic Methylations and Carbamoylations

The RNA‐world hypothesis assumes that life on Earth started with small RNA molecules that catalyzed their own formation. Vital to this hypothesis is the need for prebiotic routes towards RNA. Contemporary RNA, however, is not only constructed from the four canonical nucleobases (A, C, G, and U), it also contains many chemically modified (noncanonical) bases. A still open question is whether these noncanonical bases were formed in parallel to the canonical bases (chemical origin) or later, when life demanded higher functional diversity (biological origin). Here we show that isocyanates in combination with sodium nitrite establish methylating and carbamoylating reactivity compatible with early Earth conditions. These reactions lead to the formation of methylated and amino acid modified nucleosides that are still extant. Our data provide a plausible scenario for the chemical origin of certain noncanonical bases, which suggests that they are fossils of an early Earth.