An Engineered Biliverdin-Compatible Cyanobacteriochrome Enables a Unique Ultrafast Reversible Photoswitching Pathway

Cyanobacteriochromes (CBCRs) are promising optogenetic tools for their diverse absorption properties with a single compact cofactor-binding domain. We previously uncovered the ultrafast reversible photoswitching dynamics of a red/green photoreceptor AnPixJg2, which binds phycocyanobilin (PCB) that is unavailable in mammalian cells. Biliverdin (BV) is a mammalian cofactor with a similar structure to PCB but exhibits redder absorption. To improve the AnPixJg2 feasibility in mammalian applications, AnPixJg2_BV4 with only four mutations has been engineered to incorporate BV. Herein, we implemented femtosecond transient absorption (fs-TA) and ground state femtosecond stimulated Raman spectroscopy (GS-FSRS) to uncover transient electronic dynamics on molecular time scales and key structural motions responsible for the photoconversion of AnPixJg2_BV4 with PCB (Bpcb) and BV (Bbv) cofactors in comparison with the parent AnPixJg2 (Apcb). Bpcb adopts the same photoconversion scheme as Apcb, while BV4 mutations create a less bulky environment around the cofactor D ring that promotes a faster twist. The engineered Bbv employs a reversible clockwise/counterclockwise photoswitching that requires a two-step twist on ~5 and 35 picosecond (ps) time scales. The primary forward P_fr → P_o transition displays equal amplitude weights between the two processes before reaching a conical intersection. In contrast, the primary reverse P_o → P_fr transition shows a 2:1 weight ratio of the ~35 ps over 5 ps component, implying notable changes to the D-ring-twisting pathway. Moreover, we performed pre-resonance GS-FSRS and quantum calculations to identify the Bbv vibrational marker bands at ~659,797, and 1225 cm⁻¹. These modes reveal a stronger H-bonding network around the BV cofactor A ring with BV4 mutations, corroborating the D-ring-dominant reversible photoswitching pathway in the excited state. Implementation of BV4 mutations in other PCB-binding GAF domains like AnPixJg4, AM1_1870g3, and NpF2164g5 could promote similar efficient reversible photoswitching for more directional bioimaging and optogenetic applications, and inspire other bioengineering advances.     

Identification of Tumor Suppressive Genes Regulated by miR-31-5p and miR-31-3p in Head and Neck Squamous Cell Carcinoma

We identified the microRNA (miRNA) expression signature of head and neck squamous cell carcinoma (HNSCC) tissues by RNA sequencing, in which 168 miRNAs were significantly upregulated, including both strands of the miR-31 duplex (miR-31-5p and miR-31-3p). The aims of this study were to identify networks of tumor suppressor genes regulated by miR-31-5p and miR-31-3p in HNSCC cells. Our functional assays showed that inhibition of miR-31-5p and miR-31-3p attenuated cancer cell malignant phenotypes (cell proliferation, migration, and invasion), suggesting that they had oncogenic potential in HNSCC cells. Our in silico analysis revealed 146 genes regulated by miR-31 in HNSCC cells. Among these targets, the low expression of seven genes (miR-31-5p targets: CACNB2 and IL34; miR-31-3p targets: CGNL1, CNTN3, GAS7, HOPX, and PBX1) was closely associated with poor prognosis in HNSCC. According to multivariate Cox regression analyses, the expression levels of five of those genes (CACNB2: p = 0.0189; IL34: p = 0.0425; CGNL1: p = 0.0014; CNTN3: p = 0.0304; and GAS7: p = 0.0412) were independent prognostic factors in patients with HNSCC. Our miRNA signature and miRNA-based approach will provide new insights into the molecular pathogenesis of HNSCC.     

Synthesis and electronic property of platinum nanowire and nanoparticle in mesoporous silica template

Platinum nanowires and nanoparticles were selectively synthesized in mesoporous silicas FSM-16 and HMM-1. The nanowires are 3 nm in diameter and several hundred nm to μm in length with high crystallinity. Pt nanowires and nanoparticles can be isolated by dissolving silica matrix with HF. The Pt wires extracted from organosilica HMM-1 have a nanonecklace structure, while the wires from siliceous FSM-16 have a nanorod structure. The extracted Pt nanoparticles (3 nm in size) on HOPG show the Coulomb staircase phenomena in STM/STS analysis. The mechanism for formation of the Pt nanowires is based on the migration of Pt ions in the mesoporous channels.     

Preparation of Protein-Stabilized β-Carotene Nanodispersions by Emulsification–Evaporation Method

This work was initiated to prepare protein-stabilized β-carotene nanodispersions using emulsification–evaporation. A pre-mix of the aqueous phase composed of a protein and hexane containing β-carotene was subjected to high-pressure homogenization using a microfluidizer. Hexane in the resulting emulsion was evaporated under reduced pressures, causing crystallization and precipitation of β-carotene inside the droplets and formation of β-carotene nanoparticles. Sodium caseinate (SC) was the most effective emulsifier among selected proteins in preparing the nanodispersion, with a monomodal β-carotene particle-size distribution and a 17-nm mean particle size. The results were confirmed by transmission-electron microscopy analysis. SC-stabilized nanodispersion also had considerably high ζ-potential (−27 mV at pH 7), suggesting that the nanodispersion was stable against particle aggregation. Increasing the SC concentration decreased the mean particle size and improved the polydispersity of the nanodispersions. Nanodispersions prepared with higher β-carotene concentrations and higher organic-phase ratios resulted in larger β-carotene particles. Although increased microfluidization pressure did not decrease particle size, it did improve the polydispersity of the nanodispersions. Repeating the microfluidization process at 140 MPa caused the nanodispersions to become polydisperse, indicating the loss of emulsifying capacity of SC due to protein denaturation.     

A Practical Model for the Interactions Between Hydrating Portland Cements and Poly-β-Naphthalene Sulfonate Condensate Superplasticizers

The performance of poly-β-naphthalene sulfonate condensate superplasticizer (BNS) as a dispersant for cement in concrete is affected severely by slight differences in the characteristics of the cement. In order to be able to predict these effects, a model for estimating the fluidity of cement paste containing BNS is proposed. This model is based on an assumption that the fluidity of cement paste is proportional to the BNS adsorption amount per surface area of hydrated cement (Ad/Hy). BNS is known to show two types of sorption on hydrated cement: one is the bulk absorption into initial hydrates and the other one is the superficial adsorption onto hydrates. Only the superficially adsorbed BNS is expected to work as a dispersant. By assuming a competitive Langmuir-type adsorption on hydrates between BNS and SO₄²⁻, a simple method to estimate Ad/Hy is developed, with the concentrations of BNS and SO₄²⁻ as the only two independent parameters. The resulting estimates of Ad/Hy show a good correlation with paste flow and its change with elapsed time for a broad range of cements. The SO₄²⁻ concentration in the aqueous phase of the cement paste just after the beginning of the mixing is known to affect the performance of BNS as a dispersant. By using the proposed model to discriminate between the superficial adsorption and bulk absorption of BNS, this phenomenon is explained quantitatively.     

Fast computation of computer-generated hologram using Xeon Phi coprocessor

We report fast computation of computer-generated holograms (CGHs) using Xeon Phi coprocessors, which have massively x86-based processors on one chip, recently released by Intel. CGHs can generate arbitrary light wavefronts, and therefore, are promising technology for many applications: for example, three-dimensional displays, diffractive optical elements, and the generation of arbitrary beams. CGHs incur enormous computational cost. In this paper, we describe the implementations of several CGH generating algorithms on the Xeon Phi, and the comparisons in terms of the performance and the ease of programming between the Xeon Phi, a CPU and graphics processing unit (GPU).     

Fabrication of Nonadditive Mica Ceramics by Hot Isostatic Processing

Powder compacts of synthetic mica (fluorphlogopite) encapsulated in a boro–silicate glass tube were isostatically hot–pressed in a Roy–Tuttle–type pressure vessel. Synthetic mica was sintered to a density of 2.60 g/cm³ (91.2% of theoretical density) without additives under 98 MPa of water at 800°C for 45 min.     

A PRACTICAL METHOD FOR RECTIFYING INTERFACIAL TENSION DATA TO PREDICT THE SHAPE OF INTERFACES IN AN IMMISCIBLE LIQUID/LIQUID/GAS SYSTEM

The shape of interfaces formed by the contact of two liquid phases, immiscible with each other, and a gaseous phase can be predicted on the condition that the tension to work at each interface is known with a sufficient accuracy. In general, interfacial tension data available are not so accurate, however, as to be useful as they are in predicting the shape of interfaces, particularly when the spreading coefficient of either liquid (liquid 1) on the other (liquid 2) has a negative value of a small magnitude. Presented in this note is a simple method to rectify the interfacial tension data, with the aid of a measurement of the radius of a lens of liquid 1 of a known volume placed on the horizontal surface of liquid 2, and thereby make them usable for predicting interfacial geometries. The method is tested by applying it to benzene/water and n-pentane/water systems.     

Role of tungsten in promoting selective reduction of NO with CO over Ir/WO3–SiO2 catalysts

Catalytic hydrogenation of naphthalene to decalin was studied over a carbon-supported rhodium catalyst in supercritical carbon dioxide solvent at 333 K, and the results were compared with those in an organic solvent. cis-, trans-Decalin and tetralin were formed from the beginning of the reaction in supercritical carbon dioxide. Higher concentration of hydrogen in carbon dioxide solvent and on the active site, and also the suppression of desorption of partially hydrogenated tetralin molecules from the active site would be responsible for higher selectivity to cis-decalin in supercritical carbon dioxide than that in an organic solvent.     

Effect of cation structure on the electrochemical and thermal properties of ion conductive polymers obtained from polymerizable ionic liquids

Several onium cations having vinyl group formed ionic liquids after coupling with bis(trifluoromethanesulfonyl)imide. These monomers were polymerized, and the relation between onium cation structure and properties of thus polymerized ionic liquids was investigated. The polymerized ionic liquid having ethylimiadzolium cation unit showed the highest ionic conductivity of around 10⁻⁴ S cm⁻¹ at 30 °C among the obtained polymers reflecting the lowest glass transition temperature of −59 °C. These polymers were thermally stable and their decomposition temperatures were about 350 °C. The ionic conductivity of the polymerized ionic liquids decreased by both the addition of lithium bis(trifluoromethanesulfonyl)imide and the polymerization in the presence of cross-linker. However, the polymerized ionic liquid having 1-methylpiperidinium cation structure showed good lithium ion transference number of 0.43 at room temperature.