Hydrogenases (H2ases) are benchmark electrocatalysts for H2 production, both in biology and (photo)catalysis in vitro. We report the tailoring of a p‐type Si photocathode for optimal loading and wiring of H2ase through the introduction of a hierarchical inverse opal (IO) TiO2 interlayer. This proton‐reducing Si|IO‐TiO2|H2ase photocathode is capable of driving overall water splitting in combination with a photoanode. We demonstrate unassisted (bias‐free) water splitting by wiring Si|IO‐TiO2|H2ase to a modified BiVO4 photoanode in a photoelectrochemical (PEC) cell during several hours of irradiation. Connecting the Si|IO‐TiO2|H2ase to a photosystem II (PSII) photoanode provides proof of concept for an engineered Z‐scheme that replaces the non‐complementary, natural light absorber photosystem I with a complementary abiotic silicon photocathode.

Atomic layer deposition (ALD) of ultrathin aluminum oxide (AlOx) films was systematically studied on supported chemical vapor deposition (CVD) graphene. We show that by extending the precursor residence time, using either a multiple-pulse sequence or a soaking period, ultrathin continuous AlOx films can be achieved directly on graphene using standard H2O and trimethylaluminum (TMA) precursors even at a high deposition temperature of 200 °C, without the use of surfactants or other additional graphene surface modifications. To obtain conformal nucleation, a precursor residence time of >2s is needed, which is not prohibitively long but sufficient to account for the slow adsorption kinetics of the graphene surface. In contrast, a shorter residence time results in heterogeneous nucleation that is preferential to defect/selective sites on the graphene. These findings demonstrate that careful control of the ALD parameter space is imperative in governing the nucleation behavior of AlOx on CVD graphene. We consider our results to have model system character for rational two-dimensional (2D)/non-2D material process integration, relevant also to the interfacing and device integration of the many other emerging 2D materials.

Breast cancer (BC) is the most common malignant tumor among women worldwide. Development of novel molecular targets is important to improve prognosis of BC patients. Derlin 3 (DERL3) gene is a member of derlin family, and its coding protein is critical to the endoplasmic reticulum-associated degradation mechanism. However, its oncological role in breast cancer remains unclear. This study evaluated DERL3 expression and function in BC. We analyzed DERL3 mRNA in 13 BC and two non-cancerous cell lines, and explored effects of DERL3 knockdown on BC proliferation, invasion and migration. We also evaluated correlation of DERL3 mRNA expression levels with clinicopathological factors and prognosis in 167 BC patients. DERL3 mRNA expression was detected in five (38%) BC cell lines. Inhibiting DERL3 expression significantly decreased proliferation and invasion in BC cells. Specimens from patients with lymph node metastasis had higher DERL3 mRNA expression than those without (P=0.030). Patients in the highest quartile for DERL3 mRNA expression (n=42) were more likely to experience shorter overall survival than other patients (P=0.032). These findings indicate that DERL3 promotes malignant phenotype in BC cells. DERL3 may serve as a potential prognostic marker and therapeutic target for BC.

Surfaces consisting of sub micron holes (0.420-0.765 μm) engineered into nanoparticle (12 nm) coatings were examined for marine antifouling behaviour that defines early stage settlement. Immersed surfaces were found to be resistant to a 5-hour attachment assay of Amphora coffeaeformis, a marine organism commonly found in abundance on fouled substrates such as foul-releasing paints and self-polishing coatings. Attachment inhibition was attributed to the accessibility of diatoms to the surface. This was governed by the size and morphology of trapped interfacial air pockets measured in-situ using synchrotron small angle x-ray scattering. Surfaces containing larger pores (0.765 μm) exhibited the highest resistance. Macroscopic wettability via contact angle measurements however remained at 160° and sliding angle of < 5° and was found to be independent of pore size and not indicative of early stage fouling behaviour. The balance of hierarchical nano/micro length scales was critical in defining the early stage stability of biofouling character of the interface.

We determine the pH dependency of the mid-infrared spectra in aqueous solution of the organic dissociative materials in the metabolic pathway: saccharide phosphates (G6P, F6P), adenosine, and its phosphates (ATP, ADP, AMP). The series of molar absorbance spectra for these reagents were obtained in a pH range of about 2 to 11 with a Fourier transform infrared (FT-IR) spectrometer equipped with a horizontal diamond attenuated total reflection (ATR) sampling accessory. We also provide a method of infrared spectral extraction of ionic dissociative materials by performing a linear least-square fitting utilizing the formulas of ionic dissociation equilibrium shift, and we obtain the infrared spectrum of each ionic species of the dissociative materials: G6P-, G6P2-; F6P-, F6P2-; ATP2-, ATP3-, ATP4-; ADP-, ADP2-, ADP3-; AMP, AMP-, AMP2-; and adenosine+, adenosine0. The infrared spectral structure of each ionic species of the dissociative materials in the metabolic pathway are discussed. Additionally, the possibility for a quantification system of the concentrations of the organic dissociative materials in varying pH is suggested.