Electrochemical water splitting for H2 production is limited by the sluggish anode oxygen evolution reaction (OER), thus using hydrazine oxidation reaction (HzOR) to replace OER has received great attention. Here we report the hierarchical porous nanosheet arrays with abundant Ni3N‐Co3N heterointerfaces on Ni foam with superior hydrogen evolution reaction (HER) and HzOR activity, realizing working potentials of −43 and −88 mV for 10 mA cm−2, respectively, and achieving an industry‐level 1000 mA cm−2 at 200 mV for HzOR. The two‐electrode overall hydrazine splitting (OHzS) electrolyzer requires the cell voltages of 0.071 and 0.76 V for 10 and 400 mA cm−2, respectively. The H2 production powered by a direct hydrazine fuel cell (DHzFC) and a commercial solar cell are investigated to inspire future practical applications. DFT calculations decipher that heterointerfaces simultaneously optimize the hydrogen adsorption free energy (ΔGH*) and promote the hydrazine dehydrogenation kinetics. This work provides a rationale for advanced bifunctional electrocatalysts, and propels the practical energy‐saving H2 generation techniques.

A variety of multisubstituted cyclooctenes were prepared and employed as monomers for ring-opening metathesis polymerization using the Grubbs second or third generation catalysts. The resulting polymers were characterized by NMR spectroscopy, size exclusion chromatography, and differential scanning calorimetry. Monomers possessing a substituent at the 3-position afforded highly regio- and stereoregular polyalkenamers, from which the corresponding sequence-specific vinyl quaterpolymers were obtained upon hydrogenation. Simultaneous control of tacticity was also demonstrated by employing monomers with defined stereochemistry.

Replacing sluggish oxygen evolution reaction (OER) with hydrazine oxidation reaction (HzOR) to produce hydrogen has been considered as a more energy-efficient strategy than water splitting. However, the relatively high cell voltage in two-electrode system and the required external electric power hinder its scalable applications, especially in mobile devices. Herein, we report a bifunctional P, W co-doped Co 3 N nanowire array electrode with remarkable catalytic activity towards both HzOR (−55 mV at 10 mA cm −2) and hydrogen evolution reaction (HER, −41 mV at 10 mA cm −2). Inspiringly, a record low cell voltage of 28 mV is required to achieve 10 mA cm −2 in two-electrode system. DFT calculations decipher that the doping optimized H* adsorption/desorption and dehydrogenation kinetics could be the underlying mechanism. Importantly, a self-powered H 2 production system by integrating a direct hydrazine fuel cell with a hydrazine splitting electrolyzer can achieve a decent rate of 1.25 mmol h −1 at room temperature.

Both groups of patients achieved almost the same satisfactory outcome at an average of 7.8 years of follow-up. Fresh-frozen hamstring tendon allograft is a reasonable alternative choice to autograft for anterior cruciate ligament reconstruction.

The effect of using gamma irradiation to sterilize bone-patellar tendon-bone (BPTB) allograft on the clinical outcomes of anterior cruciate ligament (ACL) reconstruction with irradiated allograft remains controversial. Our study was aimed to analyze the clinical outcomes of arthroscopic ACL reconstruction with irradiated BPTB allograft compared with non-irradiated allograft and autograft. All BPTB allografts were obtained from a single tissue bank and the irradiated allografts were sterilized with 2.5 Mrad of irradiation prior to distribution. A total of 102 patients undergoing arthroscopic ACL reconstruction were prospectively randomized consecutively into three groups. The same surgical technique was used in all operations done by the same senior surgeon. Before surgery and at the average of 31 months follow-up (range 24-47 months) patients were evaluated by the same observer according to objective and subjective clinical evaluations. Of these patients, 99 (autograft 33, non-irradiated allograft 34, irradiated allograft 32) were available for full evaluation. When compared the irradiated allograft group to non-irradiated allograft group or autograft group at 31 months follow-up by the Lachman test, ADT, pivot shift test and KT-2000 arthrometer testing, statistically significant differences were found. Most importantly, 87.8% of patients in the Auto group, 85.3% in the Non-Ir-Auto group and just only 31.3% in the Ir-Allo group had a side-to-side difference of less than 3 mm according to KT-2000. The failure rate of the ACL reconstruction with irradiated allograft (34.4%) was higher than that with autograft (6.1%) and non-irradiated allograft (8.8%). The anterior and rotational stability decreased significantly in the irradiated allograft group. According to the overall IKDC, functional, subjective evaluations and activity level testing, no statistically significant differences were found between the three groups. However, there was a trend that the functional and activity level decreased and the patients felt uncomfortable more often in the irradiated allograft group. The statistical analysis showed no significant difference between the non-irradiated allograft group and the autograft group according to the aforementioned evaluations, except that patients in the allograft group had a shorter operation time and a longer duration of postoperative fever. When comparing the postoperative duration of fever of the two allograft groups, there was also a trend that the irradiated allograft group was longer than the non-irradiated allograft group, but no significant difference was found. When the patients had a fever, the laboratory examinations of all patients were almost normal (Blood routine was normal, the values of ESR were 5 - 16 mm/h, CRP were 3 - 10 mg/l). On the basis of our study, we concluded that patients undergoing ACL reconstruction with BPTB non-irradiated allograft or autograft had similar clinical outcomes. Non-irradiated BPTB allograft is a reasonable alternative to autograft for ACL reconstruction. Whi...

Tensile tests were conducted on a Rheometrics Scientific Minimat Instrument at a crosshead extension rate of 10 mm/min at room temperature. Dogbone samples (8 mm gage length, 0.5 mm gage thickness, 3 mm gage width) were prepared by stamping of compression molded film.Reported values are averages and standard deviations of four or five samples (see Figure S60 and S61).Wide-angle X-ray scattering (WAXS) measurements were performed on a Bruker D8 Discover diffractometer using a Cu Kα radiation point source. The data was collected and analyzed by Bruker GADDS software.Computational Methods. Calculation were performed at M06-2X/SDD|6-311+G(2df,p) // M06-L/SDD|6-31G(d) level of theory 3 with Gaussian 09 revision A.02. 4 Analytic frequency calculations were done for all structures in order to characterize their nature as either minima or TS structures, and also to compute thermal contributions to enthalpy and free energy. The effect of solvation by CHCl3 was computed from the SMD continuum solvation model. 5 Composite free energies in solution were computed by summing gas-phase M06-L thermal contributions with single point SMD/M06-2X single-point energies. Correction from the gas phase to the solution was made by adding -1.9 kcal/mol (RT Ln ([Sln]/[Gas])) to the free energy of each molecule.

The structural, electronic, and optical properties of a g-C3N4(001)/BiVO4(010) nanocomposite have been investigated using first-principles calculations. The results indicate that g-C3N4(001) can stably adsorb onto the BiVO4(010) surface, and it tends to form a regular wavy shape. The calculated band gap of the g-C3N4(001)/BiVO4(010) nanocomposite is narrower compared with that of BiVO4 or BiVO4(010), primarily due to the introduction of N 2p states near the Fermi level. The g-C3N4(001)/BiVO4(010) nanocomposite has a favorable type-II band alignment; thus, photoexcited electrons can be injected into the conduction band of g-C3N4(001) from the conduction band of BiVO4(010). The proper interface charge distribution facilitates carrier separation in the g-C3N4(001)/BiVO4(010) interface region. The electron injection and carrier separation can prevent the recombination of electron-hole pairs. The calculated absorption coefficients indicate an obvious redshift of the absorption edge, which is in good agreement with the experimental results. Our calculation results suggest that the g-C3N4(001)/BiVO4(010) nanocomposite has significant advantages for visible-light photocatalysis.

Poly-beta-peptides are attractive for biomedical applications because the backbone is similar enough to that of proteins for biocompatibility, but the backbone is sufficiently unnatural that these polymers evade proteolytic degradation. Prior investigations of poly-beta-peptides have been hindered by two principal limitations: (1) most known examples are insoluble, and (2) the range of accessible side chain functionality has been quite limited (mostly simple hydrocarbon units). The present study describes innovations in poly-beta-peptide synthesis that enable the preparation of diversely functionalized examples and provide the basis for broad exploration of the properties and applications of these nylon-3 materials. We describe several beta-lactams with a protected amino group in their side chain that readily undergo ring-opening polymerization (ROP). These monomers are available in large quantities via N-chlorosulfonylisocyanate (CSI) cycloaddition reactions with functionalized alkenes; previously CSI reactions have been limited to alkenes with hydrocarbon substituents. Postpolymerization deprotection of the amino groups leads to water-soluble poly-beta-peptides. In addition, we introduce a simple co-initiation strategy that allows placement of a wide variety of functional groups at the N-termini of poly-beta-peptide chains. ROP involving the new beta-lactams and co-initiation strategy exhibits characteristics of a controlled polymerization and enables the preparation of amphiphilic block copolymers. We have recently shown that cationic copoly-beta-peptides made available by these innovations mimic the selective antibacterial activity of host-defense peptides; the results described here provide the foundation for further exploration of this valuable activity and for the pursuit of other biological applications such as DNA/siRNA delivery and tissue engineering.