Building Atomic Scale and Dense Fe─N4 Edge Sites of Highly Efficient Fe─N─C Oxygen Reduction Catalysts Using a Sacrificial Bimetallic Pyrolysis Strategy.

Replacing high-cost and scarce platinum (Pt) with transition metal and nitrogen co-doped carbon (M/N/C, M = Fe, Co, Mn, and so on) catalysts for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells has largely been impeded by the unsatisfactory ORR activity of M/N/C due to the low site utilization and inferior intrinsic activity of the M─N4 active center. Here, these limits are overcome by using a sacrificial bimetallic pyrolysis strategy to synthesize Fe─N─C catalyst by implanting the Cd ions in the backbone of ZIF-8, leading to exposure of inaccessible FeN4 edge sites (that is, increasing active site density (SD)) and high fast mass transport at the catalyst layer of cathode. As a result, the final obtained Fe(Cd)─N─C catalyst has an active site density of 33.01 µmol g-1 (with 33.01% site utilization) over 5.8 times higher than that of Fe─N─C catalyst. Specially, the optimal catalyst delivers a high ORR performance with a half-wave potential of 0.837 (vs RHE) in a 0.1 m HClO4 electrolyte, which surpasses most of Fe-based catalysts.

Engineering Energy Level of FeN4 Sites via Dual-Atom Site Construction Toward Efficient Oxygen Reduction.

Single-atom catalysts based on metal-N4 moieties and embedded in a graphite matrix (defined as MNC) are promising for oxygen reduction reaction (ORR). However, the performance of MNC catalysts is still far from satisfactory due to their imperfect adsorption energy to oxygen species. Herein, single-atom FeNC is leveraged as a model system and report an adjacent Ru-N4 moiety modulation effect to optimize the catalyst's electronic configuration and ORR performance. Theoretical simulations and physical characterizations reveal that the incorporation of Ru-N4 sites as the modulator can alter the d-band electronic energy of Fe center to weaken the FeO binding affinity, thus resulting in the lower adsorption energy of ORR intermediates at Fe sites. Thanks to the synergetic effects of neighboring Fe and Ru single-atom pairs, the FeN4 /RuN4 catalyst exhibits a half-wave potential of 0.958 V and negligible activity degradation after 10 000 cycles in 0.1 m KOH. Metal-air batteries using this catalyst in the cathode side exhibit a high power density of 219.5 mW cm-2 and excellent cycling stability for over 2370 h, outperforming the state-of-the-art catalysts.

ß-Glucan-based superabsorbent hydrogel acts as a gastrointestinal exoskeleton enhancing satiety and interfering fat hydrolysis.

Fat and its hydrolysis products, fatty acids, are indispensable nutritional components; however, prolonged excessive fat consumption, particularly in western diets, contributes to the onset of obesity and multiple metabolic disorders. In this study, we propose a daily-ingestible hydrogel (denoted as ßC-MA hydrogel) composed of natural ß-glucan and sodium carboxymethylcellulose crosslinked by malic acid at 120 °C. This hydrogel exhibits rapid swelling performance, up to 24-fold within 1 min and 176-fold after 1 h in deionized water. It also lengthens gastric retention and increases endogenous satiety signal levels, potentially controlling appetite and reducing food intake. Furthermore, ßC-MA hydrogels that enter the small intestine can effectively inhibit fat hydrolysis and decrease triglyceride synthesis and transport. Specifically, the hydrogels inhibit the release of free fatty acids (FFAs) by approximately 50 % during digestion, influence the translocation of triglycerides and FFAs across the intestinal epithelium, and reduce the serum triglyceride levels by 22.2 %. These findings suggest that ßC-MA hydrogels could serve as a noninvasive gastrointestinal device for weight control, with the advantage of reducing food intake and restoring lipid metabolism homeostasis.

Modified whey protein isolate gel prepared by thermal aggregation combined with transglutaminase crosslinking achieves Casein-like slow digestion in vitro and in vivo.

Our study aimed to fabricate a modified slow-digestive whey protein isolate (WPI), which can supply enough branched-chain amino acids (BCAAs) during long-term fasting. The WPI aqueous solution (10 % w/v) was treated by heat (80 ℃) to unfold the protein tertiary structure, and subsequently treated with transglutaminase to form a gel via cross-linking. The powder of the WPI gel was obtained by spray drying, which can dissolve in water easily and self-assemble into gels again. This modified WPI contained protein aggregates with high molecular weight, and kept a stable gel-like structure under simulated gastric digestion conditions (pH = 3, 37 ℃). A dense honeycomb internal microstructure of the freeze-dried gel was observed. Further, we found that the WPI gel successfully achieved a casein-like digestible ratio (37.37 %) and released more BCAAs (0.18 mg/mL) than casein during the 4 h of in vitro simulated digestion based on the INFOGEST method. Finally, our results showed that the C57BL/6 mice oral administrated with the modified WPI gel had consistently higher BCAAs concentration (0.052 mg/mL) in their blood serum than the mice with normal WPI intake during the 6 h of in vivo digestion.

Modulating Water Splitting Kinetics via Charge Transfer and Interfacial Hydrogen Spillover Effect for Robust Hydrogen Evolution Catalysis in Alkaline Media.

Designing and synthesizing advanced electrocatalysts with superior intrinsic activity toward hydrogen evolution reaction (HER) in alkaline media is critical for the hydrogen economy. Herein, a novel Ir@Rhene heterojunction electrocatalyst is synthesized via epitaxially confining ultrasmall and low-coordinate Ir nanoclusters on the ultrathin Rh metallene accompanying the formation of Ir/IrO2 Janus nanoparticles. The as-prepared heterojunctions display outstanding alkaline HER activity, with an overpotential of only 17 mV at 10 mA cm-2 and an ultralow Tafel slope of 14.7 mV dec-1 . Both structural characterizations and theoretical calculations demonstrate that the Ir@Rhene heterointerfaces induce charge density redistribution, resulting in the increment of the electron density around the O atoms in the IrO2 site and thus delivering much lower water dissociation energy. In addition, the dual-site synergetic effects between IrO2 and Ir/Rh interface trigger and improve the interfacial hydrogen spillover, thereby subtly avoiding the steric blocking of the active site and eventually accelerating the alkaline HER kinetics.

Differential phase-diversity electrooptic modulator for cancellation of fiber dispersion and laser noise.

Bandwidth and noise are fundamental considerations in all communication and signal processing systems. The group-velocity dispersion of optical fibers creates nulls in their frequency response, limiting the bandwidth and hence the temporal response of communication and signal processing systems. Intensity noise is often the dominant optical noise source for semiconductor lasers in data communication. In this paper, we propose and demonstrate a class of electrooptic modulators that is capable of mitigating both of these problems. The modulator, fabricated in thin-film lithium niobate, simultaneously achieves phase diversity and differential operations. The former compensates for the fiber's dispersion penalty, while the latter overcomes intensity noise and other common mode fluctuations. Applications of the so-called four-phase electrooptic modulator in time-stretch data acquisition and in optical communication are demonstrated.

Novel Broccoli-Derived Peptides Hydrolyzed by Trypsin with Dual-Angiotensin I-Converting Enzymes and Dipeptidyl Peptidase-IV-Inhibitory Activities.

Broccoli-derived peptides show beneficial metabolic effects, and it is necessary to examine their exact functional sequences. First, peptides from the trypsin hydrolysate of broccoli proteins were isolated and identified using column chromatography and quadrupole time-of-flight mass spectrometry. After that, their functions were verified by oral administration. The results identified two novel peptides as Leu-Pro-Gly-Val-Leu-Pro-Val-Ala (LPGVLPVA) and Tyr-Leu-Tyr-Ser-Pro-Ala-Tyr (YLYSPAY). LPGVLPVA exhibited an ACE IC50 value of 0.776 ± 0.03 µM and a DPP-IV IC50 value of 392 ± 24 µM; YLYSPAY showed an ACE IC50 value of 8.52 ± 0.63 µM and a DPP-IV IC50 value of 181 ± 4 µM. Administration of the peptides reduced the blood pressure of spontaneously hypertensive rats and reduced blood glucose levels in the oral glucose tolerance test in mice. The results indicated that LPGVLPVA and YLYSPAY could be potential nutritional candidates for hypertensive and diabetic people, especially for those with diabetes associated with hypertension.

Transport, In Vivo Antihypertensive Effect, and Pharmacokinetics of an Angiotensin-Converting Enzyme (ACE) Inhibitory Peptide LVLPGE.

The angiotensin-converting enzyme (ACE) inhibitory peptide LVLPGE provides outstanding antihypertensive effects in vivo, with a maximum systolic blood pressure (SBP) drop of 39 mmHg at a dose of 10 mg/kg. We evaluated the gastrointestinal digestion, transport, and in vivo antihypertensive effects of LVLPGE at different doses. LVLPGE was resistant to gastrointestinal enzymes with a stability of 97.8% and a permeability Papp of (5.09 ± 0.94) × 10-7 cm/s. LVLPGE was mainly transported through the Caco-2 cell monolayer by the peptide transporter PepT 1 and passive-mediated transport. LVLPGE at doses of 30 and 50 mg/kg had a positive antihypertensive effect in vivo; 30 mg/kg had a more significant effect than 50 mg/kg. After oral administration, the pharmacokinetics of LVLPGE showed that the Cmax was 4.65 ng/mL at 2 min. The blood pressure-lowering effect increased as the concentration of LVLPGE increased in the plasma of spontaneous hypertensive rats (SHRs).

Angiotensin I-Converting Enzyme (ACE) Inhibitory and Antioxidant Activity of Umami Peptides after In Vitro Gastrointestinal Digestion.

Umami peptides can help reduce the salt content in foods while still maintaining a savory taste. Few studies have reported the bioactivity of umami peptides after consumption. We studied the bioactivities of 12 umami peptides after gastrointestinal digestion. Three umami peptides exhibited angiotensin I-converting enzyme (ACE) inhibitory and antioxidant activity after digestion. Six novel peptides were identified from digestion solutions of the peptides by HPLC-MS/MS. Among them, CC, CCNK, and HCHT had both ACE inhibitory activity (IC50 values were 9.81, 9.00, and 114.99 µM, respectively) and antioxidant activity (strong 1,1-Diphenyl-2-pycryl-hydrazyl (DPPH) and 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS) free radical scavenging activities). AHSVRF had strong ACE inhibitory activity. These peptides increased the nitric oxide concentration and decreased the content of endothelin-1 in a medium of human umbilical vein endothelial cells in a dose-dependent manner. Experiments with damaged HepG2 cells showed that peptides CC, CCNK, and HCHT had antioxidant activity through their cytoprotective effects and by reducing the reactive oxygen species content. The results indicated that umami peptides may provide many health benefits after consumption.

Establishment of new assessment method for the synergistic effect between umami peptides and monosodium glutamate using electronic tongue.

In order to investigate the synergistic effect between umami peptides and monosodium glutamate (MSG), a new assessment method was established using electronic tongue. After 36 kinds of umami peptides synthesized by peptide solid phase synthesis, their taste characteristics were preliminarily explored by electronic tongue technology, and then the umami intensity was ranked before and after addition of MSG, using a concentration of 0.35% of MSG as control. In addition, the sensory evaluation was utilized to verify the results of the electronic tongue. Finally, the umami intensity and the synergistic effect of umami peptides and MSG were also investigated by the aroma chicken model (ACM). Results showed that peptide Lys-Gly-Ser-Leu-Ala-Asp-Glu-Glu (KE-8) and Arg-Leu (RL) have the strongest umami taste, Asp-Asp-Asp (DDD) and Glu-Ser-Val (ESV) have the strongest synergistic effect with MSG, which could increase the umami intensity. The ESV and Glu-Asp-Asp (EDD) showed the strongest synergistic effect with ACM. The evaluation method could provide the objective data for further investigating for the synergistic theory.

In Vitro and in Vivo Studies on the Angiotensin-Converting Enzyme Inhibitory Activity Peptides Isolated from Broccoli Protein Hydrolysate.

In the present study we purified and identified peptides from broccoli protein hydrolysates and evaluated their angiotensin-converting enzyme (ACE) inhibitory activity in vitro and hypotensive effect in vivo. Three ACE inhibitory peptides were isolated and identified as IPPAYTK, LVLPGELAK, and TFQGPPHGIQVER, and their inhibitory IC50 values were 23.5, 184.0, and 3.4 µM, respectively. We then investigated the effect of gastrointestinal digestion on ACE inhibitory activity. We detected almost two times the ACE inhibitory activity of the peptide LVLPGELAK following simulated digestion than prior to digestion. LVLPGE and LAK, two novel peptides exhibiting high ACE inhibitory activity, were discovered following digestion and possessed IC50 values of 13.5 and 48.0 µM, respectively. The hypotensive effect of the peptides was assessed after oral administration to spontaneous hypertensive rats (SHRs). We found that LVLPGE and LAK demonstrated a significant hypotensive effect in vivo. Protein from broccoli may thus constitute a potential antihypertensive peptide source.

Molecular and biological characterization of the 5 human-bovine rotavirus (WC3)-based reassortant strains of the pentavalent rotavirus vaccine, RotaTeq.

RotaTeq is a pentavalent rotavirus vaccine that contains five human-bovine reassortant strains (designated G1, G2, G3, G4, and P1) on the backbone of the naturally attenuated tissue culture-adapted parental bovine rotavirus (BRV) strain WC3. The viral genomes of each of the reassortant strains were completely sequenced and compared pairwise and phylogenetically among each other and to human rotavirus (HRV) and BRV reference strains. Reassortants G1, G2, G3, and G4 contained the VP7 gene from their corresponding HRV parent strains, while reassortants G1 and G2 also contained the VP3 gene (genotype M1) from the HRV parent strain. The P1 reassortant contained the VP4 gene from the HRV parent strain and all the other gene segments from the BRV WC3 strain. The human VP7s had a high level of overall amino acid identity (G1: 95-99%, G2: 94-99% G3: 96-100%, G4: 93-99%) when compared to those of representative rotavirus strains of their corresponding G serotypes. The VP4 of the P1 reassortant had a high identity (92-97%) with those of serotype P1A[8] HRV reference strains, while the BRV VP7 showed identities ranging from 91% to 94% to those of serotype G6 HRV strains. Sequence analyses of the BRV or HRV genes confirmed that the fundamental structure of the proteins in the vaccine was similar to those of the HRV and BRV references strains. Sequences analyses showed that RotaTeq exhibited a high degree of genetic stability as no mutations were identified in the material of each reassortant, which undergoes two rounds of replication cycles in cell culture during the manufacturing process, when compared to the final material used to fill the dosing tubes. The infectivity of each of the reassortant strains of RotaTeq, like HRV strains, did not require the presence of sialic acid residues on the cell surface. The molecular and biologic characterization of RotaTeq adds to the significant body of clinical data supporting the consistent efficacy, immunogenicity, and safety of RotaTeq.