Dissecting amide-I vibrations in histidine dipeptide.

The amide-I vibrational characteristics and conformational preferences of the model compound - histidine dipeptide (Ac-His-NHCH3, HISD) in gas phase and solution have been revealed with the help of ab initio calculations and wavefunction analyses. The Gibbs free energy surfaces (FESs) of solvated HISD were smoothed by solvent effect to exhibit different structural populations concerning various external environments. It was shown that the most stable conformations of HISD in CHCl3 and gas phase are C7eq, while those in DMSO and water are ß and PPII, respectively. Compared with ALAD, the number of accessible conformational states on these FESs was predicted to be reduced due to the steric effect of imidazole group. The two amide-I normal modes of HISD were found to have intrinsically secondary structural dependencies, and be sensitive to surrounding environments. The average amide-Ia frequencies of HISD isomers in these environments were predicted to be almost the same as those of ALAD, while the amide-Ib mean frequencies were estimated to be lower than ALAD due to the intramolecular interactions between the imidazole group and amino-terminal amide unit. The good linear correlations between amide-I frequencies and the atomic electrostatic potentials (ESPs) of amide groups were also found to interpret the solvent-induced amide-I frequency shifts of HISD at the electronic structure level. These results allow us to gain a deep understanding of amide-I vibrations of HISD, and would be helpful for the site-specific conformational monitoring and spectral interpretation of solvated polypeptides.

Broad-Spectrum Clearance of Lipopolysaccharides from Blood Based on a Hemocompatible Dihistidine Polymer.

Blood infection can release toxic bacterial lipopolysaccharides (LPSs) into bloodstream, trigger a series of inflammatory reactions, and eventually lead to multiple organ dysfunction, irreversible shock, and even death, which seriously threatens human life and health. Herein, a functional block copolymer with excellent hemocompatibility is proposed to enable broad-spectrum clearance of LPSs from whole blood blindly before pathogen identification, facilitating timely rescue from sepsis. A dipeptide ligand of histidine-histidine (HH) was designed as the LPS binding unit, and poly[(trimethylamine N-oxide)-co-(histidine-histidine)], a functional block copolymer combining the LPS ligand of HH and a zwitterionic antifouling unit of trimethylamine N-oxide (TMAO), was then designed by reversible addition-fragmentation chain transfer (RAFT) polymerization. The functional polymer achieved effective clearance of LPSs from solutions and whole blood in a broad-spectrum manner and had good antifouling and anti-interference properties and hemocompatibility. The proposed functional dihistidine polymer provides a novel strategy for achieving broad-spectrum clearance of LPSs, with potential applications in clinical blood purification.

Effects of ß-Alanine Supplementation on Carnosine Elevation and Physiological Performance.

ß-Alanine is one of the more popular sport supplements used by strength/power athletes today. The popularity of ß-alanine stems from its ability to enhance intracellular muscle-buffering capacity thereby delaying fatigue during high-intensity exercise by increasing muscle carnosine content. Recent evidence also suggests that elevated carnosine levels may enhance cognitive performance and increase resiliency to stress. These benefits are thought to result from carnosine's potential role as an antioxidant. This review will discuss these new findings including recent investigations examining ß-alanine supplementation and increased resiliency to posttraumatic stress and mild traumatic brain injury. This review will focus on the physiology of carnosine, the effect of ß-alanine ingestion on carnosine elevations, and the potential ergogenic benefits it has for competitive and tactical athletes.

ß-Alanine supplementation elevates intramuscular carnosine content and attenuates fatigue in men and women similarly but does not change muscle l-histidine content.

ß-Alanine (BA) supplementation results in elevated intramuscular carnosine content, enhancing buffering capacity during intense exercise. Although men have greater muscle carnosine content than women, elevations still appear to occur despite high baseline levels. Recent research has suggested that BA supplementation may also reduce muscle l-histidine. Thus, the purpose of this investigation was to compare 28 days of BA (6 g·d-1) supplementation in men and women on performance and muscle carnosine, l-histidine, and BA. We hypothesized that supplementation would result in similar elevations in carnosine and performance between sexes and decrease l-histidine. Twenty-six men and women were assigned either BA or placebo (PLA). At baseline, a trend toward greater carnosine (P = .069) was observed in men, and intramuscular BA content was significantly (P ≤ .05) greater in men. Statistical analysis was performed using magnitude-based inferences. Changes in muscle carnosine were likely and very likely greater after BA supplementation compared with PLA in men and women, respectively, but changes were unclear between sexes (mean sex difference: 2.50 ± 4.30 mmol·kg-1 ww). The attenuation of exercise fatigue was likely greater in BA compared with PLA, but the change was unclear between sexes (mean sex difference: 14.0 ± 39.0 Nm). Changes in muscle BA following supplementation was unclear in men, likely elevated in women, but unclear between sexes (mean sex difference: 0.03 ± 0.42 mmol·kg-1 ww). Changes in muscle l-histidine were unclear in men and women, and unclear between sexes (mean sex difference: 0.09 ± 0.13 mmol·kg-1 ww). In conclusion, BA supplementation increased muscle carnosine and attenuated fatigue in men and women similarly but did not reduce muscle l-histidine.