Accurate ab initio based potential energy surface and kinetics of the Cl + NH3 → HCl + NH2 reaction.

The gas-phase reaction Cl + NH3 → HCl + NH2 is a prototypical hydrogen abstraction reaction, whose minimum energy path involves several intermediate complexes. In this work, a full-dimensional, spin-orbit corrected potential energy surface (SOC PES) is constructed for the ground electronic state of the Cl + NH3 reaction. About 52 000 energy points are sampled and calculated at the UCCSD(T)-F12a/aug-cc-pVTZ level, in which the data points located in the entrance channel are spin-orbit corrected. The spin-orbit corrections are predicted by a fitted three-dimensional energy surface from about 7520 energy points in the entrance channel at the level of CASSCF (15e, 11o)/aug-cc-pVTZ. The fundamental-invariant neural network method is utilized to fit the SOC PES, resulting in a total root mean square error of 0.12 kcal mol-1. The calculated thermal rate constants of the Cl + NH3 → HCl + NH2 reaction on the SOC PES with the soft-zero-point energy constraint agree reasonably well with the available experimental values.

Theoretical studies on the kinetics and dynamics of the BeH+ + H2O reaction: comparison with the experiment.

The reaction of BeH+ with background gaseous H2O may play a role in qubit loss for quantum information processing with Be+ as trapped ions, and yet its reaction mechanism has not been well understood until now. In this work, a globally accurate, full-dimensional ground-state potential energy surface (PES) for the BeH+ + H2O reaction was constructed by fitting a total of 170 438 ab initio energy points at the level of RCCSD(T)-F12/aug-cc-pVTZ using the fundamental invariant-neural network method. The total root-mean-square error of the final PES was 0.178 kcal mol-1. For comparison, quasi-classical trajectory calculations were carried out on the PES at an experimental temperature of 150 K. The obtained thermal rate constant and product branching ratio of the BeD+ + H2O reaction agreed quite well with experimental results. In addition, the vibrational state distributions and energy disposals of the products were calculated and rationalized using the sudden vector projection model.

Hierarchical Porous Protein Scaffold Templated from High Internal Phase Emulsion Costabilized by Gelatin and Gelatin Nanoparticles.

Recently, three-dimensional (3D) scaffolds produced using poly-Pickering high internal phase emulsions (polyHIPEs) technology are particularly attractive in biomedical application. However, until now the most investigated polyHIPEs are hydrophobic composites originating from synthetic polymers. Here we present an investigation of a hierarchical porous protein scaffold templated from oil-in-water (O/W) HIPEs costabilized by fully natural materials, gelatin, and gelatin nanoparticles. Fairly monodispersed gelatin nanoparticles were first synthesized through a two-step desolvation method, and then they were used as emulsifiers together with gelatin to fabricate stable HIPEs with adjustable droplet size distribution and rheology. Monolithic scaffolds were formed by cross-linking the HIPEs with polymers as low as 2.5 wt % in the continuous phase, which appropriately presented a general high porosity and had an interconnected porous morphology with smooth pore walls and textured structures. Furthermore, the scaffolds were degradable and showed reasonably good biocompatibility; L929 cells could adhere to the surface of the materials and exhibited intensive growth and well-spread morphology. This hierarchical porous protein scaffold could, therefore, have important application as a 3D scaffold that offers enhanced cell adhesion and functionality.

Screening of Tumor Antigens and Construction of Immune Subtypes for mRNA Vaccine Development in Head and Neck Squamous Cell Carcinoma.

BACKGROUND: A growing number of clinical studies have confirmed that mRNA vaccines are effective in the treatment of malignant tumors; however, their efficacy in head and neck squamous cell carcinoma (HNSCC) has not been determined. This study aimed to identify the potential antigens of HNSCC for mRNA vaccine development and further distinguish the immune subtypes of HNSCC to select suitable patients for vaccination. METHODS: We obtained gene expression profiles and corresponding clinical information of HNSCC from Gene Expression Omnibus (GEO) and The Cancer Genome Atlas (TCGA). We visualized the genetic alterations of potential antitumor antigens using cBioPortal and obtained the immune gene set from Immport. The correlation between the expression of the identified antigens and the infiltration of antigen-presenting cells was visualized by Tumor Immune Estimation Resource (TIMER). We evaluated the potential biological functions of different samples and described the immune landscape. RESULTS: Increased expression of three potential tumor antigens, CCR4, TMCO1, and SPACA4, associated with superior prognoses and infiltration of antigen-presenting cells, was identified in HNSCC. Three immune subtypes (C1-C3) with different molecular, cellular, and clinical characteristics were defined. Patients with C3 tumor had a better prognosis, representing an immune "cold" phenotype, which may be more suitable for mRNA vaccination. In addition, different immune characteristics were observed among the three immune subtypes, including markers of immune cells, mutation burden, expression of immune checkpoints, and immune modulators. Finally, the immune landscape of HNSCC showed a high degree of heterogeneity between individual patients. CONCLUSION: CCR4, TMCO1, and SPACA4 may be potential antigens for developing mRNA vaccines against HNSCC, especially for patients with C3 tumor. This study could provide a theoretical basis for the development of an mRNA vaccine against HNSCC.