Europium (Eu)-cyclootetatrene (COT = C(8)H(8)) multidecker clusters (Eu(n)COT(n+1), n = 1-4) are studied by relativistic density functional theory calculations. These clusters are found to be thermodynamically stable with freely rotatable COT rings, and their total magnetic moments (MMs) increase linearly along with the number of Eu atoms. Each Eu atom contributes about 7 mu(B) to the cluster. Meanwhile, the internal COT rings have little MM contribution while the external COT rings have about 1 mu(B) MM aligned in opposite direction to that of the Eu atoms. The total MM of the Eu(n)COT(n+1) clusters can thus be generalized as 7n - 2 mu(B) where n is the number of Eu atoms. Besides, the ground states of these clusters are ferromagnetic and energetically competitive with the antiferromagnetic states, meaning that their spin states are very unstable, especially for larger clusters. More importantly, we uncover an interesting bonding characteristic of these clusters in which the interior ionic structure is capped by two hybrid covalent-ionic terminals. We suggest that such a characteristic makes the Eu(n)COT(n+1) clusters extremely stable. Finally, we reveal that for the positively charged clusters, the hybrid covalent-ionic terminals will tip further toward the interior part of the clusters to form deeper covalent-ionic caps. In contrast, the negatively charged clusters turn to pure ionic structures.

A systematic theoretical study of the structural and magnetic properties of small transition metal oxide clusters TM(n)O(m) (TM = Sc, Ti, V, Cr and Mn; n = 1, 2; m = 1-6) has been carried out by using an ab initio density functional theory approach. The O atoms are partly molecularly adsorbed in O-rich and few-valence electron TM oxide clusters like ScO(3), TiO(3), Sc(2)O(4-6), Ti(2)O(5-6), and V(2)O(6). The binding energy increases monotonously with increasing O atoms and decreases with the appearance of the peroxide unit, with the exception of ScO(3). The Sc-, Ti- and V- oxide clusters have a stronger binding than the Cr- and Mn-oxide ones. The magnetic properties are dependent on the TM element and on the density of O. The successive addition of an O atom to Mn(2) induces an odd-even magnetic oscillation from antiferromagnetic to ferrimagnetic and to nonmagnetic state. In the V-, Cr- and Mn-oxide clusters, the O atoms play a negligible role in the magnetism and they are generally antiferromagnetic when coupled with TM atoms, while the O atoms possess large magnetic moments in some Sc- and Ti- oxide clusters.

Locking compression plates can be used as external fixators and provide a high rate of union, comfortable clinical course and excellent ankle-joint motion. Although indications are limited, this method is a suitable surgical approach for treating closed distal tibial fractures with soft tissue compromise.

The competition between the Eley−Rideal (ER) and the Langmuir−Hinshelwood mechanisms of CO oxidation on Cu n and Cu n O (n = 6, 7) clusters was explored by means of spin-polarized density functional theory calculations. The separate and successive adsorptions of CO and O 2 on the clusters were studied. CO and O 2 molecules exhibit different adsorption behaviors, and a cooperative effect was noted for their coadsorption. The reaction pathways of CO oxidization were then investigated by locating the transition-state and intermediate structures. The ER mechanism was more favorable for the reactions on Cu 6,7 and Cu 6 O but was less favorable on Cu 7 O. The ER or LH preference of the CO + O 2 reaction on the clusters was further rationalized. We found that activation of O 2 is the key issue that affects the ER−LH competition. The pathway, either ER or LH, in which O 2 is highly activated is always preferred, while the O 2 activation depends on its adsorption pattern, site, and sequence in the presence of CO.

Background Homeobox D11 (HOXD11) plays an important role in a variety of cancers, but its precise role in gliomas remains unclear. This study aimed to explore the relationship between HOXD11 and gliomas by combining bioinformatics methods with basic experimental validation. Materials and methods Obtain gene expression information and clinical information of glioma and non-tumor brain tissue samples from multiple public databases such as TCGA (666 glioma samples), CGGA (749 glioma samples), GEPIA(163 glioblastoma samples and 207 normal control samples), GEO (GSE4290 and GSE15824). Nine cases of glioma tissue and five cases of normal control brain tissue were collected from the clinical department of Henan Provincial People’s Hospital for further verification. A series of bioinformatic analysis methods were used to confirm the relationship between HOXD11 expression and overall survival and clinical molecular characteristics of patients with glioma. RT-qPCR was used to verify the change of expression level of HOXD11 in glioma cells and tissues. MTT assay, colony formation assay, wound-healing assay, immunofluorescence staining, flow cytometry and western blotting were used to detect the effect of HOXD11 on the biological behavior of glioma cell line U251. Results The high expression of HOXD11 was significantly related to age, World Health Organization (WHO) grade, chemotherapy status, histological type, and even 1p19q codeletion data and isocitrate dehydrogenase (IDH) mutation. HOXD11, as an independent risk factor, reduces the overall survival of glioma patients and has diagnostic value for the prognosis of glioma. Gene Set Enrichment Analysis (GSEA) showed that HOXD11 was significantly enriched in cell signaling pathway such as cell cycle, DNA replication and so on. Finally, we confirmed that the knockout of HOXD11 can inhibit the proliferation and invasion of U251 glioma cells, and change the biological behavior of tumor cells by preventing the progression of cell cycle. Conclusions HOXD11 may be used as a candidate biomarker for the clinical application of targeted drug and prognostic assessment treatment of glioma. In addition, This study will help to explore the pathological mechanism of glioma.