Heterotopic ossification (HO), acquired or hereditary, endochondral or intramembranous, is the formation of true bone outside the normal skeleton. Since perivascular Gli1+ progenitors contribute to injury induced organ fibrosis, and CD133 is expressed by a variety of populations of adult stem cells, this study utilized Cre-lox based genetic lineage tracing to test the contribution to endochondral HO of adult stem/progenitor cells that expressed either Gli1 or CD133. We found that both lineages contributed broadly to different normal tissues with distinct patterns, but that only Gli1-creERT labeled stem/progenitor cells contributed to all stages of endochondral HO in a BMP dependent, injury induced, transgenic mouse model. Hedgehog (Hh) signaling was abnormal at endochondral HO lesion sites with increased signaling surrounding the lesion but diminished signaling within it. Thus, local dysregulation of Hh signaling participates in the pathophysiology of endochondral HO. However, unlike a previous report of intramembranous HO, systemic inhibition of Hh signaling was insufficient to prevent the initiation of the endochondral HO process or to treat the existing endochondral HO, suggesting that Hh participates in, but is not essential for endochondral HO in this model. This could potentially reflect the underlying difference between intramembranous and endochondral HO. Nevertheless, identification of this novel stem/precursor cell population as a HO-contributing cell population provides a potential drugable target.

On the basis of the famous staggered biphenalenyl diradical π dimer 1, the eclipsed biphenalenyl (1 a), with no centrosymmetry, was obtained by rotating a layer of 1 by 60° around its central axis. Furthermore, the central carbon atoms of 1 and 1 a were substituted by boron and nitrogen atoms to form 2 and 2 a with a novel 2e–12c bond. We found that the novel 2e–12c bond is formed by the electron pair of the occupied orbital of the phenalenyl monomer substituted by the nitrogen atom and the unoccupied orbital of the phenalenyl monomer substituted by the boron atom. As a result of the novel 2e–12c bond, 2 and 2 a exhibit a fascinating interlayer charge‐transfer transition character, which results in a significant difference in the dipole moments (Δμ) between the ground state and the crucial excited state. The values of Δμ for 2 and 2 a are 6.4315 and 6.9253 Debye, clearly larger than the values of 0 and 0.0015 Debye for 1 and 1 a. Significantly, the boron/nitrogen substitution effect can greatly enhance the first hyperpolarizabilities (β0) of 2 and 2 a with a novel 2e–12c bond compared with 1 and 1 a with a traditional 2e–12c bond: 0 and 19 a.u. for 1 and 1 a are much lower than 3516 and 12272 a.u. for 2 and 2 a. Furthermore, the interaction energies (Eint)of 2 and 2 a are larger than those of 1 and 1 a, which could be considered as a signature of reliability for the newly designed dimers. Our present work will be beneficial for further theoretical and experimental studies on the properties of molecules with the novel 2e–12c bond.

How do the number and location of lithium atoms affect the first hyperpolarizability (β tot ) of graphene? In this paper, based on pentacene, a series of graphene (multi)lithium salts Li n @pentacene (n ) 1, 2, 3, 4, 5, and 6) have been designed to answer this question. β tot obviously increases stepwise with an increase in the number of lithium atoms: 1369-1843 for Li@pentacence < 3510-4081 for Li 2 @pentacence < 6933-7934 for Li 3 @pentacence < 11 188-12 145 for Li 4 @pentacence < 14 904 au for Li 5 @pentacence, which are much larger than pentacence. This pattern suggests that the lithium salt effect on the first hyperpolarizability is very large. Unexpectedly, when an additional lithium atom is doped into the graphene multilithium salt Li 5 @pentacence, which leads to Li 6 @pentacence, the β tot value dramatically increases to a value of 4 501 764 au with a remarkable increase of 302-fold in contrast to Li 5 @pentacence. On the other hand, when the number of lithium atoms is equal, the location of lithium atoms also affects the β tot value: the closer the lithium atoms are clustered, the larger the β tot value: for Li 3 @pentacence, 6933 au of system 10 < 7401 au of system 9 < 7934 au of system 8. Furthermore, their transition energies (∆E) are also obtained. The results show that ∆E decreases stepwise with an increase in the number of the lithium atoms, and ∆E of Li 6 @pentacence sharply decreases to 0.299 eV, which may explain the huge β tot value. This study may stimulate the search for new types of graphene NLO materials based on alkali metals for NLO application.

Heterotopic ossification (HO), a serious disorder of extra-skeletal bone formation, occurs as a common complication of trauma or in rare genetic disorders. Many conserved signaling pathways have been implicated in HO; however, the exact underlying molecular mechanisms for many forms of HO are still unclear. The emerging picture is that dysregulation of bone morphogenetic protein (BMP) signaling plays a central role in the process, but that other conserved signaling pathways, such as Hedgehog (HH), Wnt/β-catenin and Fibroblast growth factors (FGF), are also involved, either through cross-talk with BMP signaling or through other independent mechanisms. Deep understanding of the conserved signaling pathways is necessary for the effective prevention and treatment of HO. In this review, we update and integrate recent progress in this area. Hopefully, our discussion will point to novel promising, druggable loci for further translational research and successful clinical applications.

On the basis of the n-acenes (n = 1, 2, 3 and 4), the α-Li@n-acenes and β-Li@n-acenes salts were selected to investigate how increasing the number n of conjugated benzenoid rings affects the linear and nonlinear optical responses. The α-Li@n-acenes and β-Li@n-acenes salts are obtained by a lithium atom substituting the α-H and β-H, respectively. In the present work, both ab initio (HF and MP2) and DFT (B3LYP, BhandHLYP, M05-2X, and CAM-B3LYP) methods are adopted to calculate the polarizability (α(0)) and first hyperpolarizability (β(tot)) of the α-Li@n-acenes and β-Li@n-acenes salts. MP2 results show that the α(0) values of both classes of lithium salts increase with increasing number n of conjugated benzenoid rings. Interestingly, we found that the β(tot) values of α-Li@n-acenes and β-Li@n-acenes salts take on opposite trends: the β(tot) values of α-Li@n-acenes are decreasing slowly (2187 for α-Li@benzene > 1978 for α-Li@naphthalene > 1898 for α-Li@anthrecene > 1830 au for α-Li@tetracene) and inceasing remarkably (2738 for β-Li@naphthalene < 3186 for β-Li@anthrecene < 3314 au for β-Li@tetracene) for β-Li@n-acenes. Furthermore, we found that the β(tot) values (2738-3314 au) of the β-Li@n-acenes are larger than those of the α-Li@n-acenes (1830-2187 au). On the other hand, comparing the results of different methods, the β(tot) values obtained by the M05-2X and CAM-B3LYP methods reproduce the polarizability and first hyperpolarizability of the α-Li@n-acenes and β-Li@n-acenes salts well, which test and verify the results of the MP2 method. Our present work may be beneficial to development of high-performance organic NLO optical materials.

Trumpet-shaped carbon nanocone (CNC) is used as a π-conjugated bridge to design high-performance nonlinear optical (NLO) material. Owing to the attractive trumpet-shaped structure, O 2 NÀ CNCÀNH 2 exhibits nonlinear optical behavior that is both surprisingly and qualitatively distinct from conventional π-conjugated organic species. It has been shown that the electron-acceptor nitryl (ÀNO 2 ) at the apex of the trumpet and the electron-donor amino (ÀNH 2 ) at the bottom edge of the trumpet to form O 2 NÀCNCÀNH 2 is beneficial to improve the NLO response of CNC. Significantly, the first hyperpolarizabilities (β tot ) of O 2 NÀCNCÀNH 2 show an arc-shaped change as ÀNH 2 substituting different H atoms along the arc-shaped bottom edge of CNC. Interestingly, the β tot values of HÀCNCÀNH 2 also show an arc-shaped change. By comparison of the β tot values of O 2 NÀCNCÀNH 2 and HÀCNCÀNH 2 , it has been found that no matter which bottom H of HÀCNCÀH is substituted by NH 2 , the β tot value of HÀCNCÀNH 2 will be increased about 1.6 times after substituting the top H with ÀNO 2 into the corresponding molecule. This study may stimulate the search for new types of NLO materials based on CNC for application.

Five new organic–inorganic hybrid compounds based on the Keggin-type polyoxoanion [SiW12O40]4−, namely [Cu3(2,2′-bpy)3(inic)(μ2-OH)(H2O)][SiW12O40]·2H2O (1), [Cu6(phen)6(μ3-Cl)2(μ2-Cl)2Cl2(inic)2][SiW12O40]·6H2O (2), [Cu2(hnic)(2,2′-bpy)2Cl]2[H2SiW12O40] (3), [Cu2(nic)(phen)2Cl2]2[SiW12O40] (4) and [Cu2(pic)(2,2′-bpy)2Cl]2[SiW12O40] (5) (inic = isonicotinic acid, hnic = 2-hydroxy-nicotinic acid, nic = nicotinic acid, pic = picolinic acid, 2,2′-bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline) have been synthesized and characterized by IR, UV-Vis, XPS, XRD, cyclic voltammetric measurements, photoluminescence analysis and single crystal X-ray diffraction analysis. Crystal analysis reveals that compound 1 exhibits a 2-D double layered framework structure constructed from [SiW12O40]4− and copper-aqua-2,2′-bipy-hydroxyl-isonicotinate complexes. Compound 2 is a 0-D discrete structure formed by [SiW12O40]4− and copper-chloro-isonicotinate-phenanthroline complexes. Compound 3 shows a 1-D single chain structure based on the linkage of copper-2,2-bpy-chloro-2-hydroxy-nicotinate complexes and [SiW12O40]4−. Compounds 4 and 5 both contain polyoxometalate supported transition metal complexes, one is a polyoxometalate supported copper-chloro-nicotinate-phenanthroline complex in 4, and the other is a polyoxometalate supported copper-2,2-bpy-chloro-nicotinate complex in 5. It should be noted that nicotinic, isonicotinic and picolinic acids are structural isomers and 2-hydroxy-nicotinic acid is an in situ hydroxylated product of nicotinic acid. In addition, photocatalytic degradation of Rhodamine B (RhB) by compounds 1–5 has been investigated in aqueous solutions.

We have fabricated an Yb-doped passively Q-switching fiber laser based on WS(2) saturable absorber. Both the operating wavelength and the repetition rate can be tuned in a wide range. The operating wavelength can be continuously tuned from 1027 nm to 1065 nm under the Q-switching state at a fixed pump power, while the repetition rate increases from 60.2 kHz to 97.0 kHz by varying pump power at a fixed wavelength of 1048.1 nm. The shortest pulse duration of 1.58 µs was observed. To the best of our knowledge, it's the first demonstration of WS(2)-based passively Q-switching fiber laser with a wide tunable range at 1.0 μm band.