Supramolecular self-assembly for designing non-centrosymmetric crystals based on Keggin polyoxometallates and crown ether.

We report the synthesis of five novel crystals [(4-BrAni+)(DB[18]crown-6)]2[SMo12O402-]·2CH3CN (1), [(4-BrAni+)(B[18]crown-6)]2[SMo12O402-]·CH3CN (2), [(4-BrAni+)(B[18]crown-6)]3[PMo12O402-]·2CH3CN (3), [(3-AP+)3(B[18]crown-6)2][PMo12O403-] (4) and [NBu4+][(3-AP2+)(DB[30]crown-10)][PMo12O403-]·CH3CN (5) (4-BrAni+ = 4-bromoanilinium; B[18]crown-6 = benzo[18]-crown-6; DB[18]crown-6 = dibenzo[18]-crown-6; DB[30]crown-10 = dibenzo[30]-crown-10; 3-AP+ = 3-aminopyridinium; 3-AP2+ = 3-ammoniumpyridinium; NBu4+ = tetrabutylammonium). In order to construct non-centrosymmetric crystals, the five crystals were designed using a method to gradually introduce asymmetry into the building units. Crystal 1 was constructed with a symmetric supramolecular cation (SPC) [(4-BrAni+)(DB[18]crown-6)], resulting in a P21/n space group. The asymmetric SPC [(4-BrAni+)(B[18]crown-6)] was introduced into [SMo12O402-] to obtain crystal 2, which belongs to the symmetric P1[combining macron] space group. Introducing trivalent [PMo12O403-], [(4-BrAni+)(B[18]crown-6)] produced crystal 3 with a non-centrosymmetric Pc space group. The asymmetric sandwich SPC [(3-AP+)3(B[18]crown-6)2] was designed with multiple hydrogen bonding sites on the 3-AP+ cation, and crystal 4 was obtained with trivalent [PMo12O403-]. Crystal 4 has the properties of the chiral P1 space group. The distorted SPC (3-AP2+)(DB[30]crown-10) was constructed using flexible DB[30]crown-10, resulting in crystal 5 which matched the chiral P21 space group with trivalent [PMo12O403-]. This work focuses on strategies for the rational design of novel non-centrosymmetric crystals without a chiral synthon.

Maintenance of cyclic GMP-AMP homeostasis by ENPP1 is involved in pseudorabies virus infection.

In a previous study, we demonstrated that porcine cyclic GMP-AMP (cGAMP) synthase (cGAS) catalyzes cGAMP production and is an important DNA sensor for the pseudorabies virus (PRV)-induced activation of interferon ß (IFN-ß). Ectonucleotide pyrophosphatase phosphodiesterase 1 (ENPP1) has recently been identified as the hydrolase of cGAMP in rodents, but its role in porcine cells is not clear. Our recent study demonstrated that porcine ENPP1 is responsible for the homeostasis of cGAMP and is critical for PRV infection. Porcine ENPP1 mRNA is predominantly expressed in muscle. PRV infection was enhanced by ENPP1 overexpression and attenuated by silencing of ENPP1. During PRV infection, the activation of IFN-ß and NF-κB was reduced in ENPP1 overexpressed cells and promoted in ENPP1 knockdown cells. Investigation of the molecular mechanisms of ENPP1 during PRV infection showed that ENPP1 hydrolyzed cGAMP in PRV-infected or cGAMP-transfected cells and inhibited IRF3 phosphorylation, reducing IFN-ß secretion. These results, combined with those for porcine cGAS, demonstrate that ENPP1 acts coordinately with cGAS to maintain the reservoir of cGAMP and participates in PRV infection.

Cholesterol 25-hydroxylase acts as a host restriction factor on pseudorabies virus replication.

Cholesterol 25-hydroxylase (CH25H) catalyses the production of 25-hydroxycholesterol (25HC) from cholesterol by adding a second hydroxyl group at position 25. The aim of this study was to examine the antiviral effect of CH25H on pseudorabies virus (PRV), a swine pathogen that can cause devastating disease and economic losses worldwide. The results showed that porcine ch25h was induced by either interferon or PRV infection. PRV infection of porcine alveolar macrophages (3D4/21 cells) was attenuated by CH25H overexpression and enhanced by silencing of CH25H. Furthermore, treatment of 3D4/21 cells with 25HC inhibited the growth of PRV in vitro, suggesting that CH25H may restrict PRV replication by 25HC production. We further identified that the anti-PRV role of CH25H and 25HC was subject to their inhibitory effect on PRV attachment and entry. Collectively, these findings demonstrate that CH25H is an intrinsic host restriction factor in PRV infection of porcine alveolar macrophages.

[Comparison of green coffee beans volatiles chemical composition of Hainan main area].

Chemical component of Hainan green coffee beans was analyzed with solid phase microextraction-gas chromatography-mass spectrometry, and the discrepancy between two green coffee beans was differentiated through the spectrum database retrieval and retention index of compound characterization. The experimental results show that: the chemical composition of Wanning coffee beans and Chengmai coffee beans is basically the same. The quantity of analyzed compound in Wanning area coffee is 91, and in Chengmai area coffee is 106, the quantity of the same compound is 66, and the percent of the same component is 75.52%. The same compounds accounted for 89.86% of the total content of Wanning area coffee, and accounted for 85.70% of the total content of Chengmai area coffee.

Meta-barium borate, II-BaB2O4, at 163 and 293 K.

The single-crystal X-ray diffraction structure analysis of an excellent non-linear optical material, viz. II-BaB2O4 or Ba3(B3O6)2, has been carried out at 163 and 293 K. The two sets of structural data are compared and indicate a significant shortening of the c axial length in the unit cell at 163 K, whereas the a and b axial lengths essentially do not change.

A novel left-handed double helicate constructed from L-tartrate bridged molybdenum(vi) and gadolinium(iii) atoms.

The one-dimensional double helicate, [NH4][Mo2O4Gd(H2O)6(L-C4H2O6)2] x 4H2O (1), which was synthesized by the reaction of GdCl3, L-tartaric acid and ammonium molybdate in acidified water solution, is built up by two heft-handed single-helical chains, linked up further by eight-coordinated GdIII pieces in an enantiopure left-handed double helical configuration, of which each helix is formed by L-tartrate bridged six-coordinated MoVI atoms.

A three-dimensional zeolite-like organic-inorganic hybrid material constructed from (CuMo2O8N)n double helical chains linked via [Cu(4,4'-bpy)]n fragments.

The three-dimensional microporous [Cu2Mo2O8(4,4'-bpy)]n.3nH2O 1 contains (CuMo2O8N) double helical chains, which are built up from (CuIIO4N) square pyramids linked by (MoVIO4) tetrahedra and further connected to each other by 4,4'-bpy coordinated (CuIIO5N); the study of the physical properties of 1 demonstrates it is a paramagnetic semiconductor and a zeolite material; the specific channeling cavities in 1 have potential adsorption activities, indicating that 1 might be an attractive functional microporous solid material.

Synthesis and Structural Characterization of an Unusual Oxygen-Linked Double Cubane-Like Cluster {[Mo(3)PbOS(3)](OAc)(2)(py)(3)(dtp)(2)O}(2).

The unusual oxygen-linked double cubane-like cluster compound {[Mo(3)PbOS(3)](OAc)(2)(py)(3)(dtp)(2)O}(2) (A) (dtp = S(2)P(OEt(2))(-), OAc = CH(3)COO(-), py = C(5)H(5)N) was obtained for the first time by the reaction of the mixed S/O-bridged cluster [Mo(3)(&mgr;(3)-O)(&mgr;-S)(3)(dtp)(4)H(2)O] (B) with Pb(OAc)(2).3H(2)O in the presence of excess CH(3)COOH and pyridine. It has been characterized by IR, Raman, UV-vis, and X-ray structure analysis. The molecule contains a crystallographic center of inversion and can be viewed as consisting of two [Mo(3)PbOS(3)](6+) cubane-like cores linked through a pair of oxygen bridges with Mo-(&mgr;-O) bond lengths of ca. 1.89 Å. The cell dimensions are a = 11.705(8) Å, b = 19.527(8) Å, c = 20.670(9) Å, beta = 98.14(4) degrees, V = 4677(8) Å(3), Z = 2 in the space group P2(1)/n. The final R = 0.056, R(w) = 0.068 for 5424 reflections with I >/= 3sigma(I). The average Mo-Mo bond distance is 2.613(1) Å and the nonbonding Mo-Pb distances lie in the range from 3.997(1) to 4.090(1) Å. The spectra of IR, Raman, and UV-vis spectra are also shown in this paper.