We report here a new class of ammonium metal-formate frameworks of [NH 2 NH 3 ][M(HCOO) 3 ] (M = Mn 2+ , Zn 2+ , Co 2+ and Mg 2+ ) incorporating hydrazinium as the cationic template and component.The perovskite Mn and Zn members possess anionic 4 12•6 3 metal-formate frameworks with cubic cavities occupied by the NH 2 NH 3 + cations, while the Co and Mg members have chiral 4 9 •6 6 metal-formate frameworks, with chiral hexagonal channels accommodating NH 2 NH 3 + cations. On heating, the Mn and Zn members undergo phase transitions around 350 K. The structures change from low temperature (LT) polar phases in Pna2 1 to high temperature (HT) non-polar phases in Pnma, due to the thermally activated librational movement of the NH 2 end of the NH 2 NH 3 + in the cavity and significant framework regulation.The Co and Mg members in LT belong to non-polar P2 1 2 1 2 1 , are probably antiferroelectric, and they show phase transitions at 380 K (Co) and 348 K (Mg), and the structures change to polar HT phases in P6 3 , triggered by the order-disorder transition of the cation from one unique orientation in LT to three of trigonally-disorder state in HT. Accompanying the phase transitions, which are ferro-to para-electric for Mn and Zn members while antiferro-to ferro-electric for Co and Mg, prominent anisotropic thermal expansions including negative ones, and dielectric anomalies, are observed. The spontaneous polarization values are estimated at 3.58 (Mn, 110 K), 3.48 (Zn, 110 K), 2.61 (Co, 405 K) and 3.44 (Mg, 400 K) μC cm −2 , respectively, based on the positive and negative charge separations in the polar structures. The structureproperty relevance is established based on the order-disorder transitions of NH 2 NH 3 + and the conformity and adaptability of the metal-formate frameworks to match such order-disorder alternations. The Mn and Co members show spin-canted antiferromagnetic long-range-ordering, with Néel temperatures of 7.9 K and 13.9 K, respectively. Therefore, the two members show coexistence of electric and magnetic orderings in the low temperature region, and they are possible molecule-based multiferroics.
Selective formation of amorphous, nematic (N), and beta phases in poly(9,9-di-n-octyl-2,7-fluorene) (PFO) films was achieved via judicious choice of process parameters. Phase structure and film morphology were carefully examined by means of X-ray diffraction as well as electron microscopy. "Amorphous" thin films were obtained by quick evaporation of solvent. Slow solvent removal during film formation or extended treatment of the amorphous film with solvent vapor resulted in predominantly the beta phase, which corresponds to a frozen (due to decreased segmental mobility upon solvent removal) and intrinsically metastable state of transformation midway between a solvent-induced clathrate phase and the equilibrium crystalline order in the undiluted state. The frozen transformation process is reactivated upon an increase in temperature beyond 100 degrees C. Compared to the amorphous film, extended backbone conjugation in the beta phase is evidenced from the emergence of a characteristic absorption peak around 430 nm near the absorption edge. For films of frozen nematic order (obtained by quenching from the nematic state), the conjugation length is also greater than the amorphous films as revealed by an absorption shoulder around 420 nm. Well-behaved single-chromophore emission with single-mode phonon coupling was observed for the beta phase; in the case of nematic films, dual-mode phonon coupling must exist if single-chromophore emission is assumed. In comparison, the emission spectrum of the amorphous film of generally shorter conjugation lengths exhibited mixed characteristics of nematic and beta phases, implying the presence of minor populations of extended conjugation similar to those in nematic and beta phases, which are of biased weightings in the emission spectra. All these films consist of nanograins (ca. 10 nm in size) of collapsed chains; the films are therefore inherently inhomogeneous in this length scale. In combination with previous observations on the crystalline (alpha and alpha') forms, the phase behavior of PFO is then generally summarized in terms of relative thermodynamic stability.
A large number of signalling pathways converge on p53 to induce different cellular stress responses that aim to promote cell cycle arrest and repair or, if the damage is too severe, to induce irreversible senescence or apoptosis. The differentiation of p53 activity towards specific cellular outcomes is tightly regulated via a hierarchical order of post-translational modifications and regulated protein-protein interactions. The mechanisms governing these processes provide a model for how cells optimize the genetic information for maximal diversity. The p53 mRNA also plays a role in this process and this review aims to illustrate how protein and RNA interactions throughout the p53 mRNA in response to different signalling pathways control RNA stability, translation efficiency or alternative initiation of translation. We also describe how a p53 mRNA platform shows riboswitch-like features and controls the rate of p53 synthesis, protein stability and modifications of the nascent p53 protein. A single cancer-derived synonymous mutation disrupts the folding of this platform and prevents p53 activation following DNA damage. The role of the p53 mRNA as a target for signalling pathways illustrates how mRNA sequences have co-evolved with the function of the encoded protein and sheds new light on the information hidden within mRNAs.
Here we report the phase behavior of poly(9,9-di-n-hexyl-2,7-fluorene) (PFH), which previously received little attention as compared to its homologues poly(9,9-di-n-octyl-2,7-fluorene) (PFO) and poly(9,9-di-(2'-ethylhexyl)-2,7-fluorene) (PFEH). By means of differential scanning calorimetry, X-ray diffraction, and electron microscopy, we show that there exist four different phases in PFH. The as-cast film is mainly composed of a mesomorphic beta phase with layer spacing of ca. 1.4 nm. This beta phase is inherently metastable and, upon heating above 175 degrees C, transforms into a crystalline (alpha) form that melts into a nematic (N) liquid above 250 degrees C. Upon stepwise cooling, the nematic melt crystallizes into the alpha phase first, followed by solid-solid transformation into another crystalline (alpha') form. Unit cell structure of the alpha form is monoclinic whereas that of the alpha' form is triclinic, but departures from strict orthogonality are slight (by ca. 6 degrees). These observations not only support our previous assignment of two crystalline forms (both orthorhombic in structure) in PFO but also provide insights to the crystalline nature of the polyfluorene series.
A niccolite series of [bnH2 2+][M(HCOO)3]2 (bnH2 2+=1,4‐butyldiammonium) shows four kinds of metal‐dependent phase transitions, from high temperature para‐electric phases to low‐temperature ferro‐, antiferro‐, glass‐like, and para‐electric phases. The conformational flexibility of bnH2 2+ and the different size, mass, and bonding character of the metal ion lead to various disorder‐order transitions of bnH2 2+ in the lattice and relevant framework modulations, thus different phase transitions and dielectric responses. The magnetic members display a coexistence or combination of electric and magnetic orderings in the low‐temperature region.
We present here the compound [NH4][Cu(HCOO)3], a new member of the [NH4][M(HCOO)3] family. The Jahn-Teller Cu(2+) ion leads to a distorted 4(9)⋅6(6) chiral Cu-formate framework. In the low-temperature (LT) orthorhombic phase, the Cu(2+) is in an elongated octahedron, and the NH₄⁺ ions in the framework channel are off the channel axis. From 94 to 350 K the NH₄⁺ ion gradually approaches the channel axis and the related modulation of the framework and the hydrogen-bond system occurs. The LT phase is simple antiferroelectric (AFE). The material becomes hexagonal above 355 K. In the high-temperature (HT) phase, the Cu(2+) octahedron is compressed, and the NH₄⁺ ions are arranged helically along the channel axis. Therefore, the phase transition is one from LT simple AFE to HT helical AFE. The temperature-dependent structure evolution is accompanied by significant thermal and dielectric anomalies and anisotropic thermal expansion, due to the different status of the NH₄⁺ ions and the framework modulations, and the structure-property relationship was established based on the extensive variable-temperature single-crystal structures. The material showed long range ordering of antiferromagnetism (AFM), with low dimensional character and a Néel temperature of 2.9 K. Therefore, within the material AFE and AFM orderings coexist in the low-temperature region.
The employment of linear di-, tri-, and tetra-ammoniums has generated a hierarchy in the binodal (412⋅63)(49⋅66)n topologies with n = 1, 2, and 3, respectively, for the cobalt formate frameworks with increasing length of the cavities to match the ammoniums. This indicates the length-directing effect of the polyammoniums. The dynamic movements of polyammoniums between favored sites or orientations within the cavities lead to slow dielectric relaxations. All materials are spin-canted antiferromagnets in low temperatures and show reduced spontaneous magnetizations from di- and tri-, to tetra-ammoniums, because of the increased number of unique Co ions or the antiferromagnetically coupled sublattices.
The compound [CH3 CH2 NH3][Cu(HCOO)3] undergoes a phase transition at 357 K, from a perovskite to a diamond structure, by heating. The backward transition can be driven by pressure at room temperature but not cooling under ambient or lower pressure. The rearrangement of one long copper-formate bond, the switch of bridging-chelating mode of the formate, the alternation of N-H⋅⋅⋅O H-bonds, and the flipping of ethylammonium are involved in the transition. The strong N-H⋅⋅⋅O H-bonding probably locks the metastable diamond phase. The two phases display magnetic and electric orderings of different characters.
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