264 research outputs found
Triammonium Trimetaphosphimate Monohydrate
Crystals of triammonium cyclo-tri-Ό-imido-triphosphate monohydrate, (NH4)3(PO2NH)3.H20, are composed of three ammonium cations, a trimetaphosphimate anion with a chair conformation and a water molecule per asymmetric unit. A three-dimensional network is formed by N--H...O and O--H...O hydrogen bonds
Tetraammonium Tetrametaphosphimate Tetrahydrate
The tetrametaphosphimate ring in the title compound, (NH4)4+(PO2NH)4-.4H2O exhibits a chair conformation. The tetrametaphosphimate rings are linked by N-HO bonds forming columns along [100]. These columns are interconnected by O-HO and N-HO hydrogen bonds through water molecules and ammonium ions. All H atoms are involved in hydrogen bonding
Trisodium Trimetaphosphimate Monohydrate
The trimetaphosphimate anion (PO2NH)33- in trisodium cyclo-tri--imidotriphosphate monohydrate, Na3(PO2NH)3.H2O, exhibits a chair conformation. Two trimetaphosphimate rings are linked to each other by six N-HO hydrogen bonds forming pairs. These units are interconnected by O-HO hydrogen bonds through water molecules forming columns
Poly[(ÎŒ3-benzene-1,3,5-tricarboxylÂato-Îș3 O 1:O 3:O 5)(ÎŒ2-2-methylÂimidazolato-Îș2 N:NâČ)trisÂ(2-methylÂimidazole-ÎșN)dizinc(II)]
HydroÂthermal reaction involving zinc nitrate hexaÂhydrate, trisÂodium benzene-1,3,5-tricarboxylÂate (Na3BTC) and 2-methylÂimidazole (2-MeImH) yielded the title compound, [Zn2(C9H3O6)(C4H5N2)(C4H6N2)3]. In this mixed-ligand metal-organic compound, Zn2+ ions are coordinated by N atoms from 2-MeImH molÂecules and (2-MeIm)â ions, as well as by O atoms from (BTC)3â ions. This results in two different distorted tetraÂhedra, viz. ZnN3O and ZnN2O2. These tetraÂhedra are interÂconnected via (BTC)3â ions and N:NâČ-bridging (2-MeIm)â ions, thus forming a layered structure in the bc plane. Hydrogen bonds between the O atoms of carboxylÂate ions and NH groups of 2-MeImH ligands link the layers into a three-dimensional structure
Vibrational analysis of Ag3(PO2NH)3, Na3(PO2NH)3.H2O, Na3(PO2NH)3.4H2O, [C(NH2)3]3(PO2NH)3.H2O and (NH4)4(PO2NH)4.4H2O
FT IR and FT Raman spectra of Ag3(PO2NH), (Compound I), Na3(PO2NH)3.H2O (Compound II), Na3(PO2NH)3.4H2O (Compound III), [C(NH2)3]3(PO2NH)3.H2O (Compound IV) and (NH4)4(PO2NH)4.4H2O (Compound V) are recorded and analyzed on the basis of the anions, cations and water molecules present in each of them. The PO2NHâ anion ring in compound I is distorted due to the influence of Ag+ cation. Wide variation in the hydrogen bond lengths in compound III is indicated by the splitting of the v2 and v3 modes of vibration of water molecules. The NH4 ion in compound V occupies lower site symmetry and exhibits hindered rotation in the lattice. The correlations between the symmetric and asymmetric stretching vibrations of P-N-P bridge and the P-N-P bond angle have also been discussed
Controlled modification of the inorganic and organic bricks in an Al-based MOF by direct and post-synthetic synthesis routes
Four new porous CAU-1 derivatives CAU-1–NH2 ([Al4(OH)2(OCH3)4(BDC–NH2)3]·xH2O, BDC–NH22− = aminoterephthalate), CAU-1–NH2(OH) ([Al4(OH)6(BDC–NH2)3]·xH2O), CAU-1–NHCH3 ([Al4(OH)2(OCH3)4(BDC–NHCH3)3]·xH2O) and CAU-1–NHCOCH3 ([Al4(OH)2(OCH3)4(BDC–NHCOCH3)3]·xH2O) all containing an octameric [Al8(OH)4+y(OCH3)8−y]12+ cluster, with y = 0–8, have been obtained by MW-assisted synthesis and post-synthetic modification. The inorganic as well as the organic unit can be modified. Heteronuclear 1H–15N, 1H–13C and homonuclear 1H–1H connectivities determined by solid-state NMR spectroscopy prove the methylation of the NH2 groups when conventional heating is used. Varying reaction times and temperatures allow controlling the degree of methylation of the amino groups. Short reaction times lead to non-methylated CAU-1 (CAU-1–NH2), while longer reaction times result in CAU-1–NHCH3. CAU-1–NH2 can be modified chemically by using acetic anhydride, and the acetamide derivative CAU-1–NHCOCH3 is obtained. Thermal treatment permits us to change the composition of the Al-containing unit. Methoxy groups are gradually exchanged by hydroxy groups at 190 °C in air. Solid-state NMR spectra unequivocally demonstrate the presence of the amino groups, as well as the successful post-synthetic modification. Furthermore 1H–1H correlation spectra using homonuclear decoupling allow the orientation of the NHCOCH3 groups within the pores to be unravelled. The influence of time and temperature on the synthesis of CAU-1 was studied by X-ray powder diffraction, elemental analyses, and 1H liquid-state NMR and IR spectroscopy
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Biocompatible, Crystalline, and Amorphous Bismuth-Based Metal-Organic Frameworks for Drug Delivery.
The synthetic flexibility of metal-organic frameworks (MOFs) with high loading capacities and biocompatibility makes them ideal candidates as drug delivery systems (DDSs). Here, we report the use of CAU-7, a biocompatible bismuth-based MOF, for the delivery of two cancer drugs, sodium dichloroacetate (DCA) and α-cyano-4-hydroxycinnamic acid (α-CHC). We achieved loadings of 33 and 9 wt % for DCA and α-CHC, respectively. Interestingly, CAU-7 showed a gradual release of the drugs, achieving a release time of up to 17 days for DCA and 31 days for α-CHC. We then performed mechanical and thermal amorphization processes to attempt to delay the delivery of guest molecules even more. With the thermal treatment, we were able to achieve an outstanding 32% slower release of α-CHC from the thermally treated CAU-7. Using in vitro studies and endocytosis inhibitors, confocal microscopy, and fluorescence-activated cell sorting, we also demonstrated that CAU-7 was successfully internalized by cancer cells, partially avoiding lysosome degradation. Finally, we showed that CAU-7 loaded either with DCA or α-CHC had a higher therapeutic efficiency compared with the free drug approach, making CAU-7 a great option for biomedical application
The role of sulfonate groups and hydrogen bonding in the proton conductivity of two coordination networks
The proton conductivity of two coordination networks, [Mg(H(2)O)(2)(H(3)L)]·H(2)O and [Pb(2)(HL)]·H(2)O (H(5)L = (H(2)O(3)PCH(2))(2)-NCH(2)-C(6)H(4)-SO(3)H), is investigated by AC impedance spectroscopy. Both materials contain the same phosphonato-sulfonate linker molecule, but have clearly different crystal structures, which has a strong effect on proton conductivity. In the Mg-based coordination network, dangling sulfonate groups are part of an extended hydrogen bonding network, facilitating a âproton hoppingâ with low activation energy; the material shows a moderate proton conductivity. In the Pb-based metal-organic framework, in contrast, no extended hydrogen bonding occurs, as the sulfonate groups coordinate to Pb(2+), without forming hydrogen bonds; the proton conductivity is much lower in this material
Isostructural Family of RareâEarth MOFs Synthesized from 1,1,2,2âTetrakis(4âphosphonophenyl)ethylene
The tetraphosphonic acid 1,1,2,2-tetrakis(4-phosphonophenyl)ethylene (H8L) was used as linker in the synthesis of eight new isostructural, phosphonate-based metal-organic frameworks of composition [M2(H2O)2(H2L)]ââ
âxH2O (M=Y3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Lu3+; 1.5<x<4), denoted as M-CAU-34. The compounds were synthesized under hydrothermal reaction conditions, using the corresponding metal nitrates as starting materials. The determination of the crystal structure was achieved by a combination of electron and powder X-ray diffraction (PXRD) data. In addition, a thorough characterization by thermogravimetric and elemental analysis, IR- and Raman-spectroscopy as well as H2O-sorption is given
New multifunctional sulfonato-containing metal phosphonates proton conductors
Anchoring of acidic functional groups to organic linkers acting as ligands in metal phosphonates has been demonstrate to be a valid strategy to develop new proton conductor materials, which exhibit tunable properties and are potentially applicable to proton exchange membranes, such as those used in PEMFCs [1,2].
In this work, the structural and proton conductivity properties of several families of divalent and trivalent metal amino-sulfophosphonates are presented. The chosen ligand, (H2O3PCH2)2-N-(CH2)2-SO3H, was reacted with the appropriate metal salt using highthrough-put screening and/or microwave-assisted synthesis. Different crystal structures haven been solved displaying a variety of metal ligand coordination modes, in whose frameworks acidic groups contribute to create strong H-bond networks; together with lattice and bound water molecules. Proton conductivity values oscillate between 10-4 and 10-2 S.cm-1, at 80 ÂșC and 95 % relative humidity, most of them showing activation energies characteristic of a Grotthuss-type proton transport mechanism.Universidad de MĂĄlaga. Campus de Excelencia Internacional AndalucĂa Tech.
MINECO: MAT2016-77648-R
Junta de AndalucĂa: P-12-FQM-1656 y FQM-11
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