Dihydroxamic acid complexes of iron (III): ligand pKa and coordinated water hydrolysis constants

Valorising biomass waste and producing renewable energy or materials is the aim of several conversion technologies. In this work, we consider two residues from different production chains: lignocellulosic residues from agriculture and wool residues from sheep husbandry. These materials are produced in large quantities, and their disposal is often costly and challenging for farmers. For their valorisation, we focus on slow pyrolysis for the former and water hydrolysis for the latter, concisely presenting the main literature related to these two processes. Pyrolysis produces the C-rich biochar, suitable for soil amending. Hydrolysis produces a N-rich fertiliser. We demonstrate how these two processes could be fruitfully integrated, as their products can be flexibly mixed to produce fertilisers. This solution would allow the achievement of balanced and tuneable ratios between C and N and the enhancement of the mechanical properties. We propose scenarios for this combined valorisation and for its coupling with other industries. As a result, biomass waste would be returned to the field, following the principles of circular economy.

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Water Molecule Dispositions in the Cesium Sulfate α- and β-Alums: Single-Crystal Neutron Diffraction Studies of CsM(SO4)2.12H2O (M=V, Rh)

Australian Journal of Chemistry ◽

10.1071/ch9931337 ◽

1993 ◽

Vol 46 (9) ◽

pp. 1337 ◽

Cited By ~ 12

Author(s):

JK Beattie ◽

SP Best ◽

FH Moore ◽

BW Skelton ◽

AH White

Keyword(s):

Neutron Diffraction ◽

Water Molecule ◽

Single Crystal ◽

Tilt Angle ◽

Room Temperature ◽

Bond Angle ◽

Sulfate Salt ◽

Cell Dimensions ◽

Coordinated Water ◽

Unit Cell Dimensions

Room-temperature single-crystal neutron diffraction studies are recorded for two alums, Cs( Rh /V)(SO4)2.12H2O [cubic, Pa3, a 12.357(5) ( Rh ), 12.434(1)Ǻ (V)], residuals 0.037 and 0.068 for 328 and 164 'observed' reflections, with the intention of defining water molecule hydrogen atom orientations. Whereas the two tervalent hexaaqua cations are similar in size [ rM -O = 2.010(6)Ǻ (M = V) and 2.006(2)Ǻ (M = Rh )] the vanadium salt adopts the β alum modification while rhodium gives an α alum. Significantly, the water coordination geometry is different in the two cases with the tilt angle between the plane of the water molecule and the M-O bond vector being 1° (M = V) and 35° (M = Rh ). The tilt angle for water coordinated to rhodium in CsRh (SeO4)2.12H2O is inferred from the unit cell dimensions to be similar to that of the corresponding sulfate salt and not that which generally pertains for caesium selenate alums. Significant differences in the H-O-H bond angle are found for trigonal planar and trigonal pyramidal water coordination, suggesting that differences in the metal(III)-water interaction are a determinant of the geometry of the coordinated water molecule in the caesium sulfate/ selenate alum lattices.

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Entropy-driven binding of gut bacterial β-glucuronidase inhibitors ameliorates irinotecan-induced toxicity

Communications Biology ◽

10.1038/s42003-021-01815-w ◽

2021 ◽

Vol 4 (1) ◽

Author(s):

Hsien-Ya Lin ◽

Chia-Yu Chen ◽

Ting-Chien Lin ◽

Lun-Fu Yeh ◽

Wei-Che Hsieh ◽

...

Keyword(s):

Cancer Metabolism ◽

Glucuronic Acid ◽

Intestinal Epithelial Cells ◽

Primary Treatment ◽

Water Molecules ◽

Intestinal Epithelial ◽

E Coli ◽

Severe Diarrhea ◽

Coordinated Water ◽

Consequent Increase

AbstractIrinotecan inhibits cell proliferation and thus is used for the primary treatment of colorectal cancer. Metabolism of irinotecan involves incorporation of β-glucuronic acid to facilitate excretion. During transit of the glucuronidated product through the gastrointestinal tract, an induced upregulation of gut microbial β-glucuronidase (GUS) activity may cause severe diarrhea and thus force many patients to stop treatment. We herein report the development of uronic isofagomine (UIFG) derivatives that act as general, potent inhibitors of bacterial GUSs, especially those of Escherichia coli and Clostridium perfringens. The best inhibitor, C6-nonyl UIFG, is 23,300-fold more selective for E. coli GUS than for human GUS (Ki = 0.0045 and 105 μM, respectively). Structural evidence indicated that the loss of coordinated water molecules, with the consequent increase in entropy, contributes to the high affinity and selectivity for bacterial GUSs. The inhibitors also effectively reduced irinotecan-induced diarrhea in mice without damaging intestinal epithelial cells.

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New insights about the hostguest chemistry of the tungsten oxo complex of calix[4]arene, and novel "one pot" difunctionalizations of calix[4]arene using tetrachlorometal(VI) oxide (M = Mo, W)

Canadian Journal of Chemistry ◽

10.1139/v04-097 ◽

2004 ◽

Vol 82 (10) ◽

pp. 1452-1461 ◽

Cited By ~ 9

Author(s):

Pascal Mongrain ◽

Jasmin Douville ◽

Jonathan Gagnon ◽

Marc Drouin ◽

Andreas Decken ◽

...

Keyword(s):

Water Molecule ◽

Lewis Acid ◽

Chemical Shifts ◽

Strong Interactions ◽

Ir Absorption ◽

One Pot ◽

X Ray ◽

Strong Lewis Acid ◽

Successful Removal ◽

Coordinated Water

The strong Lewis acid tungsten oxo complex of calix[4]arene can be obtained in both hydrated and non-hydrated forms. This complex coordinates a water molecule inside the cavity via strong O···W interactions with relatively short distances of 2.284(4) and 2.329(2) Å for the tungsten oxo complex of calix[4]arene··H2O·aniline (1), and the tungsten oxo complex of calix[4]arene·H2O·toluene (2·toluene), respectively. The strong interactions are also deduced by the relatively high H2O elimination temperature observed by TGA and DSC (above 200 °C). The coordinated water molecule inside the calix[4]arene cavity is characterized by a strong IR absorption at 3616 cm1, and a narrow resonance at ~1.2 ppm (the chemical shifts of the uncoordinated water are 1.55 and 1.60 ppm in C6D6 and CDCl3, respectively). This water molecule gives rise to H-bonds with aniline in 1. The tungsten oxo complex of 5,11,17,23-tetrabromocalix[4]arene (4), also binds H2O as the characteristic signatures are observed. The successful removal of H2O in 2, is performed under mild conditions using bis(tetrahydrofuran)-uranyl nitrate as a competitive Lewis acid. When this reaction is performed in acetonitrile, butyronitrile or tert-butylnitrile, the corresponding tungsten oxo complexes of calix[4]arene·acetonitrile (3), ·butyronitrile (5), and ·tert-butylnitrile (6) are obtained. The use of uranyl as a H2O abstractor is unprecedented. The X-ray structure of 3 consists of a tungsten oxo complex of calix[4]arene coordinated by an acetonitrile molecule (d(W···N = 2.412(2) Å). The tetra-5,11,17,23-choromethyl-25,26,27,28-tetrahydroxycalix[4]arene reacts with M(O)Cl4 (M = Mo, W) in a 1:1 stoichiometry, via a tetra FriedelCrafts addition of benzene or toluene, followed by a lower-rim complexation of the metal oxide, to form "flower-shaped" calix[4]arenes. This "one pot" double functionalization is unprecedented.Key words: calix[4]arene, tungsten, molybdenum, X-ray, hostguest, FriedelCrafts, Lewis acid, uranyl, DSC, TGA.

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