3 research outputs found
Experimental and Quantum Chemical Modeling Studies of the Interactions of lâPhenylalanine with Divalent Transition Metal Cations
Encoded
by the UUU and UUC codons of the genetic code, l-phenylalanine
(LPA) serves as an important precursor for tyrosine
and various other compounds that are necessary to support life on
earth. Here, we report the synthesis (both in solid and solvent phases)
and characterization of the Ni<sup>2+</sup>, Cu<sup>2+</sup>, and
Zn<sup>2+</sup> complexes of LPA by several analytical, spectral,
thermal, and electrochemical techniques. The results reveal that the
products formed by following the two synthetic approaches are the
same, and the metal ions bind to the LPA molecules in a 1:2 molar
ratio (M<sup>+2</sup>/LPA). Complementary geometries of the metal
complexes are modeled involving the most predominant LPA conformers
predicted at the MP2/6-311++GÂ(d,p) level. The gaseous and aqueous
phase interaction enthalpies and free energies; theoretical IR and
UVâvis spectra; HOMOâLUMO energy gaps; dipole moments;
Wiberg bond indices as well as the partial atomic charges in LPA and
its metallic complexes are calculated and evaluated using B3LYP/6-311++GÂ(d,p)
as the main computational method. This study also incorporates analyses
on the efficacy of the DFT-D2 level in describing dispersion contributions,
performance of the BHandHLYP functional for the open-shell Cu<sup>2+</sup>-LPA system, and relative metal binding affinities of the
singlet versus triplet states of the Ni<sup>2+</sup>-LPA complex.
MetalâÏ interactions established via the aromatic side
chain of LPA add to the thermodynamic stability of the complexes,
whereas metal coordination induces considerable intrinsic structural
rearrangements in the molecular geometry of LPA. The LPA binding affinity
order of the three Lewis acids investigated emerges as Cu<sup>2+</sup> > Ni<sup>2+</sup> > Zn<sup>2+</sup>, paralleling the IrvingâWilliams
series. The illustrative evidence offered by the present work suggests
that the B3LYP/6-311++GÂ(d,p) level in combination with an empirical
dispersion-correction term performs well in describing the vibrational
frequencies and cationâÏ interactions, which are undoubtedly
of immense significance for natural sciences
Amberlyst A21 Catalyzed Chromatography-Free Method for Multicomponent Synthesis of Dihydropyrano[2,3â<i>c</i>]pyrazoles in Ethanol
Amberlyst
A21 was found to be an extremely efficient catalyst for
synthesis of a series of 6-amino-4-alkyl/aryl-3-methyl-2,4-dihydropyranoÂ[2,3-<i>c</i>]Âpyrazole-carbonitriles by a four-component reaction of
a mixture of ethyl acetoacetate, hydrazine hydrate, aldehyde, and
malononitrile in ethanol at room temperature. The catalytic efficiency
of Amberlyst A21 was compared with some other resin-bound free and
anionic bases in order to ascertain the best catalyst for the said
conversion. The catalyst was found to work extremely well also for
acyclic/cyclic ketones to give corresponding dihydropyranoÂ[2,3-<i>c</i>]Âpyrazoles or their spirocyclic variants. Easy recovery
of the catalyst and its reusability, room temperature reaction conditions,
short reaction time, excellent yields, no chromatographic purification,
and evasion of environmentally hazardous solvents in the entire reaction
process may make this protocol very useful for academia and industry
Metalation of Glycylglycine: An Experimental Study Performed in Tandem with Theoretical Calculations
Interactions
of the Ni<sup>2+</sup>, Cu<sup>2+</sup>, and Zn<sup>2+</sup> ions
with the simplest dipeptide glycylglycine (GlyGly)
are explored using various experimental and computational techniques.
Solid and aqueous phase syntheses of the metalated GlyGly complexes
(by solid-state grinding and by coprecipitation respectively) lead
to the same products, as confirmed by physicochemical and spectral
properties which indicate metal-coordination through the âNH<sub>2</sub> and âCO<sub>2</sub><sup>â</sup> groups of the
dipeptide. Phase-diagram and kinetic studies of the solid-phase reaction
between GlyGly and copper acetate suggest that complexation occurs
in 1:2 (metal/ligand) stoichiometry via a facile kinetic pathway (a
barrier of only 22.22 kJ/mol). The right-handed α-helical conformer
of GlyGly is considered in DFT modeling studies in gas and aqueous
phases elucidating the effects of metalation and solvation upon structural,
electronic, and vibrational properties of the complexes. The complexes
are found to follow the stability order Cu<sup>2+</sup> > Ni<sup>2+</sup> > Zn<sup>2+</sup> corroborating the Irving-Williams series.
The
NiÂ(GlyGly)<sub>2</sub> complex is predicted to exist in its low-spin
state. Hydration effects on structural aspects of the complexes are
also investigated computationally. The BHandHLYP/6-311++GÂ(d,p) level
describes the CuÂ(GlyGly)<sub>2</sub> complex more efficiently than
the B3LYP/6-311++GÂ(d,p) level (which, however, better predicts the
vibrational spectra of the systems). Absorption titration experiments
with calf thymus DNA together with in silico docking and molecular
mechanical studies reveal that these metalâdipeptide complexes
are DNA minor-groove binders primarily through H-bonding interactions,
yielding a DNA-binding affinity order of Ni<sup>2+</sup> > Zn<sup>2+</sup> > Cu<sup>2+</sup>