Presence Of H-bonding Interactions Research Articles

The Role of H-Bonds in the Excited-State Properties of Multichromophoric Systems: Static and Dynamic Aspects.

Given their importance, hydrogen bonds (H-bonds) have been the subject of intense investigation since their discovery. Indeed, H-bonds play a fundamental role in determining the structure, the electronic properties, and the dynamics of complex systems, including biologically relevant materials such as DNA and proteins. While H-bonds have been largely investigated for systems in their electronic ground state, fewer studies have focused on how the presence of H-bonds could affect the static and dynamic properties of electronic excited states. This review presents an overview of the more relevant progress in studying the role of H-bond interactions in modulating excited-state features in multichromophoric biomimetic complex systems. The most promising spectroscopic techniques that can be used for investigating the H-bond effects in excited states and for characterizing the ultrafast processes associated with their dynamics are briefly summarized. Then, experimental insights into the modulation of the electronic properties resulting from the presence of H-bond interactions are provided, and the role of the H-bond in tuning the excited-state dynamics and the related photophysical processes is discussed.

Insights into Nitrosoalkane Binding to Myoglobin Provided by Crystallography of Wild-Type and Distal Pocket Mutant Derivatives.

Nitrosoalkanes (R-N═O; R = alkyl) are biological intermediates that form from the oxidative metabolism of various amine (RNH2) drugs or from the reduction of nitroorganics (RNO2). RNO compounds bind to and inhibit various heme proteins. However, structural information on the resulting Fe-RNO moieties remains limited. We report the preparation of ferrous wild-type and H64A sw MbII-RNO derivatives (λmax 424 nm; R = Me, Et, Pr, iPr) from the reactions of MbIII-H2O with dithionite and nitroalkanes. The apparent extent of formation of the wt Mb derivatives followed the order MeNO > EtNO > PrNO > iPrNO, whereas the order was the opposite for the H64A derivatives. Ferricyanide oxidation of the MbII-RNO derivatives resulted in the formation of the ferric MbIII-H2O precursors with loss of the RNO ligands. X-ray crystal structures of the wt MbII-RNO derivatives at 1.76-2.0 Å resoln. revealed N-binding of RNO to Fe and the presence of H-bonding interactions between the nitroso O-atoms and distal pocket His64. The nitroso O-atoms pointed in the general direction of the protein exterior, and the hydrophobic R groups pointed toward the protein interior. X-ray crystal structures for the H64A mutant derivatives were determined at 1.74-1.80 Å resoln. An analysis of the distal pocket amino acid surface landscape provided an explanation for the differences in ligand orientations adopted by the EtNO and PrNO ligands in their wt and H64A structures. Our results provide a good baseline for the structural analysis of RNO binding to heme proteins possessing small distal pockets.

Tuning the Redox Activity of Metal-Organic Frameworks for Enhanced, Selective O2 Binding: Design Rules and Ambient Temperature O2 Chemisorption in a Cobalt-Triazolate Framework.

Metal-organic frameworks (MOFs) with coordinatively unsaturated metal sites are appealing as adsorbent materials due to their tunable functionality and ability to selectively bind small molecules. Through the use of computational screening methods based on periodic density functional theory, we investigate O2 and N2 adsorption at the coordinatively unsaturated metal sites of several MOF families. A variety of design handles are identified that can be used to modify the redox activity of the metal centers, including changing the functionalization of the linkers (replacing oxido donors with sulfido donors), anion exchange of bridging ligands (considering μ-Br-, μ-Cl-, μ-F-, μ-SH-, or μ-OH- groups), and altering the formal oxidation state of the metal. As a result, we show that it is possible to tune the O2 affinity at the open metal sites of MOFs for applications involving the strong and/or selective binding of O2. In contrast with O2 adsorption, N2 adsorption at open metal sites is predicted to be relatively weak across the MOF dataset, with the exception of MOFs containing synthetically elusive V2+ open metal sites. As one example from the screening study, we predicted that exchanging the μ-Cl- ligands of M2Cl2(BBTA) (H2BBTA = 1H,5H-benzo(1,2-d:4,5-d')bistriazole) with μ-OH- groups would significantly enhance the strength of O2 adsorption at the open metal sites without a corresponding increase in the N2 affinity. Experimental investigation of Co2Cl2(BBTA) and Co2(OH)2(BBTA) confirms that the former exhibits weak physisorption of both N2 and O2, whereas the latter is capable of chemisorbing O2 at room temperature in a highly selective manner. The O2 chemisorption behavior is attributed to the greater electron-donating character of the μ-OH- ligands and the presence of H-bonding interactions between the μ-OH- bridging ligands and the reduced O2 adsorbate.

Insights into the Mechanisms and Chemoselectivities of Carbamates and Amides in Reactions Involving Rh(II)-Azavinylcarbene: A Computational Study.

Reactions involving Rh(II)-azavinylcarbenes (Rh(II)-AVCs) to synthesize nitrogen-containing compounds have attracted significant research interest. Despite the importance of these reactions, controlling the chemoselectivities in the reactions involving Rh(II)-AVC remains a challenge. To understand the mechanisms and factors controlling the chemoselectivities between N-H and C═O groups of carbamates and amides in reactions involving Rh(II)-AVC, computational studies were employed. The results reveal that not only the greater nucleophilicity of the N-H group than that of the carbonyl group, but also the presence of H-bonding interactions, could favor the addition of the N-H group of primary carbamates to Rh(II)-AVC. However, for secondary carbamates and amides, they could undergo either chemoselective N-H or C═O addition. Secondary carbamates with less steric hindrance, such as oxazolidinone, prefer the N-H addition mode. However, a switch in chemoselectivity (preference for the C═O addition) was revealed for the sterically hindered secondary carbamates/amides. In addition, a possible O-H addition pathway via the keto-enol tautomerization for isatin and isatoic anhydride was disregarded due to the energetically demanding barrier. Instead, a pathway involving the chemoselective C═O addition, formal [3 + 2] cycloaddition, followed by ring opening was proposed. The origins of the chemoselectivity and the factors responsible were addressed.

Conductivity and dielectric relaxation in various polyvinyl alcohol/ammonium salt composites

We studied electrical conductivity and dielectric relaxation in polyvinyl alcohol/ammonium chloride and polyvinyl alcohol/ammonium acetate composite films. Infrared absorbance showed the presence of H-bonding interaction between the salt and the polymer. X-ray diffraction showed the reduction of the grain size of ordered regions in the polymer matrix after adding salt. Thermo gravimetric analysis (TGA) showed water wt% content between 4.2 and 5.8%. Differential Scanning Calorimetry (DSC) showed the decrease of the glass transition due to retained water indicating its plasticizer effect. The ac conductivity studied in the frequency range from 10−1 Hz to 1 MHz and the temperature range from 10 to 150°C is described by the universal law of Jonsher characterizing the charge transport in disordered materials. With NH4Cl inclusion, the dc conductivity showed a higher value in the vicinity of 4% but with NH4CH3CO2 the dc conductivity decreases monotonically by increasing the salt amount. By using the dielectric permittivity and dielectric modulus we detected three relaxation processes which we attributed to electrode/sample polarization, alpha relaxation and conductivity relaxation respectively.

Structural Basis for the Exceptional Stability of Bisaminoacylated Nucleotides and Transfer RNAs

At least one bisaminoacyl-tRNA is synthesized in nature (by Thermus thermophilus phenylalanyl-tRNA synthetase), and many disubstituted tRNAs have been prepared in vitro. Such misacylated tRNAs are able to participate in protein synthesis, even though they lack the free 2'-OH group of the 3'-terminal adenosine moiety. Their ready participation in protein synthesis implies significant chemical reactivity. The basis for this reactivity has been documented previously. Surprisingly, the aminoacyl moieties of these tRNAs also exhibit exceptional chemical stability. In the present report, bisaminoacylated nucleotides are investigated computationally and experimentally to define the basis for the stability of such species. Molecular modeling of bisalanyl-AMP in the absence of solvent and in the presence of a limited number of water molecules revealed two common features among the low-energy structures. The first was the presence of H-bonding interactions between the two aminoacyl moieties. The second was the presence of a H-bonding interaction between the 2'-O-alanyl moiety and the N-3 atom of the adenine nucleobase, typically mediated through a water molecule. The prediction of an interaction between an aminoacyl moiety and the adenine nucleobase was confirmed experimentally by comparing the behavior of bisalanyl-AMP and bisalanyl-UMP in the presence of model nucleophiles. This study suggests a possible role for the adenosine moiety at the 3'-end of aminoanyl-tRNAs in controlling the stability and reactivity of the aminoacyl moiety and has important implications for the reactivity and stability of normal aminoacyl-tRNAs.

Polyadenylic acid binding on cationic liposomes doped with the non-ionic nucleolipid Lauroyl Uridine

In this work unilamellar liposomes doped with a novel non-ionic 5′-Uridine-head nucleolipid, Lauroyl Uridine (LU), were prepared and characterized for their ability to interact with the polynucleotide polyadenylic acid (poly-A). Vesicles, were made up of the cationic lipid DOTAP (1,2-Dioleoyl-3-Trimethylammonium-Propane), the zwitterionic lipid DOPE (1,2-Dioleoyl-sn-Glycero-3-Phosphoethanolamine), and the novel amphiphile Lauroyl Uridine. The influence of the non-ionic nucleolipid on essential liposomes properties, such as the structure and net charge was first investigated by a comparative analysis performed on the different lipoplex preparations by means of ζ-potential and size measurements. Both structure and net charge of liposomes were shown to be not modified by the presence of the non-ionic nucleolipid. The role of the synthetic lipid inserted as anchor in the liposome bilayer in the condensation process between vesicles and the polynucleotide poly-A was then analyzed by UV–vis, Circular Dichroism (CD) and nuclear magnetic resonance (NMR) spectroscopies. The data presented comparative UV–vis analyses that evidenced the occurrence of staking interactions in the poly-A only in LU containing lipoplexes. CD and NMR studies indicated the presence of H-bonding interaction between Lauroyl Uridine containing vesicles and the polynucleotide poly-A. The results presented in this work support a role for Lauroyl Uridine in A-U molecular recognition, thus, suggesting that cationic liposomes doped with the non-ionic nucleolipid Lauroyl Uridine could represent a model system to study molecular interactions among single stranded polynucleotides and lipid anchor bearing the complementary bases.

An Unprecedented-Type Intramolecular Redox Reaction of Solid Tetraamminecopper(2+) Bis(permanganate) ([Cu(NH3)4](MnO4)2) – A Low-Temperature Synthesis of Copper Dimanganese Tetraoxide-Type (CuMn2O4) Nanocrystalline Catalyst Precursors

b ), Istva ¬ n Sajo ¬ a ), Ja ¬ nos Kristo ¬f c Tetraamminecopper(2) bis(permanganate) ((Cu(NH3)4)(MnO4)2; 1) was prepared, and its properties were studied in both aqueous solution and the solid phase. The presence of H-bond interactions between the ammonia ligand of the complex cation and an O-atom of the permanganate ion was detected by IR and Raman methods. The solid-phase thermal deammoniation of 1 led to an unusual intramolecular redox reaction between the MnO¥¥¥H N linkage with formation of NH4NO3 and CuMn2O4-type mixed oxides instead of stepwise deammoniation, even below 100. The thermal deammoniation of 1 in aqueous solution led, instead of to hydrated copper(2) bis(permanganate), to the formation of NH4MnO4 (2). Since the temperature of the thermal deammoniation of 1 is lower than the decomposition temperature of the permanganate ion, the regulated solid-phase decomposition of 1 allowed preparation of CuMn2O4-type oxides with mixing of copper and manganese at the atomic level.