Global minimum and a heap of low-lying isomers with planar tetracoordinate carbon in the CAl3MgH2- system.

A global minimum and a heap of low-lying isomers with planar tetracoordinate carbon (ptC) are identified in the CAl3MgH2- system by computational quantum chemical investigations. The nature of the chemical bonding in the global minimum ptC isomer is examined using the conceptual quantum chemical tools. The atoms in molecule (AIM) analysis reveals that the global minimum isomer possesses a ptC geometry. Additionally, the adaptive natural density partitioning (AdNDP), electron localization function (ELF), and nucleus-independent chemical shifts (NICS) analysis corroborate the presence of delocalization in the ptC isomer. The delocalization of electron density in the global minimum ptC isomer contributes to attaining structural stability. The results also suggest that the bridging hydrogen plays a crucial role in stabilizing the ptC system. Furthermore, the ab initio molecular dynamics study supports the structural stability of the ptC isomer.

Theoretical Studies on the Isomerization Kinetics of Low-Lying Isomers of the SiC4H2 System.

The low-lying isomers of SiC4H2 are investigated to understand the kinetics of isomerization pathways using density functional theory. In our earlier work, we studied the various possible isomers (J. Phys. Chem. A, 2020, 124, 987-1002) and the chemical bonding of low-lying isomers of SiC4H2 (J. Phys. Chem. A, 2022, 126, 9366-9374). Among them, four isomers, 1-ethynyl-3-silacycloprop-1-en-3-ylidene (1), 3-silapent-1,4-diyn-3-ylidene (2), 1-silapent-1,2,3,4-tetraen-1-ylidene (4), and 1-silapent-2,4-diyn-1-ylidene (5) have already been identified in the laboratory. The previously known theoretical isomer 2-methylene-1-silabicyclo[1.1.0]but-1(3)-en-4-ylidene (3) and the newly identified unknown isomer through the present kinetic studies 5-silabicyclo[2.1.0]pent-1(4),2-dien-5-ylidene (N6) remain elusive in the laboratory to date. The isomerization pathways of the low-lying isomers of SiC4H2 are predicted through the transition state structures. Intrinsic reaction coordinate analysis identifies the minimum energy reaction pathways connecting the transition state from one isomer to another of the investigated system. The present kinetic data reveal the isomerization of global minimum energy isomer 1 to thermodynamically stable low-lying isomers, 2 and 5. Interestingly, isomer 3 interconverts to the experimentally known low-energy isomer 4, the second most thermodynamically stable isomer among them. The thermodynamic and kinetic parameters of the low-lying isomers of SiC4H2 are also documented in this work. The rate coefficient and equilibrium constant for isomerization reactions are calculated using the Rice-Ramsperger-Kassel-Marcus theory. The equilibrium constant delineates the difficulties in forming N6 and 3 through the isomerization pathways. Furthermore, ab initio molecular dynamics studies dictate the stability of low-lying isomers of SiC4H2 within the time scale of the simulation.

Attenuation of Quorum Sensing Mediated Virulence Factors and Biofilm Formation in Pseudomonas Aeruginosa PAO1 by Substituted Chalcones and Flavonols.

Flavonoids epitomize structural scaffolds in many biologically active synthetic and natural compounds. They showcase a diverse spectrum of biological activities including anticancer, antidiabetic, antituberculosis, antimalarial, and antibiofilm activities. The antibiofilm activity of a series of new chalcones and flavonols against clinically significant Pseudomonas aeruginosa PAO1 strain was studied. Antivirulence activities were screened by analysing the effect of compounds on the production of virulence factors like pyocyanin, LasA protease, cell surface hydrophobicity, and rhamnolipid. The best ligands towards the quorum sensing proteins LasR, RhlR, and PqsR were recognised using a molecular docking study. The gene expression in P. aeruginosa after treatment with test compounds was evaluated on quorum sensing genes including rhlA, lasB, and pqsE. The antibiofilm potential of chalcones and flavonols was confirmed by the efficient reduction in the production of virulence factors and downregulation of gene expression.

In Silico Drug Design and Analysis of Dual Amyloid-Beta and Tau Protein-Aggregation Inhibitors for Alzheimer's Disease Treatment.

Alzheimer's disease (AD) is a progressive and irreversible neurodegenerative disorder that gradually leads to the state of dementia. The main features of AD include the deposition of amyloid-beta peptides (Aß), forming senile plaques, and the development of neurofibrillary tangles due to the accumulation of hyperphosphorylated Tau protein (p-tau) within the brain cells. In this report, seven dual-inhibitor molecules (L1-7) that can prevent the aggregation of both Aß and p-tau are suggested. The drug-like features and identification of the target proteins are analyzed by the in silico method. L1-7 show positive results in both Blood-Brain Barrier (BBB) crossing and gastrointestinal absorption, rendering to the results of the permeation method. The molecular docking test performed for L1-7 shows binding energies in the range of -4.9 to -6.0 kcal/mol towards Aß, and -4.6 to -5.6 kcal/mol for p-tau. The drug's effectiveness under physiological conditions is assessed by the use of solvation models on the investigated systems. Further, the photophysical properties of L1-3 are predicted using TD-DFT studies.

Rational Computational Approaches in Drug Discovery: Potential Inhibitors for Allosteric Regulation of Mutant Isocitrate Dehydrogenase-1 Enzyme in Cancers.

Mutations in homodimeric isocitrate dehydrogenase (IDH) enzymes at specific arginine residues result in the abnormal activity to overproduce D-2 hydroxyglutarate (D-2HG), which is often projected as solid oncometabolite in cancers and other disorders. As a result, depicting the potential inhibitor for D-2HG formation in mutant IDH enzymes is a challenging task in cancer research. The mutation in the cytosolic IDH1 enzyme at R132H, especially, may be associated with higher frequency of all types of cancers. So, the present work specifically focuses on the design and screening of allosteric site binders to the cytosolic mutant IDH1 enzyme. The 62 reported drug molecules were screened along with biological activity to identify the small molecular inhibitors using computer-aided drug design strategies. The designed molecules proposed in this work show better binding affinity, biological activity, bioavailability, and potency toward the inhibition of D-2HG formation compare to the reported drugs in the in silico approach.

Planar pentacoordinate carbon in [XC7H2]2+ (X = Be and Mg) and its derivatives.

The planar pentacoordinate carbon (ppC) atom is theoretically established here in [XC7H2]2+ and [XSi2C5H2]2+, where X = Be and Mg, using density functional theory. Inclusion compounds with alkali and alkaline earth metal ions are identified with the monomer units of tricyclic C7H2 and Si2C5H2 isomers with a planar tetracoordinate carbon (ptC) atom. While all alkali and some alkaline earth metals (Ca2+, Sr2+, and Ba2+) stabilize the ptC isomer in both cases, Be2+ and Mg2+ ions form a bond directly with the ptC atom, thus making it a ppC atom. The theoretical binding energies computed at the PBE0-D3/def2-TZVP level of theory are ∼-9.68, -10.42, -5.85, and -5.47 eV for [BeC7H2]2+, [BeSi2C5H2]2+, [MgC7H2]2+, and [MgSi2C5H2]2+, respectively.

Why an integrated approach between search algorithms and chemical intuition is necessary?

Though search algorithms are appropriate tools for identifying low-energy isomers, fixing several constraints seems to be a fundamental prerequisite to successfully running any structural search program. This causes some potential setbacks as far as identifying all possible isomers, close to the lowest-energy isomer, for any elemental composition. The number of explored candidates, the choice of method, basis set, and availability of CPU time needed to analyze the various initial test structures become necessary restrictions in resolving the issues of structural isomerism reasonably. While one could arrive at new structures through chemical intuition, reproducing or achieving those exact same structures requires increasing the number of variables in any given program, which causes further constraints in exploring the potential energy surface in a reasonable amount of time. Thus, it is emphasized here that an integrated approach between search algorithms and chemical intuition is necessary by taking the C12O2Mg2 system as an example. Our initial search through the AUTOMATON program yielded 1450 different geometries. However, through chemical intuition, we found eighteen new geometries within 40.0 kcal mol-1 at the PBE0-D3/def2-TZVP level. These results indirectly emphasize that an integrated approach between search algorithms and chemical intuition is necessary to further our knowledge in chemical space for any given elemental composition.

Chemical Bonding Perspective on Low-Lying SiC4H2 Isomers: Conceptual Quantum Chemical Views.

The nature of the chemical bonding in seven low-lying isomers of SiC4H2 is analyzed through quantum chemical concepts. Out of the seven, four isomers, 1-ethynyl-3-silacycloprop-1(2)-en-3-ylidene (1), diethynylsilylidene (2), 1-sila-1,2,3,4-pentatetraenylidene (4), and 1,3-butadiynylsilylidene (5), have already been identified in the laboratory. The other three isomers, 2-methylenesilabicyclo[1.1.0]but-1(3)-en-4-ylidene (3), 4-sila-2-methylenebicyclo[1.1.0]but-1(3)-en-4-ylidene (6), and 3-ethynyl-1-silapropadienylidene (7) remain elusive in the laboratory to date (J. Phys. Chem. A, 2020, 124, 987-1002). Deep insight into the characteristics of chemical bonding is explored with different bonding analysis tools. Quantum theory of atoms in molecules (QTAIM), interaction quantum atoms analysis, natural bond orbital analysis, adaptive natural density partitioning, electron localization function (ELF), Laplacian of electron density, energy decomposition analysis, atomic charge analysis, bond order analysis, and frontier molecular orbital analysis are employed in the present work to gain a better understanding of the chemical bonding perspective in SiC4H2 isomers. Different quantum chemical topology approaches (QTAIM, ELF, and Laplacian of electron density) are employed to complement each other. The obtained results dictate that the lone pair of the silicon atom participate in delocalization and influences the structural stability of isomers.

Why Are MgC3H Isomers Missing in the Interstellar Medium?

Considering the recent findings of linear doublet (2Σ+) MgCnH isomers (n = 2, 4, and 6) in the evolved carbon star IRC+10216, various structural isomers of MgC3H and MgC3H+ are theoretically investigated here. For MgC3H, 11 doublet and 8 quartet stationary points ranging from 0.0 to 71.8 and 0.0 to 110.1 kcal mol-1, respectively, have been identified initially at the UωB97XD/6-311++G(2d,2p) level. To get accurate relative energies, further energy evaluations are carried out for all isomers with coupled cluster methods and thermochemical modules such as G3//B3LYP, G4MP2, and CBS-QB3 methods. Unlike the even series, where the global minima are linear molecules with a Mg atom at one end, in the case of MgC3H, the global minimum geometry turns out to be a cyclic isomer, 2-magnesabicyclo[1.1.0]but-1,3,4-triyl (1, C2v, 2A1). In addition, five low-lying isomers, magnesium-substituted cyclopropenylidene (2, Cs, 2A'), 1-magnesabut-2,3-dien-1-yl-4-ylidene (3, Cs, 2A″), 1-magnesabut-2-yn-1-yl-4-ylidene (4, Cs, 2A″), 2λ3-magnesabicyclo[1.1.0]but-1,3-diyl-4-ylidene (5, C2v;, 2A1), and 1-magnesabut-2,3-dien-2-yl-4-ylidene (6, C∞v, 2Σ+), were also identified. The doublet linear isomer of MgC3H, 1-magnesabutatrienyl (10, C∞v, 2Σ+) turns out to be a minimum but lies 54.1 kcal mol-1 above 1 at the ROCCSD(T)/cc-pVTZ level. The quartet (4Σ+) electronic state of 10 was also found to be a minimum, but it lies 8.0 kcal mol-1 above 1 at the same level. Among quartets, isomer 10 is the most stable molecule. The next quartet electronic state (of isomer 11) is 34.4 kcal mol-1 above 10, and all other quartet electronic states of other isomers are not energetically close to low-lying doublet isomers 2 to 6. Overall, the chemical space of MgC3H contains more cyclic isomers (1, 2, and 3) on the low-energy side unlike their even-numbered MgCnH counterparts (n = 2, 4, and 6). Though the quartet electronic state of 10 is linear, it is not the global minimum geometry on the MgC3H potential energy surface. Isomerization pathways among the low-lying isomers (doublets of 1-4 and a quartet of 10) reveal that these molecules are kinetically stable. For the cation, MgC3H+, the cyclic isomers (1+, 2+, and 3+) are on the low-energy side. The singlet linear isomer, 10+, is a fourth-order saddle point. The low-lying cations are quite polar, with dipole moment values of >7.00 D. The current theoretical data would be helpful to both laboratory astrophysicists and radioastronomers for further studies on the MgC3H0/+ isomers.

Chiral discrimination in a mutated IDH enzymatic reaction in cancer: a computational perspective.

Chiral discrimination in biological systems, such as L-amino acids in proteins and d-sugars in nucleic acids, has been proposed to depend on various mechanisms, and chiral discrimination by mutated enzymes mediating cancer cell signaling is important in current research. We have explored how mutated isocitrate dehydrogenase (IDH) catalyzes the oxidative decarboxylation of isocitrate to α-ketoglutarate which in turn is converted to d-2-hydroxyglutatrate (d-2HG) as a preferred product instead of l-2-hydroxyglutatrate (l-2HG) according to quantum chemical calculations. Using transition state structure modeling, we delineate the preferred product formation of d-2HG over l-2HG in an IDH active site model. The mechanisms for the formation of d-2HG over l-2HG are assessed by identifying transition state structures and activation energy barriers in gas and solution phases. The calculated reaction energy profile for the formation of d-2HG and l-2HG metabolites shows a 29 times higher value for l-2HG as compared to d-2HG. Results for second-order Møller-Plesset perturbation theory (MP2) do not alter the observed trend based on Density Functional Theory (DFT). The observed trends in reaction energy profile explain why the formation of D-2HG is preferred over l-2HG and reveal why mutation leads to the formation of d-2HG instead of l-2HG. For a better understanding of the observed difference in the activation barrier for the formation of the two alternative products, we performed natural bond orbital analysis, non-covalent interactions analysis and energy decomposition analysis. Our findings based on computational calculations clearly indicate a role for chiral discrimination in mutated enzymatic pathways in cancer biology.

Si2C5H2 isomers - search algorithms versus chemical intuition.

The pros and cons of using search algorithms alone in identifying new geometries have been discussed by using the Si2C5H2 elemental composition as an example. Within 30 kcal mol-1 at the CCSD(T)/def2-TZVP//PBE0/def2-TZVP level of theory, the coalescence kick and cuckoo methods postulate merely four isomers (1, 3, 6, and 7) for Si2C5H2 (O. Yañez et. al., Chem. Commun., 2017, 53, 12112). On the contrary, chemical intuition yields fourteen (2, 4, 5, and 8-18) new isomers within the same energy range at the B3LYP/6-311++G(2d,2p) level of theory. Based on the relative energies of the first eleven isomers of Si2C5H2 (1, C2v, 0.00; 2, Cs, 21.39; 3, Cs, 21.95; 4, Cs, 22.76; 5, Cs, 24.74; 6, Cs, 25.34; 7, Cs, 25.64; 8, Cs, 25.79; 9, Cs, 27.20; 10, C2v, 28.59; and 11, C2v, 29.16 kcal mol-1) calculated at the CCSD(T)/cc-pVTZ level of theory, it is evident that the search algorithms had missed at least seven isomers in the same energy range. The relative energy gaps of isomers 12-18 fall in the range of 30-40 kcal mol-1 at the latter level of theory. Consequentially, this scenario triggers a speculation going forward with search algorithms alone in the search of all new isomers. While one cannot underestimate the power of these algorithms, the role of chemical intuition may not be completely neglected. Retrospectively, the fourteen new isomers found by chemical intuition may help in writing better search algorithms. All eighteen isomers - including the most stable isomer with a planar tetracoordinate carbon atom 1- remain elusive in the laboratory to date. Thus, structural and spectroscopic parameters have been presented here, which may possibly aid the future experimental studies.

Theoretical Studies of SiC4H2 Isomers Delineate Three Low-Lying Silylidenes Are Missing in the Laboratory.

Eleven isomers of SiC4H2 lying within 50 kcal mol-1 have been theoretically investigated using density functional theory and high-level coupled-cluster methods. Among them, four isomers, 1-ethynyl-3-silacycloprop-1(2)-en-3-ylidene (1), diethynylsilylidene (2), 1-sila-1,2,3,4-pentatetraenylidene (4), and 1,3-butadiynylsilylidene (5), have already been identified in the laboratory. The current investigation reports three low-lying (<1 eV) silylidenes [2-methylenesilabicyclo[1.1.0]but-1(3)-en-4-ylidene (3), 4-sila-2-methylenebicyclo[1.1.0]but-1(3)-en-4-ylidene (6), and 3-ethynyl-1-silapropadienylidene (7)] and three high-lying (>1 eV) silylidenes [2-sila-(didehydrovinylidene)cyclopropene (8), an isomer with a planar tetracoordinate carbon (ptC) atom (10), and 1-ethynyl-1-silapropadienylidene (11)], which remain elusive in the laboratory to date. Isomer 9 also contains a ptC atom, which turned out to be a transition state at all levels. Though all isomers are polar (µ ≠ 0), rotational spectrum is available only for 4. Using matrix isolation, three isomers (1, 2, and 5) have been trapped in the laboratory at 10 K. Considering the astrochemical relevance of silicon-carbide clusters in the interstellar medium, the current theoretical data demand new molecular spectroscopic studies on SiC4H2. Surprisingly, unlike the isovalent C5H2 isomers, where the bent carbenes are yet to be identified in the laboratory, the bent silylidenes (2 and 5) have been trapped in the case of SiC4H2. In both the cases, molecules with transannular C-C and/or Si-C bonds remain elusive, though they lie in the low-lying region. Using suitable precursors, whether these peculiar geometries (especially 3 and 6) would be identified or not in the laboratory needs to be addressed by molecular spectroscopists. The present investigation documents structural and spectroscopic information of SiC4H2 isomers, which may compliment future molecular spectroscopic observations including radioastronomical searches.

(Tetrahydrodibenzo[a,i]phenanthridin-5-yl)phenol as a Fluorescent Probe for the Detection of Aniline.

Two (tetrahydrodibenzo[a,i]phenanthridin-5-yl)phenols that differ in their substituents at the para position (P1, R = H and P2, R = NEt2) were designed and synthesized. The presence of a -NEt2 group in probe P2 facilitates the twisted intramolecular charge transfer (TICT) process, making P2 emissive, which distinctly coordinated with boron trifluoride in the presence of different amines with different electronic properties. A substantial increase in emission intensity with increasing viscosity of the surrounding environment and smooth formation of a planar complex with boron and Zn2+ ions concluded the presence of a TICT process. The selective reactivity of P2 toward a tetracoordinated boron complex has been explored as a potential tool for colorimetric and fluorescent discrimination of aromatic primary amines, i.e., anilines. Selective detection of aniline with probe P2 can be viewed through the naked eye, and the corresponding fluorescence turn-on detection limit was found to be 12.65 nM. In addition, the detection of aniline on precoated aluminum-backed thin-layer chromatography plates and Whatman filter paper strips was found to be in good agreement with the color change of P2 in solution and in vapor phase.

From High-Energy C7H2 Isomers with A Planar Tetracoordinate Carbon Atom to An Experimentally Known Carbene.

In this work, we use high-level ab initio procedures to show that the high-energy isomers of C7H2 with a planar tetracoordinate carbon (ptC) atom serve as reactive intermediate leading to the formation of an experimentally known ring-chain carbene, 1-(buta-1,3-diynyl)cyclopropenylidene (2). Among the experimentally known isomers of C7H2, the latter is the only low-lying ring-chain carbene identified by Fourier-transform microwave spectroscopy. Here we investigate the ring-opening pathways of C-C single bonds connected to the ptC atom in three different C7H2 isomers using coupled-cluster and density functional theory methods. These three isomers [ptC1 ( C2 v; X̃1A1), ptC2 ( C s; X̃1A'), and ptC3 ( C s; X̃1A')] are found to be local minima on the C7H2 potential-energy surface at both CCSD(T)/cc-pVTZ and B3LYP/6-311+G(d,p) levels of theory. The transition states and minimum-energy pathways connecting the reactants (ptC isomers) and the products have been found via intrinsic reaction coordinate calculations at the B3LYP/6-311+G(d,p) level of theory. The high-energy ptC isomers (ptC2 and ptC3) lead to the formation of 2, while the low-energy ptC isomer, ptC1, rearranges to a bicyclic carbene, bicyclo[4.1.0]hepta-4,6-diene-2-yne-7-ylidene (6). In the latter, we note that both the reactant and the product are yet to be identified in the laboratory. Relative energies, activation energies, reaction energies, and nucleus independent chemical shift values have been calculated to access the thermodynamic and kinetic stabilities and the aromatic nature of these peculiar molecules. Rotational and centrifugal distortion constants have also been estimated for all ptC isomers, which may assist the efforts of microwave spectroscopists.

Synthesis and study of antibiofilm and antivirulence properties of flavonol analogues generated by palladium catalyzed ligand free Suzuki-Miyaura coupling against Pseudomonas aeruginosa PAO1.

The Suzuki-Miyaura coupling is one of the ubiquitous method for the carbon-carbon bond-forming reactions in organic chemistry. Its popularity is due to its ability to undergo extensive coupling reactions to generate a broad range of biaryl motifs in a straightforward manner displaying a high level of functional group tolerance. A convenient and efficient synthetic route to arylate different substituted flavonols through the Suzuki-Miyaura cross-coupling reaction has been explained in this study. The arylated products were acquired by the coupling of a variety of aryl boronic acids with flavonols under Pd(OAc)2 catalyzed reaction conditions in a ligand-free reaction strategy. Subsequently, the antibiofilm and antivirulence properties of the arylated flavonols against Pseudomonas aeruginosa PAO1 were studied thoroughly. The best ligands for quorum sensing proteins LasR, RhlR, and PqsR were identified using molecular docking study. These best fitting ligands were then studied for their impact on gene expression level of P. aeruginosa by RT-PCR towards quorum sensing genes lasB, rhlA, and pqsE. The downregulation in the gene expression with the effect of synthesized flavonols endorse the antibiofilm efficiency of the compounds.

Oxoperoxovanadium Complexes of Hetero Ligands: X-Ray Crystal Structure, Density Functional Theory, and Investigations on DNA/BSA Interactions, Cytotoxic, and Molecular Docking Studies.

Oxoperoxovanadium (V) complexes [VO (O)2 (nf) (bp)] (1) and [VO (O)2 (ox) (bp)] (2) based on 5-nitro-2-furoic acid (nf), oxine (ox) and 2, 2' bipyridine (bp) bidentate ligands have been synthesized and characterized by FT-IR, UV-visible, mass, and NMR spectroscopic techniques. The structure of complex 2 shows distorted pentagonal-bipyramidal geometry, as confirmed by a single-crystal XRD diffraction study. The interactions of complexes with bovine serum albumin (BSA) and calf thymus DNA (CT-DNA) are investigated using UV-visible and fluorescence spectroscopic techniques. It has been observed that CT-DNA interacts with complexes through groove binding mode and the binding constants for complexes 1 and 2 are 8.7 × 103 M-1 and 8.6 × 103 M-1, respectively, and BSA quenching constants for complexes 1 and 2 are 0.0628 × 106 M-1 and 0.0163 × 106 M-1, respectively. The ability of complexes to cleave DNA is investigated using the gel electrophoresis method with pBR322 plasmid DNA. Furthermore, the cytotoxic effect of the complexes is evaluated against the HeLa cell line using an MTT assay. The complexes are subjected to density functional theory calculations to gain insight into their molecular geometries and are in accordance with the results of docking studies. Furthermore, based on molecular docking studies, the intermolecular interactions responsible for the stronger binding affinities between metal complexes and DNA are discussed.

"Turn-on" unsymmetrical azine based fluorophore for the selective detection of diethylchlorophosphate via photoinduced electron transfer to intramolecular charge transfer pathway.

The detection of chemical warfare agents (CWAs) in a highly selective, sensitive and speedy manner is essential for public safety in the case of terrorist attacks and achieving this is a challenging task. This study involves in developing a new unsymmetrical azine based fluorophore 4-((E)-(((E)-2-methoxybenzylidene)hydrazono)methyl)benzonitrile[A1] which shows high selectivity and sensitivity to the nerve agent mimic molecule, diethylchlorophosphate (DCP) through fluorescence switch on mechanism. In a fascinating manner, DCP sensing by A1 operates via solvent dependent optical output mechanisms. In the absence of DCP, the fluorescence of A1 was in the off state through photoinduced electron transfer process. In the presence of DCP, a nucleophilic substitution reaction occurs at the imine nitrogen is closer to the anisole moiety that results in the formation of a new intramolecular charge transfer state along with fluorescence enhancement. In acetonitrile, A1 shows 1763-fold fluorescence enhancement in the presence of DCP with a detection limit of 9.86 nM. In Acetonitrile/water (2:8) mixture, protonation at the imine nitrogen leads to 1188-fold fluorescence enhancement. The sensing mechanisms are confirmed by both experimental and time dependent density functional theoretical studies.

Closed-cage tungsten oxide clusters in the gas phase.

During the course of a study on the clustering of W-Se and W-S mixtures in the gas phase using laser desorption ionization (LDI) mass spectrometry, we observed several anionic W-O clusters. Three distinct species, W(6)O(19)(-), W(13)O(29)(-), and W(14)O(32)(-), stand out as intense peaks in the regular mass spectral pattern of tungsten oxide clusters suggesting unusual stabilities for them. Moreover, these clusters do not fragment in the postsource decay analysis. While trying to understand the precursor material, which produced these clusters, we found the presence of nanoscale forms of tungsten oxide. The structure and thermodynamic parameters of tungsten clusters have been explored using relativistic quantum chemical methods. Our computed results of atomization energy are consistent with the observed LDI mass spectra. The computational results suggest that the clusters observed have closed-cage structure. These distinct W(13) and W(14) clusters were observed for the first time in the gas phase.

NLO-active Y-shaped ferrocene conjugated imidazole chromophores as precursors for SHG polymeric films.

New Y-shaped ferrocene conjugated imidazole chromophores were prepared and fully characterized. The Y-shaped structure was confirmed by the single crystal X-ray diffraction technique. The chromophores show interesting second-order nonlinear optical (NLO) properties in solution, as determined by the Electric-Field Induced Second Harmonic generation (EFISH) technique. Remarkably, the trifluoro substituted compound 3 is characterized by a high µßEFISH value and has good potential as a molecular building block for composite films with Second Harmonic Generation (SHG) properties. For all compounds, the dipole moments and frontier orbital energies were calculated by the Density Functional Theoretical method.

The molecular recognition of dipeptide by oligoglycyl head group of amphiphile: a quantum chemical study.

In the present work, we presented an analysis of the unusual recognition specificity exhibited by marked difference in the binding behavior of dipeptide with amphiphilic head group when subtle relative change of N-terminal and C-terminal of the dipeptide are made. Recently, in a series of detailed experiments, binding of aqueous dipeptides, GlyX and X/Gly (X = Leu, Phe, Pro, Ala; X/ = Leu, Phe) with dialkyl oligoglycyl amphiphiles is studied [X. Cha, K. Ariga, M. Onda, and T. Kunitake, J. Am. Chem. Soc. 117, 11833 (1995)]. It is observed that GlyX are specifically bound to 2C18BGly2NH2 while X/Gly are insignificantly bound. We first studied the conformational energy variation of GlyPhe, PheGly and model of 2C18BGly2NH2 amphiphile using semi-empirical and ab-initio methods in vacuum. Using the individual energy optimized monomer structure of amphiphile and peptide, we studied the binding energy of optimized GlyPhe: amphiphile pair and PheGly: amphiphile pair structures at 1:1 and 1:2 ratio at the same level of theory using a population of structures. Binding of GlyPhe is favorable over the binding of PheGly at various levels of theory (semi-empirical and ab-initio). It is noted that the hydrogen bonding pattern in the GlyPhe binding is more effective than that in the PheGly binding. In the population of low energy structures, PheGly: amphiphile structures have more exposed area around the hydrophobic Phe group than the GlyPhe: amphiphile structures. Relatively more PheGly: amphiphile structures have intermolecular orientation unsuitable to contribute to the population of head group structures relevant in aqueous interface. Summarizing, significantly better binding capacity of GlyPhe over the PheGly with amphiphile, is due to the difference in hydrogen bonding interaction pattern, hydrophobic effect and possible orientations of the amphiphile and peptide at interface, relevant to the condensed phase monolayer structure. All the three factors cooperatively lead to favorable recognition of GlyPhe over PheGly as observed in experiment. A calculation of the ratio of the amphiphile-peptide bound complex to the initial concentration of the amphiphile indicates that the diffusional process at the peptide interfaces could be significantly influenced by hydrogen bonding.