Understanding solvent effects on structure and reactivity of organic intermediates: a Raman study

The effect of solvent on chemical reactivity has generally been explained on the basis of the dielectric constant and viscosity. However a number of spectroscopic studies, including UV-VIS, IR and Raman, has led to numerous empirical parameters to define solvent effect based on either solvating ability or polarity scale. These parameters include solvent polarizability, dipolarity, Lewis acidity and Lewis basicity, E-T(30), pi*, alpha, beta etc. However, from a structural point of view, we can separate solvation as static and dynamic processes. The static solvation basically relates to stabilization of the molecular structure by the solvent to attain the equilibrium structure, both in the intermediate and ground state. Dynamic solvation relates to solvent reorganization-induced dynamics prior to the structural reorganization to reach the equilibrium state. In this paper, we present (a) structural distortions induced by the solvent due to preferential solvation of the triplet excited state, and (b) the importance of dynamic solvation induced by vibronic coupling (pseudo-Jahn-Teller coupling). The examples include the effect of solvent on structure and reactivity of excited states of 2,2,2-trifluoroacetophenone (TFA). Based on the comparison of time resolved resonance Raman (TR3) data of TFA and other substituted acetophenone systems, it was found that change in solvent polarity indeed results in electronic state switching and structural changes in the excited state, which explains the trend in reactivity. Further, a TR3 study of fluoranil (FA) in the triplet excited state in solvents of varying polarities indicates that the structure of FA in the triplet excited state is determined by vibronic coupling effects and thus distorted structure. These experimental results have been well supported by density functional theoretical computational studies.

Rotational isomerism about the Ca-CO bond in proline derivatives. 1H and 13C NMR studies of benzyloxycarbonyl-Pro-N-methylamide and pivaloyl-Pro-N-methylamide

The 270 MHz 1H n.m.r. spectrum of benzyloxycarbonyl-Pro-N-methylamide in CDCl3 is exchange broadened at 293° K. Spectral lines due to two species are frozen out at 253° K and a dynamically averaged spectrum is obtained at 323° K. A selective broadening of the Cβ and Cγ resonances in the 13C n.m.r. spectrum is observed at 253° K, with a splitting of the Cβ and Cγ resonances into a pair of lines of unequal intensity. A similar broadening of Cβ and Cγ peaks is also detected in pivaloyl-Pro-N-methylamide where cis-trans interconversion about the imide bond is precluded by the bulky t-butyl group. The rate process is thus attributed to rotation about the Cα-CO bond (ψ) and a barrier (ΔG#) of 14kcal mol-1 is estimated. 13C n.m.r. data for pivaloyl-Pro-N-methylamide in a number of solvents is presented and the differences in the Cβ and Cγ chemical shifts are interpreted in terms of rotational isomerism about the Cα-CO bond.

Breath Testing by Fourier Transform Infrared Spectroscopy for Solvent Intoxication Diagnostics

Technical or contaminated ethanol products are sometimes ingested either accidentally or on purpose. Typical misused products are black-market liquor and automotive products, e.g., windshield washer fluids. In addition to less toxic solvents, these liquids may contain the deadly methanol. Symptoms of even lethal solvent poisoning are often non-specific at the early stage. The present series of studies was carried out to develop a method for solvent intoxication breath diagnostics to speed up the diagnosis procedure conventionally based on blood tests. Especially in the case of methanol ingestion, the analysis method should be sufficiently sensitive and accurate to determine the presence of even small amounts of methanol from the mixture of ethanol and other less-toxic components. In addition to the studies on the FT-IR method, the Dräger 7110 evidential breath analyzer was examined to determine its ability to reveal a coexisting toxic solvent. An industrial Fourier transform infrared analyzer was modified for breath testing. The sample cell fittings were widened and the cell size reduced in order to get an alveolar sample directly from a single exhalation. The performance and the feasibility of the Gasmet FT-IR analyzer were tested in clinical settings and in the laboratory. Actual human breath screening studies were carried out with healthy volunteers, inebriated homeless men, emergency room patients and methanol-intoxicated patients. A number of the breath analysis results were compared to blood test results in order to approximate the blood-breath relationship. In the laboratory experiments, the analytical performance of the Gasmet FT-IR analyzer and Dräger 7110 evidential breath analyzer was evaluated by means of artificial samples resembling exhaled breath. The investigations demonstrated that a successful breath ethanol analysis by Dräger 7110 evidential breath analyzer could exclude any significant methanol intoxication. In contrast, the device did not detect very high levels of acetone, 1-propanol and 2-propanol in simulated breath. The Dräger 7110 evidential breath ethanol analyzer was not equipped to recognize the interfering component. According to the studies the Gasmet FT-IR analyzer was adequately sensitive, selective and accurate for solvent intoxication diagnostics. In addition to diagnostics, the fast breath solvent analysis proved feasible for controlling the ethanol and methanol concentration during haemodialysis treatment. Because of the simplicity of the sampling and analysis procedure, non-laboratory personnel, such as police officers or social workers, could also operate the analyzer for screening purposes.

Effect of pretreatment on the formation of 5-chloromethyl furfural derived from sugarcane bagasse

Chloromethylfurfural (CMF), a valuable intermediate for the production of chemicals and fuel, can be derived in high yields from the cellulose component of biomass. This study examined the effect of sugar cane bagasse components and biomass architecture on CMF/bio-oil yield using a HCl/dichloroethane biphasic system. The type of pretreatment affected bio-oil yield, as the CMF yield increased with increasing glucan content. CMF yield reached 81.9% with bagasse pretreated by acidified aqueous ionic liquid, which had a glucan content of 81.6%. The lignin content of the biomass was found to significantly reduce CMF yield, which was only 62.3% with acid-catalysed steam exploded sample having a lignin content of 29.6%. The change of CMF yield may be associated with fibre surface changes as a result of pretreatment. The hemicellulose content also impacted negatively on CMF yield. Storage of the bio-oil in chlorinated solvents prevented CMF degradation.

Evaluation of the AlgerBrush II rotating burr as a tool for inducing ocular surface failure in the New Zealand White rabbit

The New Zealand White rabbit has been widely used as a model of limbal stem cell deficiency (LSCD). Current techniques for experimental induction of LSCD utilize caustic chemicals, or organic solvents applied in conjunction with a surgical limbectomy. While generally successful in depleting epithelial progenitors, the depth and severity of injury is difficult to control using chemical-based methods. Moreover, the anterior chamber can be easily perforated while surgically excising the corneal limbus. In the interest of creating a safer and more defined LSCD model, we have therefore evaluated a mechanical debridement technique based upon use of the AlgerBrush II rotating burr. An initial comparison of debridement techniques was conducted in situ using 24 eyes in freshly acquired New Zealand White rabbit cadavers. Techniques for comparison (4 eyes each) included: (1) non-wounded control, (2) surgical limbectomy followed by treatment with 100% (v/v) n-heptanol to remove the corneal epithelium (1-2 minutes), (3) treatment of both limbus and cornea with n-heptanol alone, (4) treatment of both limbus and cornea with 20% (v/v) ethanol (2-3 minutes), (5) a 2.5-mm rounded burr applied to both the limbus and cornea, and (6) a 1-mm pointed burr applied to the limbus, followed by the 2.5-mm rounded burr applied to the cornea. All corneas were excised and processed for histology immediately following debridement. A panel of four assessors subsequently scored the degree of epithelial debridement within the cornea and limbus using masked slides. The 2.5-mm burr most consistently removed the corneal and limbal epithelia. Islands of limbal epithelial cells were occasionally retained following surgical limbectomy/heptanol treatment, or use of the 1-mm burr. Limbal epithelial cells were consistently retained following treatment with either ethanol or n-heptanol alone, with ethanol being the least effective treatment overall. The 2.5-mm burr method was subsequently evaluated in the right eye of 3 live rabbits by weekly clinical assessments (photography and slit lamp examination) for up to 5 weeks, followed by histological analyses (hematoxylin & eosin stain, periodic acid-Schiff stain and immunohistochemistry for keratin 3 and 13). All 3 eyes that had been completely debrided using the 2.5-mm burr displayed symptoms of ocular surface failure as defined by retention of a prominent epithelial defect (~40% of corneal surface at 5 weeks), corneal neovascularization (2 to 3 quadrants), reduced corneal transparency and conjunctivalization of the corneal surface (demonstrated by the presence of goblet cells and/or staining for keratin 13). In conclusion, our findings indicate that the AlgerBrush II rotating burr is an effective method for the establishment of ocular surface failure in New Zealand White rabbits. In particular, we recommend use of the 2.5-mm rotating burr for improved efficiency of epithelial debridement and safety compared to surgical limbectomy.

Trap-State Dynamics in Visible-Light-Emitting ZnO:MgO Nanocrystals

Oleate-capped ZnO:MgO nanocrystals have been synthesized that are soluble in nonpolar solvents and which emit strongly in the visible region (450−600 nm) on excitation by UV radiation. The visible emission involves recombination of trap states of the nanocrystalline ZnO core and has a higher quantum yield than the band gap UV exciton emission. The spectrally resolved dynamics of the trap states have been investigated by time-resolved emission spectroscopy. The time-evolution of the photoluminescence spectra show that there are, in fact, two features in the visible emission whose relative importance and efficiencies vary with time. These features originate from recombination involving trapped electrons and holes, respectively, and with efficiencies that depend on the occupancy of the trap density of states.

The Use of Liquid-Liquid Interface (Biphasic) for the Preparation of Benzenetricarboxylate Complexes of Cobalt and Nickel

New metal-organic frameworks (MOFs) [Ni(C12N2H10)(H2O)][C6H3(COO)2(COOH)] (I), [Co2(H2O)6][C6H3(COO)3]2·(C4N2H12)(H2O)2 (II), [Ni2(H2O)6][C6H3(COO)3]2·(C4N2H12)(H2O)2 (III), [Ni(C13N2H14)(H2O)][C6H3(COO)2(COOH)] (IV), [Ni3(H2O)8][C6H3(COO)3] (V) and [Co(C4N2H4)(H2O)][C6H3(COO)3] (VI) {C6H3(COOH)3 = trimesic acid, C12N2H10 = 1,10-phenanthroline, C4N2H12 = piperazine dication, C13N2H14 = 1,3-bis(4-pyridyl)propane and C4N2H4 = pyrazine} have been synthesized by using an interface between two immiscible solvents, water and cyclohexanol. The compounds are constructed from the connectivity between the octahedral M2+ (M = Ni, Co) ions coordinated by oxygen atoms of carboxylate groups and water molecules and/or by nitrogen atoms of the ligand amines and the carboxylate units to form a variety of structures of different dimensionality. Strong hydrogen bonds of the type O-H···O are present in all the compounds, which give rise to supramolecularly organized higher-dimensional structures. In some cases ··· interactions are also observed. Magnetic studies indicate weak ferromagnetic interactions in I, IV and V and weak antiferromagnetic interactions in the other compounds (II, III and VI). All the compounds have been characterized by a variety of techniques.

Tuning the beta-turn segment in designed peptide beta-hairpins: Construction of a stable type I ' beta-turn nucleus and hairpin-helix transition promoting segments

Designed octapeptides Boc-Leu-Val-Val-Aib-(D)Xxx-Leu- Val-Val-OMe ((D)Xxx = (D)Ala, 3a; (D)Val, 3c and (D)Pro, 5a) and Boc-Leu-Phe-Val-Aib-DAla-Leu-Phe-Val-OMe (3b) have been investigated to construct models of a stable type I' beta-turn nucleated hairpin and to generate systems for investigating helix-hairpin conformational transitions. Peptide 5a, which contains a central Aib-(D)Pro segment, is shown to adopt a stable type I' beta-turn nucleated hairpin structure, stabilized by four cross-strand hydrogen bonds. The stability of the structure in diverse solvents is established by the observation of all diagnostic NOEs expected in a beta-hairpin conformation. Replacement of (D)Pro5 by (D)Ala/(D)Val (3a-c) results in sequences that form beta-hairpins in hydrogen bonding solvents like CD3OH and DMSO-d(6). However, in CDCl3 evidence for population of helical conformations is obtained. Peptide 6b (Boc-Leu-Phe-Val-Aib-Aib-Leu-Phe-Val-OMe), which contains a centrally positioned Aib-Aib segment, provides a clear example of a system, which exhibits a helical conformation in CDCl3 and a significant population of both helices and hairpins in CD3OH and DMSO-d(6). The coexistence of multiple conformations is established by the simultaneous observation of diagnostic NOEs. Control over stereochemistry of the central beta-turn permits generation of models for robust beta-hairpins and also for the construction of systems that may be used to probe helix-hairpin conformational transitions. (c) 2006 Wiley Periodicals, Inc.

Rationalizing the effects of amino acid side chain, pyridine, and imidazole on the assembly and reversible disassembly of a octanuclear Cu(III) complex

This paper reports the observation of a reversible disassembly process for a previously reported octanuclear Cu(II) complex with imidazole. To identify the factors responsible for the process, five Cu(II) complexes of different nuclearity with different amino acid-derived tetradentate ligands were structurally characterized. The results show that the coordination geometry preference of Cu(II), the tendency of imidazole to act as in-plane ligand, and H-bonding played important role in the formation and disassembly of the octanuclear complex. A general scheme describing the effect of different amino acid side arms, solvents, and exogenous ligands on the nuclearity of the Cu(II) complexes has been presented. The crystals of the complexes also showed formation of multifaceted networks in the resulting complexes.

Synthesis and Characterization of a Class of Donor-Acceptor Conjugated Molecules: Experiments and Theoretical Calculations

A class of conjugated molecules containing donor (thiophene) and acceptor (malononitrile) is synthesized by Knoevenagel condensation reaction between 2-(2,6-dimethy1-4H-pyran-4-ylidene) malononitrile and thiophene carbaldehyde containing two and three thiophene units. The resulting molecules are characterized by H-1 and C-13 NMR. We have performed UV-vis absorption, fluorescence, and cyclic voltammetry measurements on these materials. The spectroscopic and electrochemical measurements proved beyond doubt that these materials possess lowexcitation gap and are suitable for being an active material in various electronic devices. We have also performed electronic structure calculations using density functional theory (DFT) and INDO/SCI methods to characterize the ground and excited states of this class of molecules. These donor-acceptor molecules show a strong charge transfercharacter that increases with the increase in the number of thiophene rings coupled to the malononitrile acceptor moiety. We have also calculated the pi-coherence length, Stoke's shift, and effect of solvents on excited states for this class of molecules, Our theoretical values agree well with experimental results.

Synthetic and conformational studies on dehydroalanine-containing model peptides

Three model dipeptides containing a dehydroalanine residue (Ala) at the C-terminal, Boc-X-Ala-NHCH3 [X = Ala, Val, and Phe,] have been synthesized and their solution conformations investigated by 1H-NMR, IR, and CD spectroscopy. NMR studies on these peptides in CDCl3 clearly indicate that the NH group of dehydroalanine is involved in an intramolecular hydrogen bond. This conclusion is supported by IR studies also. Nuclear Overhauser effect (NOE) studies are also accommodative of an inverse -turn-type of conformation that is characterised by conformational angles of -70° and +70° around the X residue, and a C[stack i+1 ]H-Ni+2H interproton distance of 2.5 Å. It appears that unlike dehydrophenylalanine or dehydroleucine, which tend to stabilize -turn type of structures occupying the i + 2 position of the turn, dehydroalanine favors the formation of an inverse -turn, centered at the proceeding L-residue in such solvents as CDCl3 and (CD3)2SO. A comparison of solution conformation of Boc Val-Ala-NHCH3 with the corresponding saturated analogue, Boc-Val-Ala-NHCH3, is also presented and shows that dehydroalanine is responsible for inducing the turn structure. It may be possible to design peptides with different preferred conformations using the suitable dehydroamino acid.

Synthesis and characterization of polyaniline salts with phenoxy acetic acids by emulsion polymerization

Polyaniline salts have been synthesized by chemical oxidative polymerization of aniline in the presence of phenoxy acetic acid and its two derivatives using emulsion method at room temperature and characterized by different techniques such as infrared, H-1 and C-13 NMR, UV-visible spectroscopy, SEM, wide angle X-ray diffractograms and conductivity measurements. These polyaniline salts have the desirable property of high solubility for processibility in solvents such as DNIF, DMSO and a mixture of CHCl3 and acetone and they exhibit fairly good conductivity of similar to 3.0 x 10(-3) S cm(-1). The variations in solubility, conductivity and morphology with the protonating strength of the dopants are examined.

Selective Homonuclear Decoupling in H-1 NMR: Application to Visualization of Enantiomers in Chiral Aligning Medium and Simplified Analyses of Spectra in Isotropic Solutions

The proton NMR spectral complexity arising due to severe overlap of peaks hampers their analyses in diverse situations, even by the application of two-dimensional experiments. The selective or complete removal of the couplings and retention of only the chemical shift interactions in indirect dimension aids in the simplification of the spectrum to a large extent with little investment of the instrument time. The present study provides precise enantiodiscrimination employing more anisotropic NMR parameters in the chiral liquid crystalline medium and differentiates the overlapped peaks of many organic molecules and peptides dissolved in isotropic solvents.

Antipyrine complexes of titanium(IV), zirconium(iv), thorium(IV) and uranium(VI) perchlorates

Antipyrine complexes of TiO2+, ZrO2+, Zr4+, Th4+ and UO2+2 perchlorates with molecular formulae TiO(Apy)4(ClO4)2, ZrO(Apy)3(ClO4)2, Zr(Apy)6(ClO4)4, Th(Apy)7(ClO4)4 and UO2(Apy)5(ClO4)2 have been prepared and characterized. The complexes are stable in air at room temperature and decompose exothermally at ~3OO °C. The i.r. study indicates the bonding of the antipyrine to the metal ion through its carbonyl oxygen. The nature of the bonding of the perchlorate and the stereochemistry of the complexes are discussed in the light of infrared spectra, conductivity in solvents of different polarity, and molecular weight measurements. From the UO2+2 group frequencies, the force constant K and rU-o are found to be 6.29 × 105 dynes/ cm-1 and 1.74 Å, respectively.

Reactions with disulphur monoxide solutions obtained by the reduction of cupric oxide by elemental sulphur

When the products of reaction between elemental sulphur and copper oxide at elevated temperature in vacuum are bubbled through chilled inert organic solvents like carbontetrachloride, orange-yellow solutions were obtained indicating the presence of lower oxide of sulphur. This lower oxide has been found to be disulphur monoxide as shown by three different types of reactions; (1) Mercury decomposition, (2) Reaction with hydrogen iodide and hydrolytic reaction in an alkaline homogeneous medium.