Helical supramolecular host with aquapores anchoring alternate molecules of helical water chains

Unprecedented 1D helical chains of hydrogen bonded water molecules, showing both handedness and anchored onto a helical supramolecular host formed from the self assembly of a dicopper(II) complex (1) containing pentadentate Schiff base (L) and p-hydroxycinnamate in 1.2H(2)O, propagate along the crystallographic 2(1)-screw axis and the compound shows two endotherms due to loss of water molecules at 61.5 and 88.5 degrees C in the differential scanning calorimetry giving an overall change of enthalpy value of approximately 36 kJ mol(-1) per water molecule.     

Three-propeller-blade-shaped electride: remarkable alkali-metal-doped effect on the first hyperpolarizability

Significant alkali-metal-doped effects on the structure and the first hyperpolarizability (β ₀) of effective multi-nitrogen complexant tris[(2-imidazolyl)methyl]amine (TIMA) are investigated. Three imidazoles of TIMA like three blades of propeller connect with methyls by the C–C single bonds. Because of the three C–C single-bond cooperative rotations, the TIMA behaves with great flexibility, and it is a high-performance multi-nitrogen complexant for the alkali metal doping. Thus, the new complexes A_m-TIMA (A_m = Li, Na, and K) with electride characteristic have diffuse excess electron than the reported electride-type system due to the strong interaction between the complexant TIMA and alkali metal. For the first hyperpolarizability, three engaging electrides A_m-TIMA with the diffuse excess electrons exhibit considerably large β ₀ values using the MP2 (full) method and the β ₀ values of new electrides are greatly larger (3,464–29,705 times) than that (338 au) of TIMA. Surprisingly, the K-TIMA sets a new record β ₀ value to be 1.00 × 10⁷ au which far exceeds than that (3,694–76,978 au) of the reported electride-type system Li@calix[4]pyrrole (J Am Chem Soc 127:10977–10981, 2005) and Li_n−H−(CF₂−CH₂)₃−H (n = 1, 2) (J Am Chem Soc 129:2967–2970, 2007) and 31,123 au of the organometallic system (J Am Chem Soc 121:4047–4053, 1999) Ru(trans-4,4′-diethylaminostyryl-2,2′-bipyridine)₃²⁺, as well as 1.23 × 10⁶ au of the large donor-CNT systems (Nano Lett 8:2814–2818, 2008). Clearly, the alkali-metal-doped effect on the first hyperpolarizability is very dramatic for the high-performance multi-nitrogen complexant TIMA. Considering simple possibility from molecule to material, the β ₀ values of optimized Li-TIMA-dimer and Li-TIMA-tetramer are investigated by BHandHLYP method. Interestingly, results show that the order of β ₀ value is Li-TIMA-monomer < Li-TIMA-dimer < Li-TIMA-tetramer. So the new three-propeller-blade-shaped electrides can be considered as candidates for high-performance nonlinear optical materials.     

Self-assembly of spherical colloids into helical chains with well-controlled handedness

Physical constraint and capillary force have been combined to provide a generic approach to assemble achiral building blocks such as monodisperse spherical colloids into helical mesostructures. The key component of this process is an array of V-shaped grooves anisotropically etched in the surface of a Si(100) wafer. The structural arrangement among the spherical colloids is determined by the ratio between the width of the V-grooves and the diameter of the colloids. Double-layered structures with a helical morphology will be formed when this ratio falls between 2.70 and 2.85. The exact handedness of these helical structures could be controlled by varying the relative orientation of capillary force with respect to the longitudinal axis of the spirals. The processing of an achiral material into helical mesostructures having well-controlled handedness should allow us to explore new properties that this material otherwise does not exhibit. The self-assembly process may also provide valuable insights to improve our understanding on the mechanism(s) by which pure enantiomers with a particular sense of rotation evolved in nature.     

An EPR determination of the helix pitch and relative handedness of some induced cholesteric mesophases

The pitch of weakly cholesteric mesophases obtained by dissolving a chiral compound in the nematic liquid crystal MBBA, has been determined by an EPR spin probe technique. The measured values are in excellent agreement with those obtained by the Grandjean-Cano microscopic method. Once a sufficiently large number of EPR simulated spectra have been computed, the experimental procedure for the determination of the pitch is shown to be faster and as reliable as other methods. The handedness of the mesophase can also be easily established by observing the spectral variations which follow the addition of a cholesteric of known handedness to a given sample.     

Helical silica nanotubes: Nanofabrication architecture,transfer of helix and chirality to silica nanotubes

A series of neutral gelators and cationic amphiphiles derived from 1,2 diphenylethylenediamine (I) and 1,2-cyclohexanediamine (II) was synthesised. Helical silica nanotubes were prepared utilising these organic gelators through sol-gel polycondensation of tetraethoxy silane, (TEOS-silica source). Right- and left-handed helical nanotubes respectively were obtained from a 1: 1 mass mixture of optically active, (1S,2S)-III-(1S,2S)-V neutral gelator and (1S,2S)-IV-(1S,2S)-VI cationic amphiphile and a 1: 1 mass mixture of optically active, (1R,2R)-III-(1R,2R)-V neutral gelator and (1R,2R)-IV-(1R,2R)-VI cationic amphiphile, indicating that the handedness of the helical nanotubes varied with the change in the neutral gelator precursors used. The nanotubes were characterised by SEM images.     

Well-defined, organic nanoenvironments in water: the hydrophobic effect drives a capsular assembly

The synthesis of a water-soluble, deep-cavity cavitand is reported. A blend of molecular curvature and amphiphilicity, this molecule has a hydrophobic concave surface and a hydrophilic convex surface. As a result, in aqueous solution and in the presence of a guest molecule, the host self-assembles to form a capsular assembly with an interior cavity large enough to entrap steroidal guests.     

Recent advances in solventless organic reactions: towards benign synthesis with remarkable versatility

A paradigm shift away from using solvents in organic synthesis as solventless reactions can lead to improved outcomes, and more benign synthetic procedures, in for example aldol condensation reactions, sequential aldol and Michael addition reactions en route to Kr?hnke type pyridines, reactions leading to 3-carboxycoumarins, benzylidenes, 4-aryl-1,4-dihydropyridines and 2-aryl-1,2,3,4-tetrahydroquinazolines, and oligomerisation reactions for the synthesis of cavitands; kinetic considerations for the reaction of two solids can only be explained if a eutectic melt is formed during the reaction.     

Cobalt-catalyzed asymmetric hydrogenation of ketones: A remarkable additive effect on enantioselectivity

A chiral cobalt pincer complex, when combined with an achiral electron-rich mono-phosphine ligand, catalyzes efficient asymmetric hydrogenation of a wide range of aryl ketones, affording chiral alcohols with high yields and moderate to excellent enantioselectivities (29 examples, up to 93% ee). Notably, the achiral mono-phosphine ligand shows a remarkable effect on the enantioselectivity of the reaction.     

Water superstructures within organic arrays; hydrogen-bonded water sheets, chains and clusters

A strategy for encouraging the formation of extended water arrays is presented, in which molecules that contain a 1,4-dihydroquinoxaline-2,3-dione core are used as supramolecular hosts for the accommodation of guest water molecules and arrays. These molecules were selected as they contain a hydrophilic oxalamide-based "terminus" that allows water molecules to hydrogen-bond to the host organic molecules as well as to each other. The host molecules also contain a hydrophobic "end" based upon an aromatic ring, which serves to encourage the formation of discrete water clusters in preference to three-dimensional networks, as the water molecules cannot form strong hydrogen bonds with this part of the molecule. A systematic study of several hydrated structures of four organic molecules based on 1,4-dihydroquinoxaline-2,3-dione (qd) is discussed. The organic molecules, qd, 6-methyl-1,4-dihydroquinoxaline-2,3-dione (mqd), 6,7-dimethyl-1,4-dihydroquinoxaline-2,3-dione (dmqd) and 1,4-dihydrobenzo[g]quinoxaline-2,3-dione (Phqd), act as supramolecular crystal hosts for the clusters of water, with zero-, one- and two-dimensional arrays of water being observed. The hydrogen bonding in the structures, both within the water clusters and between the clusters and organic molecules, is examined. In particular, the structure of dmqd6 H2O contains a two-dimensional water sheet composed of pentagonal and octagonal units. Phqd3 H2O forms a hydrophilic extended structure encouraging the formation of one-dimensional chains consisting entirely of water. Both qd2 H2O and dmqd2 H2O can be considered to form one-dimensional chains, but only by utilising bridging carbonyl groups of the oxalamide moieties to form the extended array; if only the water is considered, zero-dimensional water tetramers are observed. The remaining hydrated structures, [Na+dmqd-]dmqdH2O, dmqd1/3H2O and mqd1/2H2O, all contain discrete water molecules but do not form extended water structures.     

Palladium-catalyzed heck arylations of allyl alcohols in ionic liquids: remarkable base effect on the selectivity

Pd-catalyzed Heck arylation of allyl alcohols in tetraalkylammonium ionic liquids (ILs) can be made highly selective toward the formation of either aromatic carbonyl compounds or aromatic conjugated alcohols by carefully choosing both the IL and the base.     

Prediction of remarkable ambipolar charge-transport characteristics in organic mixed-stack charge-transfer crystals

We have used density functional theory calculations and mixed quantum/classical dynamics simulations to study the electronic structure and charge-transport properties of three representative mixed-stack charge-transfer crystals, DBTTF-TCNQ, DMQtT-F(4)TCNQ, and STB-F(4)TCNQ. The compounds are characterized by very small effective masses and modest electron-phonon couplings for both holes and electrons. The hole and electron transport characteristics are found to be very similar along the stacking directions; for example, in the DMQtT-F(4)TCNQ crystal, the hole and electron effective masses are as small as 0.20 and 0.26 m(0), respectively. This similarity arises from the fact that the electronic couplings of both hole and electron are controlled by the same superexchange mechanism. Remarkable ambipolar charge-transport properties are predicted for all three crystals. Our calculations thus provide strong indications that mixed-stack donor-acceptor materials represent a class of systems with high potential in organic electronics.     

Studies on the effect of column angle in centrifugal helix counter-current chromatography

The performance of the coiled column of centrifugal counter-current chromatography was investigated by changing the angle between column axis and centrifugal force in the separation of dipeptides or DNP-amino acids each with suitable two-phase solvent systems. In general, retention of the stationary phase (Sf) decreased, and peak resolution (Rs) increased as the column angle was increased. The first series of experiments was performed using a polar two-phase solvent system composed of 1-butanol–acetic acid–water (4:1:5, v/v/v) to separate two dipeptide samples, Trp-Tyr and Val-Tyr, at a flow rate of 1 ml/min at 1000 rpm. When the column angle was changed from 0° to 90°, Rs increased from 1.05 (Sf = 60.1%) to 1.17 (Sf = 38.7%) with the lower phase mobile and from 1.02 (Sf = 67.8%) to 1.14 (Sf = 47.4%) with the upper phase mobile, respectively. The second series of experiments was similarly performed with a more hydrophobic two-phase solvent system composed of hexane–ethyl acetate–methanol–0.1 M hydrochloric acid (1:1:1:1, v/v/v/v) to separate three DNP-amino acids, DNP-glu, DNP-β-ala and DNP-ala, at a flow rate of 1 ml/min at 1000 rpm. When the column angle was changed from 0° to 90°, Rs increased from 1.38 (1st peak/2nd peak) and 1.20 (2nd peak/3rd peak) (Sf = 61.1%) to 1.66 and 1.45 (Sf = 34.4%) with the lower phase mobile and from 1.14 and 0.63 (Sf = 72.2%) to 1.53 and 0.87 (Sf = 51.1%) with the upper phase mobile, respectively. The overall results of our studies indicate that increasing the column angle against the radially acting centrifugal force enhances the mixing of two phases in the column to improve the peak while decreasing the stationary phase retention by interrupting the laminar flow of the mobile phase.     

The effect of water on the rate and direction of the oxidation of organic substances

The effect of the polarity of the medium on the rate and direction of oxidation processes has been studied. It has been shown that the rate of oxidation of methyl ethyl ketone in aqueous solutions diminishes with increase in the water concentration. A considerably greater reduction in the rate of decomposition of the RO ₂ ^. radical is observed than in the rate of the interaction of this radical with methyl ethyl ketone, which results in an increase in the selectivity of the oxidation process. When methyl ethyl ketone is diluted with water in the molar ratio C₄H₈O H₂O=120, the quantity of acetic acid in the reaction products amounts to 98–99% of the methyl ethyl ketone consumed. The suggestion is made that the high selectivity of the oxidation of methyl ethyl ketone in aqueous solutions is due to the effect of the dielectric constant of the medium on the ratio between the two parallel reactions of the peroxide radical RO ₂ ^. .     

Helical stacking tuned by alkoxy side chains in pi-conjugated triphenylbenzene discotic derivatives

We report on the synthesis and self-assembly of a new series of discotic molecules containing triphenylbenzene as the core and alkoxy side chain with varying length. It was found that compounds 3 a-c, 4 b and 5 b could form stable gels in several apolar solvents. Transmission electron microscopy (TEM) images revealed that their morphologies were very different for the different alkoxy-substituted organogels. In toluene or hexane, 3 b and 3 c resulted in both left- and right-handed helical fibers, whereas 3 a resulted in straight rigid fibers; 4 b and 5 b resulted in most straight fibers with a few twisted fibers. The results from FT-IR and UV/Vis absorption spectroscopy indicated that the hydrogen bonding and pi-pi interactions were the main driving forces for the formation of the self-assembled gels. Further detailed analysis of their aggregation modes were conducted by UV-visible absorption spectra and X-ray diffraction (XRD) measurements. Based on these findings, the influence of these peripheral alkoxy substituents on the gel formation and the aggregation mode were discussed. The special enhanced fluorescent emissions, which resulted from aggregation, were also found in the gel phase.     

Side chain effect on the double helix formation of ethynylhelicene oligomers

Three series of ethynylhelicene oligomers with different side chains were synthesized: (P)-bD-n (n = 2-6) with branched alkyloxycarbonyl side chains; (P)-S-n (n = 2-7) with decylsulfanyl side chains; and (P)-DF-n (n = 4, 6, 8, 10) with alternating decyloxycarbonyl and perfluorooctyl side chains. The double helix formation of these side chain derivatives was compared to that of (P)-D-n with decyloxycarbonyl side chains. CD, UV-vis, and vapor pressure osmometry (VPO) studies showed that (P)-bD-n formed double helices as well as (P)-D-n. CD studies in trifluoromethylbenzene at different temperatures and concentrations indicated that the stability of the aggregate of (P)-bD-6 was similar to that of (P)-D-6. Bulkiness of side chains had little effect on aggregation, which indicated that π-π interactions of the aromatic moiety were essential for double helix formation. (P)-S-n were random coils in all solvents examined except in trifluoromethylbenzene. Whereas (P)-D-7 formed a double helix at 1 × 10(-3) M in toluene, (P)-S-7 was a random coil. This result indicated that the double helix forming ability of (P)-S-n was substantially lower than that of (P)-D-n. Based on the previous observation that (P)-F-n formed a more stable double helix than (P)-D-n, the order of stability may be summarized as follows: (P)-F-n > (P)-D-n and (P)-bD-n >(P)-S-n. The lower stability of (P)-S-n compared to that of (P)-F-n was ascribed to the softness and/or the electron-rich nature at the m-phenylene moiety. (P)-DF-n did not form a stable double helix. It was speculated that a regular alternating arrangement of soft/hard or electron-rich/deficient moieties is important for stable double helix formation. Side chains of ethynylhelicene oligomers can play significant roles in determining the stability of double helices.     

The effect of organic sorbates on water associated with environmentally important sorbents: estimating and the LFER analysis

The effect of organic sorbates on the water associated with naturally occurring sorbents is of significant interest since it probes the hydration of a sorbate-specific microenvironment and its role in a compound partitioning between various environmental compartments. This effect was described in a thermodynamically strict way by converting the sorption isotherms of organic vapors on variously hydrated sorbents into the derivatives relating the change in the amount of water associated with a sorbent to the change in the amount of an organic sorbate. Further, these derivatives were analyzed by means of the Linear Free Energy Relationship (LFER). The analysis included the sorption data for various organic vapors on such environmentally important sorbents as quartz, metal oxides, calcite, clay minerals and humic acid. From the LFER analysis it followed that (i) organic sorbate polarizability contributions from n- and π-electrons resulted in driving water into the sorbent phase; (ii) the increasing volume of the organic compounds involved expelling water molecules; (iii) the increasing hydrogen-bond acidity and basicity of organic sorbates resulted in expelling water from inorganic surfaces but in enhancing hydration of the humic phase. In contrast to inorganic surfaces, when sorbed on strongly hydrated humic acid, the majority of organic sorbates containing oxygen, nitrogen or sulfur atoms drive water into the sorbent phase. Several molecules of water may need to be cosorbed by a humic sorbent for each sorbed molecule of an organic compound thus supporting the possibility of the concomitant participation of a number of water molecules in organic sorbate–humic matter interactions.     

Photochemical aromatic hydroxylation by aromatic amine N-oxides: remarkable solvent effect on NIH-shift

Photooxygenations of 4-²H-anisole ($\text{3}$) and o-xylene ($\text{5}$) by 3-methylpyridazine 2-oxide ($\text{1}$) or pyridine 1-oxide ($\text{2}$) were studied in a variety of solvents at varying irradiation temperatures. Remarkable solvent effect on NIH-shift coupled with their hydroxylation processes was observed.     

A remarkable shape-catalytic effect of confinement on the rotational isomerization of small hydrocarbons

As part of an effort to understand the effect of confinement by porous carbons on chemical reactions, we have carried out density functional theory calculations on the rotational isomerization of three four-membered hydrocarbons: n-butane, 1-butene, and 1,3-butadiene. Our results show that the interactions with the carbon walls cause a dramatic change on the potential energy surface for pore sizes comparable to the molecular dimensions. The porous material enhances or hinders reactions depending on how similar is the shape of the transition state to the shape of the confining material. The structure of the stable states and their equilibrium distributions are also drastically modified by confinement. Our results are consistent with a doubly exponential behavior of the reaction rates as a function of pore size, illustrating how the shape of a catalytic support can dramatically change the efficiency of a catalyst.