Synthesis and thermoreversible gelation properties of main-chain poly(pyridine-2,6-dicarboxamide-triazole)s.

A series of main-chain poly(amide-triazole)s were prepared by copper(I)-catalyzed alkyne-azide AABB-type copolymerizatons between five structurally similar diacetylenes 1-5 with the same diazide 6. The acetylene units in monomers 1-5 possessed different degrees of conformational flexibility due to the different number of intramolecular hydrogen bonds built inside the monomer architecture. Our study showed that the conformational freedom of the monomer had a profound effect on the polymerization efficiency and the thermoreversible gelation properties of the resulting copolymers. Among all five diacetylene monomers, only the one, that is, 1-Py(NH)(2) which possesses the pyridine-2,6-dicarboxamide unit with two built-in intramolecular H bonds could produce the corresponding poly(amide-triazole) Poly-(PyNH)(2) with a significantly higher degree of polymerization (DP) than other monomers with a lesser number of intramolecular H bonds. In addition, it was found that only this polymer exhibited excellent thermoreversible gelation ability in aromatic solvents. A self-assembling model of the organogelating polymer Poly-(PyNH)(2) was proposed based on FTIR spectroscopy, XRD, and SEM analyses, in which H bonding, π-π aromatic stacking, hydrophobic interactions, and the structural rigidity of the polymer backbone were identified as the main driving forces for the polymer self-assembly process.

From nongelating to gelating: synthesis and structural self-assembling property relationships of a homologous series of oligo(amide-triazole)s.

A homologous series of oligo(amide-triazole)s (OAT) [OAT-CO2H-2 n and OAT-COPrg-(2 n+1)] with an increasing number of primary amide (CONH) and triazole hydrogen-bonding functionalities was prepared by an iterative synthetic procedure. It was found that their self-assembly and thermoreversible gelation strength had a strong correlation to the number of hydrogen-bonding moieties in the oligomers. There also existed a threshold value of the number of CONH units, above which all the oligomers became organogelators. Hence, oligomers with ≤4 CONH units are devoid of intermolecular hydrogen bonding and also non-organogelating, whereas those that contain >4 CONH units show intermolecular association and organogelating properties. For the organogelators, the T(gel) value increases monotonically with increasing number of CONH units. On the basis of FTIR measurements, both the CONH and triazole C-H groups were involved in the hydrogen-bonding process. A mixed xerogel that consisted of a 1:1 weight ratio of two oligomers of different lengths (OAT-CO2H-6 and OAT-CO2H-12) was found to show microphase segregation according to differential scanning calorimetry, thus indicating that oligomers that bear a different number of hydrogen-bonding units exhibited self-sorting to maximize the extent of intermolecular hydrogen bonding in the xerogel state.

Laser absorption spectroscopy of the d3Π(g) ← c3Σ(u)+ transition of C2.

High-resolution laser absorption spectroscopy using concentration modulation has been applied to record the near-infrared spectrum of C2 in an AC hollow-cathode discharge of acetylene/helium mixtures. The (2,1) and (1,0) vibronic bands of the d3Π(g)­ c3Σ(u)+ system have been observed in the spectral region between 12,010 and 12,540 cm(­1). While the analysis of the (1,0) band was straightforward, the (2,1) band was found to be perturbed. Using the effective Hamiltonians for 3Π and 3Σ+ states, molecular constants for the vibrational levels of the c3Σ(u)+ state were retrieved in least-squares fits of the observed spectral lines. The experimental conditions, detailed analysis of the perturbations, and the determined molecular constants are reported.

Click-dendronized poly(amide-triazole)s--effect of dendron size and polymer backbone symmetry on self-assembling and gelation properties.

Nine dendronized poly(amide-triazole)s 2-Gm Gn (m=1-3, n=1-3), were prepared by the 1:1 copolymerization between AA-type dendritic diazides 4-Gm (m=1-3) and BB-type dendritic diacetylenes 5-Gn (n=1-3) under the copper(I)-mediated click coupling conditions. The degree of polymerization value of the polymers was found to range from 15-50, and decreased with increasing size of the dendron, suggesting steric hindrance had a retardation role on the copolymerization efficiency. Based on FT-IR and (1)H NMR studies, it was found that significantly strong, interchain hydrogen bonding between the amide units was present in the solution state after copolymerization, whereas the monomers 4-Gm and 5-Gn were devoid of any intermolecular hydrogen-bonding interaction. Hence a positive allosteric hydrogen-bonding effect was observed after polymerization, and could be rationalized by the zip effect. The strength of the interchain association in polymers 2-Gm Gn was found to decrease with increasing size of the dendron (i.e., 2-G1 G1>2-G1 G2>2-G2 G1≈2-G2 G2>2-G1 G3≈2-G3 G1>2-G2 G3≈2-G3 G2>2-G3 G3). Among the nine polymers, only 2-G1 G2 and 2-G2 G1 were good organogelators for aromatic solvents, while the 2-G2 G2 polymer, bearing the closest structural resemblance to the previously reported organogelator 1-G2 prepared from the polymerization of AB-type monomers, was devoid of gelating power. Careful analysis of structures of the present polymer series 2-Gm Gn and the previously reported series 1-Gn suggested that the polymer backbone symmetry played a subtle role in controlling their self-assembling and gelating properties.

N(2) band oscillator strengths at near-threshold energies.

Band oscillator strengths for 58 bands in the near-threshold region of N(2), i.e., from 116 200 to 125 400 cm(-1), are derived from measured band-integrated optical depths. The complexity of the absorption spectrum demands that the measurements be carried out on rotationally cold supersonic jet expansions. The column density N in the absorbing path of the jet cannot be measured directly. Instead, the room temperature f values of selected calibration bands are used to convert the band-integrated optical depths of the jet-cooled calibration bands to preliminary column densities [N], which, plotted as a function of jet reservoir pressure p, scatter around a straight line passing through the origin of the graph. From the slope of the line, first estimates of the effective column density N can be derived for any value of p. Second estimates are obtained by repeating the same procedure using ab initio calculated f values based on the work of Spelsberg and Meyer [J. Chem. Phys. 115, 6438 (2001)]. Depending on the jet configuration, the two estimates differ by 3%-15%; their average is accepted as the best approximation to N. The derived band oscillator strengths are compatible with ab initio results of Spelsberg and Meyer and reproduce the observations reasonably well, even where two or more transitions combine in the formation of complex band structures. They also clarify the analysis of the absorption spectrum in the region of the 7p(0) complex [Jungen, Huber, Jungen, and Stark, J. Chem. Phys. 118, 4517 (2003)] and lead to a plausible interpretation of the spectrum in the 124 680-124 880 cm(-1) range. As a result, the lowest three vibronic levels of both the 3(')d(')sigma and the 4(')s(')sigma core excited states have now been identified.

Transition from low molecular weight non-gelating oligo(amide-triazole)s to a restorable, halide-responsive poly(amide-triazole) supramolecular gel.

A self-assembled poly(amide-triazole) physical gel (1) was found to show responsive behaviour towards halide anions, while the corresponding monomeric (2) and dimeric homologues (3) were non-gelating. In the presence of halide anions, polymer gel 1 collapsed to become a solution, but could be restored back to the gel state after addition of a AgNO3 salt.

Head-to-tail dimerization and organogelating properties of click peptidomimetics.

Click triazole-based oligopeptides 1-3 were found to self-dimerize (K(dim) ≈ 10-680 M(-1)) in a head-to-tail fashion based on (1)H variable concentration, 2D, and H/D exchange NMR, VPO, CD, FT-IR studies and Gaussian 03 simulations. The dimerization constant K(dim) was shown to increase with increasing number of the amino acid units. Within the same oligomeric series, the K(dim) value is strongly affected by the size of the C-terminal end group. The tripeptides 2 are also excellent organogelators of aromatic solvents.