Near infrared spectral investigations of hydration of 18-crown-6 in HDO-D2O solutions at different temperatures

Near infrared spectra of solution of 6.4 M HDO in D(2)O have been obtained at 15, 25, 30, and 35 degrees C. It was observed that the bands of HDO in D(2)O occur at 1416, 1525, 1556, and 1666 nm, which are in good agreement with the similar data reported earlier by Worley and Klotz. The calculations of enthalpy change for hydrogen bond formation (DeltaH degrees ) yielded the value of -2.5+/-0.4 kcal mol(-1), which is in excellent agreement with the value reported by Walrafen. Similar spectra were recorded for 1 and 2 m 18-crown-6 (18C6) dissolved in the solution of HDO in D(2)O at different temperatures. The band positions remain unchanged, however, the variation of intensity as a function of concentration of 18C6 and temperature clearly indicate that 18C6 acts as a structure making solute. The structural temperature and DeltaH degrees values have been obtained for the 18C6 solutions. These results are explained on the basis of the stabilization of 18C6 in the D(3d) conformation through hydrogen bonding of HDO molecules [doubly hydrogen bonded, i.e. bridging, and singly hydrogen bonded] to the oxygen atoms of 18C6 molecules. Slightly different DeltaH degrees values obtained can be attributed to clathrate like structure at 1 m 18C6 concentration while at 2 m 18C6 concentration it is postulated that the hydrophobic interactions are contributing additionally.     

Engineered protein cages for nanomaterial synthesis

Self-assembled particles of genetically engineered human L subunit ferritin expressing a silver-binding peptide were used as nanocontainers for the synthesis of silver nanoparticles. The inner cavity of the self-assembled protein cage displays a dodecapeptide that is capable of reducing silver ions to metallic silver. This chimeric protein cage when incubated in the presence of silver nitrate exhibits the growth of a silver nanocrystal within its cavity. Our studies indicate that it is possible to design chimeric cages, using specific peptide templates, for the growth of other inorganic nanoparticles.     

Capturing a metastable chiral polymorph of an achiral molecule--hexa-O-benzoyl-myo-inositol

myo-Inositol hexabenzoate having meso configuration produces chiral polymorph (form I) when crystallized rapidly but yields achiral polymorph (form II) when allowed to crystallize slowly; in the mother liquor form I slowly but completely disappears to give form II.     

Dip-pen nanolithography in tapping mode

Dip-pen nanolithography (DPN) is becoming a popular nano-patterning technique for depositing materials onto a substrate using the probe of an atomic force microscope (AFM). Here, we demonstrate the deposition of a short synthetic peptide by DPN using the Tapping Mode of AFM rather than the commonly used contact mode. DPN in Tapping Mode requires drive amplitude modifications for deposition, yet allows for gentle imaging of the deposited material and enables deposition on soft surfaces.     

Alkylation of catechol with methanol to guaiacol over sulphate-modified zirconia solid acid catalysts

A series of sulphate-promoted ZrO₂ solid acid catalysts with different contents of SO₄ ²⁻ were calcined at 450°C in air for 4 h and tested for the liquid-phase alkylation of catechol to guaiacol in a fixed-bed down-flow reactor. The 5 wt.% SO₄ ²⁻ on ZrO₂ showed the best conversion (82%) and selectivity for guaiacol (84%) at 200°C and 1 bar pressure. A smooth correlation was observed between the catalytical activity and surface acidity of sulphated zirconia. Based on our results, a surface mechanism is proposed.     

Electron and positron impact excitation of hydrogen from the initially excited 22S state to 32S and 32P states

The total and differential cross sections for the electron and positron impact excitation of hydrogen from its initially excited metastable 2²S state to 3²S and 3²P states are reported. A distorted-wave approximation theory is used for the calculation. The angular correlation parameters, Ly and alignment angle are also reported for 2²S-3²P excitation. For comparison, similar first Born results are also obtained. Interesting features are noted on comparing our distorted wave results with the first Born results as well as with the other available results forn ²S andn ²P (n=2,3) excitations from the ground 1²S state of hydrogen.     

Laser induced breakdown of Ar,N2 and O2 gases using 1.064, 0.532, 0.355 and 0.266 μm radiation

An experimental investigation of laser-induced breakdown using Nd:YAG laser harmonics for argon, nitrogen and oxygen gases is reported. Pressure dependence as well as wavelength dependence of the breakdown threshold irradianceI _th is investigated. The experimental observations for 1.064 and 0.532 m laser wavelengths are in agreement with theoretical calculations which include the effects of multiphoton ionization and cascade ionization.     

Thermal rearrangements of spiro[2.4]hepta-1,4,6-trienes

Thermolysis of spiro[2.4]hepta-1,4,6-triene (1a) at 50 degrees C yielded bicyclo[3.2.0]hepta-1,3,6-triene (5), which dimerized in two different fashions to form cyclobutanes. The 1,2-dimethyl and 1-propyl derivatives of 1a also rearranged at 50 degrees C, but at a faster rate, each yielding a pair of cyclobutane dimers. The structures of these symmetrical dimers were investigated by 1D and 2D NMR and NOE difference spectroscopy. Ab initio calculations indicated that the two strained olefins 1a and 5 had comparable energies about 50 kcal/mol lower than norborna-1(7),2,5-triene, which was thus excluded as a reaction intermediate.     

Self-assembly with degenerate prototropy

This work describes a rational approach for addressing the prototropy-related problems in heterocycle-based self-assembling systems by the use of degenerate prototropy. As a proof of principle, the utility of degenerate prototropy is demonstrated herein by developing heterocycle-based AADD-type self-assembling modules that exist as "single set of protameric pair (duplex)" in both solution and solid states. These self-assembling modules are quickly accessible in good yield by reacting 2-amino-5,5-disubstituted-1H-pyrimidine-4,6-diones, available in one step by the condensation of alpha,alpha-dialkyl malonates and free guanidine, with isocyanates. Evidence from NMR spectroscopy, ESI mass spectrometry, and single-crystal X-ray diffraction studies confirmed the formation of molecular duplexes. The effect of electronic repulsion in duplex formation is also investigated. Their ready synthetic accessibility, remarkably high propensity to crystal formation, and the novel property of degenerate prototropy would make these novel self-assembling molecules promising candidates for many proposed applications.     

A novel three-component reaction for the diastereoselective synthesis of 2H-pyrimido[2,1-a]isoquinolines via 1,4-dipolar cycloaddition

[reaction: see text] The 1,4-dipole derived from isoquinoline and DMAD has been shown to react readily with N-tosylimines resulting in the diastereoselective synthesis of 2H-pyrimido[2,1-a]isoquinoline derivatives.