The crystal and molecular structure of benzyloxycarbonyl-a-amino-isobutyryl-L-prolyl-methylamide. The observation of an X2-Pro3 Type III b-turn

The crystal and molecular structure of N-benzyloxycarbonyl-a-aminoisobutyryl-L-prolyl methylamide, the amino terminal dipeptide fragment of alamethicin, has been determined using direct methods. The compound crystallizes in the orthorhombic system with the space group P212-21. Cell dimensions are a = 7.705 A, b = 11.365 A, and c = 21.904 A. The structure has been refined using conventional procedures to a final R factor of 0.054. The molecular structure possesses a 4 - 1 intramolecular N-H--0 hydrogen bond formed between the CO group of the urethane moiety and the NH group of the methylamide function. The peptide backbone adopts the type 111 P-turn conformation, with 42 = -51.0°, +* = -39.7",&j = -65.0', $3 = -25.4'. An unusual feature is the occurrence of the proline residue at position 3 of the P-turn. The observed structure supports the view that Aib residues initiate the formation of type 111 @-turn conformations. The pyrrolidine ring is puckered in Cy-exo fashion.

Indian Ocean response to anomalous conditions in 2006

[1] The equatorial Indian Ocean (EIO) exhibited anomalous conditions characteristic of an Indian Ocean dipole (IOD) during 2006. The eastern EIO had cold sea surface temperature anomalies (SSTA), lower sea level, shallow thermocline and higher chlorophyll than normal. The anomalies in the east, restricted to the south of the equator, were highest off Sumatra. The western pole of the IOD was marked by warm SSTA and deeper thermocline with maxima on either side of the equator. An ocean general circulation model of the Indian Ocean forced by QuikSCAT winds reproduces the IOD of 2006 remarkably well. The switch over to cooling in the east and warming in the west happened during May and July respectively. In the east, airsea heat flux initiated cold SSTA in the model which were sustained later by oceanic processes. In the west, surface heat fluxes and horizontal advection caused warm SSTA and contribution by the latter decreased after August. Citation: Vinayachandran, P. N., J. Kurian, and C. P. Neema (2007), Indian Ocean response to anomalous conditions in 2006, Geophys. Res. Lett., 34, L15602, doi:10.1029/2007GL030194.

Indian Ocean response to anomalous conditions in 2006

The equatorial Indian Ocean (EIO) exhibited anomalous conditions characteristic of an Indian Ocean dipole (IOD) during 2006. The eastern EIO had cold sea surface temperature anomalies (SSTA), lower sea level, shallow thermocline and higher chlorophyll than normal. The anomalies in the east, restricted to the south of the equator, were highest off Sumatra. The western pole of the IOD was marked by warm SSTA and deeper thermocline with maxima on either side of the equator. An ocean general circulation model of the Indian Ocean forced by QuikSCAT winds reproduces the IOD of 2006 remarkably well. The switch over to cooling in the east and warming in the west happened during May and July respectively. In the east, air-sea heat flux initiated cold SSTA in the model which were sustained later by oceanic processes. In the west, surface heat fluxes and horizontal advection caused warm SSTA and contribution by the latter decreased after August.

Mechanisms of formation of the Arabian Sea mini warm pool in a high-resolution Ocean General Circulation Model

An Ocean General Circulation Model of the Indian Ocean with high horizontal (0.25 degrees x 0.25 degrees) and vertical (40 levels) resolutions is used to study the dynamics and thermodynamics of the Arabian Sea mini warm pool (ASMWP), the warmest region in the northern Indian Ocean during January-April. The model simulates the seasonal cycle of temperature, salinity and currents as well as the winter time temperature inversions in the southeastern Arabian Sea (SEAS) quite realistically with climatological forcing. An experiment which maintained uniform salinity of 35 psu over the entire model domain reproduces the ASMWP similar to the control run with realistic salinity and this is contrary to the existing theories that stratification caused by the intrusion of low-salinity water from the Bay of Bengal into the SEAS is crucial for the formation of ASMWP. The contribution from temperature inversions to the warming of the SEAS is found to be negligible. Experiments with modified atmospheric forcing over the SEAS show that the low latent heat loss over the SEAS compared to the surroundings, resulting from the low winds due to the orographic effect of Western Ghats, plays an important role in setting up the sea surface temperature (SST) distribution over the SEAS during November March. During March-May, the SEAS responds quickly to the air-sea fluxes and the peak SST during April-May is independent of the SST evolution during previous months. The SEAS behaves as a low wind, heat-dominated regime during November-May and, therefore, the formation and maintenance of the ASMWP is not dependent on the near surface stratification.

On the roles of the northeast cold surge, the Borneo vortex, the Madden-Julian Oscillation, and the Indian Ocean Dipole during the extreme 2006/2007 flood in southern Peninsular Malaysia

The mid-December 2006 to late January 2007 flood in southern Peninsular Malaysia was the worst flood in a century and was caused by three extreme precipitation episodes. These extreme precipitation events were mainly associated with strong northeasterly winds over the South China Sea. In all cases, the northeasterlies penetrated anomalously far south and followed almost a straight trajectory. The elevated terrain over Sumatra and southern Peninsular Malaysia caused low-level convergence. The strong easterly winds near Java associated with the Rossby wave-type response to Madden-Julian Oscillation (MJO) inhibited the counter-clockwise turning of the northeasterlies and the formation of the Borneo vortex, which, in turn, enhanced the low-level convergence over the region. The abrupt termination of the Indian Ocean Dipole (IOD) in December 2006 played a secondary role as warmer equatorial Indian Ocean helped in the MJO formation.

Observation of a thermally reversing window in bulk Ge15Te85-xInx glasses

Alternating differential scanning calorimetry measurements have been undertaken on the Ge15Te85-xInx (1 <= x <= 11) series of glasses. It is found that there is a marginal decrease in the glass transition temperature (T-g) in the composition range 1 <= x <= 3. Above x = 3, a monotonic increase is seen in T-g which indicates a continuous build-up in network connectivity and absence of any nanophase separation. The non-reversing heat flow (Delta H-NR) has been found to exhibit a broad trough between the compositions x = 3 and 7, which clearly indicates the presence of a thermally reversing window in Ge15Te85-xInx glasses in the composition range 3 <= x <= 7.

Observation of three-photon absorption and saturation of two-photon absorption in amorphous nanolayered Se/As2S3 thin film structures

We have studied the nonlinear optical properties of nanolayered Se/As2S3 film with a modulation period of 10 nm and a total thickness of 1.15 mu m at two [1064 nm (8 ns) and 800 nm (20 ps)] wavelengths using the standard Z-scan technique. Three-photon absorption was observed at off-resonant excitation and saturation of two-photon absorption at quasiresonant excitation. The observation of the saturation of two-photon absorption is because the pulse duration is shorter than the thermalization time of the photocreated carriers in their bands and three-photon absorption is due to high excitation irradiance. (c) 2007 American Institute of Physics.

Simultaneous observation of positive and negative nuclear Overhauser effects in oligopeptides due to segmental motio

Nuclear Overhauser effect (NOE) studies of the symmetrical cystine peptides (Formula: see text) (n = 1-3) in dimethylsulfoxide, have resulted in the simultaneous observation of both positive and negative NOEs. Positive NOEs are observed on the Trp C2H and C4H protons of the indole ring upon irradiation of Trp C alpha H and C beta H2 resonances in the peptides where n = 1 and 2. Negative NOEs are observed between backbone NH and C alpha H protons. The magnitudes of the observed NOEs are sensitive to changes in molecular size and solvent viscosity. The results demonstrate that NOEs may be a useful probe of sidechain segmental motion in oligopeptides.

Unraveling the packing pattern leading to gelation using SS NMR and X-ray diffraction: direct observation of the evolution of self-assembled fibers

A detailed understanding of the mode of packing patterns that leads to the gelation of low molecular mass gelators derived from bile acid esters was carried out using solid state NMR along with complementary techniques such as powder X-ray diffraction (PXRD), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and polarizing optical microscopy (POM). Solid state C-13{H-1} cross polarization (CP) magic angle spinning (MAS) NMR of the low molecularmass gel in its native state was recorded for the first time. A close resemblance in the packing patterns of the gel, xerogel and bulk solid states was revealed upon comparing their C-13{H-1} CPMAS NMR spectral pattern. A doublet resonance pattern of C-13 signals in C-13{H-1}CPMAS NMR spectra were observed for the gelator molecules, whereas the non-gelators showed simple singlet resonance or resulted inthe formation of inclusion complexes/solvates. PXRD patterns revealed a close isomorphous nature of the gelators indicating the similarity in the mode of the packing pattern in their solid state. Direct imaging of the evolution of nanofibers (sol-gel transition) was carried out using POM, which proved the presence of self-assembled fibrillar networks (SAFINs) in the gel. Finally powder X-ray structure determination revealed the presence of two non-equivalent molecules in an asymmetric unit which is responsible for the doublet resonance pattern in the solid state NMR spectra.

Observation of a chiral smectic phase in azobenzene-linked bolaamphiphiles containing free sugars

Amphiphilic sugars exhibit both lyotropic and thermotropic liquid-crystalline behavior. Interestingly, in spite of the abundance of chiral centers in amphiphilic sugars, their liquid-crystalline phases do not exhibit macroscopic chirality. Herein, we report on the first observation of macroscopic chirality in sugar-based bolaamphiphiles containing free hydroxyl groups. The manifestation of the chiral smectic C* phase in these bolaamphiphiles has been observed to be critically dependent on the presence of the azobenzene moiety and the suitable length of the methylene spacer. These results imply that by suitable selection of linker groups, mesogenic bolaamphiphiles possessing macroscopic chirality can be designed using a variety of naturally available sugar derivatives.

Stereochemical Analysis of Higher α,α-Dialkylglycine Containing Peptides. Characterization of Local Helical Conformations at Dipropylglycine Residues and Observation of a Novel Hydrated Multiple β-Turn Structure in Crystals of a Glycine Rich Peptide

The peptide Boc-Gly-Dpg-Gly-Gly-Dpg-Gly-NHMe (1) has been synthesized to examine the conformational preferences of Dpg residues in the context of a poor helix promoting sequence. Single crystals of 1 were obtained in the space group P21/c with a = 13.716(2) Å, b = 12.960(2) Å, c = 22.266(4) Å, and β = 98.05(1)°; R = 6.3% for 3660 data with |Fo| > 4σ. The molecular conformation in crystals revealed that the Gly(1)-Dpg(2) segment adopts φ, ψ values distorted from those expected for an ideal type II‘ β-turn (φGly(1) = +72.0°, ψGly(1) = −166.0°; φDpg(2) = −54.0°, ψDpg(2) = −46.0°) with an inserted water molecule between Boc-CO and Gly(3)NH. The Gly(3)-Gly(4) segment adopts φ, ψ values which lie broadly in the right handed helical region (φGly(3) = −78.0°, ψGly(3) = −9.0°; φGly(4) = −80.0°, ψGly(4) = −18.0°). There is a chiral reversal at Dpg(5) which takes up φ, ψ values in the left handed helical region. The Dpg(5)-Gly(6) segment closely resembles an ideal type I‘ β-turn (φDpg(5) = +56.0°, ψDpg(5) = +32.0°; φGly(6) = +85.0°, ψGly(6) = −3.0°). Molecules of both chiral senses are found in the centrosymmetric crystal. The C-terminus forms a hydrated Schellman motif, with water insertion into the potential 6 → 1 hydrogen bond between Gly(1)CO and Gly(6)NH. NMR studies in CDCl3 suggest substantial retention of the multiple turn conformation observed in crystals. In solution the observed NOEs support local helical conformation at the two Dpg residues.

Observation of exclusive charmonium production and gamma+gamma to mu+mu- in p+pbar collisions at sqrt{s} = 1.96 TeV

We have observed the reactions p+pbar --> p+X+pbar, with X being a centrally produced J/psi, psi(2S) or chi_c0, and gamma+gamma --> mu+mu-, in proton- antiproton collisions at sqrt{s} = 1.96 TeV using the Run II Collider Detector at Fermilab. The event signature requires two oppositely charged muons, each with pseudorapidity |eta| mu+mu-. Events with a J/psi and an associated photon candidate are consistent with exclusive chi_c0 production through double pomeron exchange. The exclusive vector meson production is as expected for elastic photo- production, gamma+p --> J/psi(psi(2S)) + p, which is observed here for the first time in hadron-hadron collisions. The cross sections ds/dy(y=0) for p + pbar --> p + X + pbar with X = J/psi, psi(2S) orchi_c0 are 3.92+/-0.62 nb, 0.53+/-0.14 nb, and 75+/-14 nb respectively. The cross section for the continuum, with |eta(mu+/-)|