Intermolecular Clamping by Hydrogen Bonds: 2-Pyridone center dot NH3

A combined spectroscopic and ab initio theoretical study of the doubly hydrogen-bonded complex of 2-pyridone (2PY) with NH3 has been performed. The S-1 <- S-0 spectrum extends up to approximate to 1200 cm(-1) above the 0(0)(0) band, close to twice the range observed for 2PY. The S-1 state nonradiative decay for vibrations above approximate to 300 cm(-1) in the NH3 complex is dramatically slowed down relative to bare 2PY. Also, the Delta v=2,4,... overtone bands of the v(1)' and v(2)' out-of-plane vibrations that dominate the low-energy spectral region of 2PY are much weaker or missing for 2PY center dot NH3, which implies that the bridging (2PY)NH center dot center dot center dot NH3 and H2NH center dot center dot center dot O=C H-bonds clamp the 2PY at a planar geometry in the S-1 state. The mass-resolved UV vibronic spectra of jet-cooled 2PY center dot NH3 and its H/D mixed isotopomers are measured using two-color resonant two-photon ionization spectroscopy. The S-0 and S-1 equilibrium structures and normal-mode frequencies are calculated by density functional (B3LYP) and correlated ab initio methods (MP2 and approximate second-order coupled-cluster, CC2). The S-1 <- S-0 vibronic assignments are based on configuration interaction singles (CIS) and CC2 calculations. A doubly H-bonded bridged structure of C-S symmetry is predicted, in agreement with that of Held and Pratt [J. Am. Chem. Soc. 1993, 115, 9718]. While the B3LYP and MP2 calculated rotational constants are in very good agreement with experiment, the calculated H2NH center dot center dot center dot O=C H-bond distance is approximate to 0.7 angstrom shorter than that derived by Held and Pratt. On the other hand, this underlines their observation that ammonia can act as a strong H-bond donor when built into an H-bonded bridge. The CC2 calculations predict the H2NH center dot center dot center dot O distance to increase by 0.2 angstrom upon S-1 <- S-0 electronic excitation, while the (2PY)NH center dot center dot center dot NH3 H-bond remains nearly unchanged. Thus, the expansion of the doubly H-bonded bridge in the excited state is asymmetric and almost wholly due to the weakening of the interaction of ammonia with the keto acceptor group.

Victim Support in a Changing Welfare State

This article discusses how new kinds of individual needs develop parallel to the changes in the welfare state. From a study of Victim Service in Sweden it is shown how this organisation has grown parallel to the changes in the welfare state. In the empirical material it is also shown that the need of support often comes from secondary victimisation. Those who are helped by Victim Support are often people with loose bonds to society and people of low class. As victims they can get help from Victim Support, but the need derives from lacking service in the welfare state. NGOs has replaced organisations in the public sector at the same time as the neo-liberal conception of crime, threats and risk has replaced the social democratic ideas of social security.

Efficient folding of proteins with multiple disulfide bonds in the Escherichia coli cytoplasm

Under physiological conditions, the Escherichia coli cytoplasm is maintained in a reduced state that strongly disfavors the formation of stable disulfide bonds in proteins. However, mutants in which the reduction of both thioredoxins and glutathione is impaired (trxB gor mutants) accumulate oxidized, enzymatically active alkaline phosphatase in the cytoplasm. These mutants grow very poorly in the absence of an exogenous reductant and accumulate extragenic suppressors at a high frequency. One such suppressor strain, FA113, grows almost as rapidly as the wild type in the absence of reductant, exhibits slightly faster kinetics of disulfide bond formation, and has fully induced activity of the transcriptional activator, OxyR. FA113 gave substantially higher yields of properly oxidized proteins compared with wild-type or trxB mutant strains. For polypeptides with very complex patterns of disulfide bonds, such as vtPA and the full-length tPA, the amount of active protein was further enhanced up to 15-fold by co-expression of TrxA (thioredoxin 1) mutants with different redox potentials, or 20-fold by the protein disulfide isomerase, DsbC. Remarkably, higher yields of oxidized, biologically active proteins were obtained by expression in the cytoplasm of E. coli FA113 compared with what could be achieved via secretion into the periplasm of a wild-type strain, even under optimized conditions. These results demonstrate that the cytoplasm can be rendered sufficiently oxidizing to allow efficient formation of native disulfide bonds without compromising cell viability.

Forced unfolding modulated by disulfide bonds in the Ig domains of a cell adhesion molecule

Cell adhesion molecules (CAMs) mediate cell attachment and stress transfer through extracellular domains. Here we forcibly unfold the Ig domains of a prototypical Ig superfamily CAM that contains intradomain disulfide bonds. The Ig domains of all such CAMs have conformations homologous to cadherin extracellular domains, titin Ig-type domains, and fibronectin type-III (FNIII) domains. Atomic force microscopy has been used to extend the five Ig domains of Mel-CAM (melanoma CAM)—a protein that is overexpressed in metastatic melanomas—under conditions where the disulfide bonds were either left intact or disrupted through reduction. Under physiological conditions where intradomain disulfide bonds are intact, partial unfolding was observed at forces far smaller than those reported previously for either titin's Ig-type domains or tenascin's FNIII domains. This partial unfolding under low force may be an important mechanism for imparting elasticity to cell–cell contacts, as well as a regulatory mechanism for adhesive interactions. Under reducing conditions, Mel-CAM's Ig domains were found to fully unfold through a partially folded state and at slightly higher forces. The results suggest that, in divergent evolution of all such domains, stabilization imparted by disulfide bonds relaxes requirements for strong, noncovalent, folded-state interactions.

Detection of alkali metal ions in DNA crystals using state-of-the-art X-ray diffraction experiments

The observation of light metal ions in nucleic acids crystals is generally a fortuitous event. Sodium ions in particular are notoriously difficult to detect because their X-ray scattering contributions are virtually identical to those of water and Na+…O distances are only slightly shorter than strong hydrogen bonds between well-ordered water molecules. We demonstrate here that replacement of Na+ by K+, Rb+ or Cs+ and precise measurements of anomalous differences in intensities provide a particularly sensitive method for detecting alkali metal ion-binding sites in nucleic acid crystals. Not only can alkali metal ions be readily located in such structures, but the presence of Rb+ or Cs+ also allows structure determination by the single wavelength anomalous diffraction technique. Besides allowing identification of high occupancy binding sites, the combination of high resolution and anomalous diffraction data established here can also pinpoint binding sites that feature only partial occupancy. Conversely, high resolution of the data alone does not necessarily allow differentiation between water and partially ordered metal ions, as demonstrated with the crystal structure of a DNA duplex determined to a resolution of 0.6 Å.

The statute law of Kentucky; with notes, prælections, and observations on the public acts. Comprehending also, the laws of Virginia and acts of Parliament in force in this commonwealth; the charter of Virginia, the federal and state constitutions, and so much of the King of England's proclamation in 1763, as relates to the titles to land in Kentucky. Together with a table of reference to the cases adjudicated in the Court of appeals ...

Imprint varies: v. 2-3, Frankfort, (Ken.) Printed for William Hunter, by Johnston & Pleasants. 1810-1811.--v. 4, Frankfort, (Ken.) Printed for William Hunter, by Robert Johnston. 1814.--v. 5, Frankfort, (Ken.) Printed for Butler & Wood. 1819.

Municipals. Committee on municipal obligations, National association of supervisors of state banks.

"First edition."

State Architect's standard mechanical specifications of November 1, 1955.

"Contained herein are general conditions, forms of proposal, agreements and bonds, State Architect's standard specifications for mechanical, electric and elevator works."

$500,000,000 general obligation bonds : series of December 1995.

"Bids will be received until 11:00 A.M. Central Standard Time Thursday, November 16, 1995 at the James R. Thompson Center, 100 West Randolph, Capital Development Board Room, 14th Floor, Chicago, Illinois. "

$250,000,000 general obligation bonds : series of January 1994.

"Bids will be received until 11:00 A.M. central standard time Thursday, January 20, 1994 at the James R. Thompson Center, 100 West Randolph, Capital Development Board Room, 14th Floor, Chicago, Illinois. "

Bonded indebtedness report of the state of Illinois.

Title from cover.

The federal role in state industrial development programs.

Item 1005-C

Digest of the United States Supreme court reports. U. S. vols. 1-206. L. ed. books 1-51. Appending all state and federal citations of each decided point to the statement thereof in the body of the digest. Containing references also to editorial notes in the Lawyers edition of these reports and in the Lawyers reports annotated.

v. 1. Abandoned, etc.-Bonds.--v. 2. Bone black-Courts.--v. 3. Courts-Martial-Internal revenue.--v. 4. International claims-Prize and Capture.--v. 5 Prize competition -Zinc.--v. 6. Table of cases. Cases affirmed or reversed. Statutes, constitutions, and treaties construed. Rules of court.

Study of neutral Fe(III) complexes of pyridoxal-N-substituted thiosemicarbazone with desolvation induced spin-state transformation above room temperature

The preparation and characterization of two new neutral ferric complexes with desolvation-induced discontinuous spin-state transformation above room temperature are reported. The compounds, Fe(Hthpy)(thpy).CH3OH.3H2O (1) and Fe(Hmthpy)(mthpy).2H2O (2), are low-spin (LS) at room temperature and below, whereas their nonsolvated forms are high-spin (HS), exhibiting zero-field splitting. In these complexes, Hthpy, Hmthpy, and thpy, mthpy are the deprotonated forms of pyridoxal thiosemicarbazone and pyridoxal methylthiosemicarbazone, respectively; each is an O,N,S-tridentate ligand. The molecular structures have been determined at 100(1) K using single-crystal X-ray diffraction techniques and resulted in a triclinic system (space group P1) and monoclinic unit cell (space group P21/c) for 1 and 2, respectively. Structures were refined to the final error indices, where RF = 0.0560 for 1 and RF = 0.0522 for 2. The chemical inequivalence of the ligands was clearly established, for the "extra" hydrogen atom on the monodeprotonated ligands (Hthpy, Hmthpy) was found to be bound to the nitrogen of the pyridine ring. The ligands are all of the thiol form; the doubly deprotonated chelates (thpy, mthpy) have C-S bond lengths slightly longer than those of the singly deprotonated forms. There is a three-dimensional network of hydrogen bonds in both compounds. The discontinuous spin-state transformation is accompanied with liberation of solvate molecules. This is evidenced also from DSC analysis. Heat capacity data for the LS and HS phases are tabulated at selected temperatures, the values of the enthalpy and entropy changes connected with the change of spin state were reckoned at DeltaH = 12.5 0.3 kJ mol-1 and DeltaS = 33.3 0.8 J mol-1 K-1, respectively, for 1 and DeltaH = 6.5 0.3 kJ mol-1 and DeltaS = 17.6 0.8 J mol-1 K-1, respectively, for 2

Identifications with an ‘aesthetic’ and ‘moral’ diaspora amongst Tamils of diverse state origins in Britain

This chapter employs Pnina Werbner's notion of diasporas as moral communities of suffering and co-responsibility, as well as aesthetic communities of shared transnational consumption of culture and performance of ritual, and relates this to the case of Tamil migrants of diverse state origins in Britain. Sri Lankan Tamil migrants I interviewed towards my research imagine membership of a Tamil diaspora as based on personal (or familial) experiences of suffering in the Sri Lankan civil war, which acts both to create bonds with other Sri Lankan Tamils, and to distinguish from Tamils of other state origins (Indian, Singaporean etc.) despite cultural commonalities (Werbner's aesthetic diaspora). Conversely, many of the non-Sri Lankan Tamil migrants I interviewed imagined these boundaries in more flexible terms, and claimed membership of the 'community of suffering' in ways which did not necessitate personal experience, but rather privileged symbolic constructions of the ethnic community, and an interpretation of historical and current events in India, Sri Lanka (and other sites of Tamil population) as components of a single narrative of Tamil victimhood.