Stereochemistry of Peptides Containing 1-AminocyclopentanecarboxylicA cid ( Am5): Solution and Solid-state Conformations of Boc-Acc '-Acc'-NHMe

The conformational analysis of a protected homodipeptide of 1-aminocyclopentanecarboxylic acid (Acc5) has been carried out. 1H-nmr studies establish a -turn conformation for Boc-Acc5-Acc5-NHMe in chloroform and dimethylsulfoxide solutions involving the methylamide NH in an intramolecular hydrogen bond. Supportive evidence for the formation of an intramolecular hydrogen bond is obtained from ir studies. X-ray diffraction studies reveal a type III -turn conformation in the solid state stabilized by a 4 1 hydrogen bond between the Boc CO and methylamide NH groups. The , values for both Acc5 residues are close to those expected for an ideal 310-helical conformation ( ± 60°, ±30°).

Solid-State Acyl Migration In Salicylamides - An X-Ray Study Of The Ortho-Propionyl And Normal-Propionyl Derivatives

In recent years there has been an upsurge of interest in the study of organic reactions in the solid state. It is now realised that the crystalline matrix provides an extra-ordinary spatial control on the initiation and progress of these reactions. Electronic and dipolar effects which are important in solution are replaced by structural and geometric effects in solids. These 'spatial' or 'topochemical' aspects are important in understanding the mechanistic details of the reaction. In our laboratory, the thermally induced acyl migration in salicylamides from 0- to N- position in the solid state has been under study (Scheme 1). The structures of the acetyl and benzoyl derivatives (Ia,IIa, Ib and IIb) have been reported.

Conformations of the amino aterminal tetrapeptide of emerimicins and antiamoebins in solution and in the solid state

The conformations of Boc-l-Phe-(AiB)3-OH (1) and Boc-l-Phe-(Aib)3-OMe (2) which correspond to the amino terminal sequence of the emerimicins and antiamoebins have been studied in solution using 270 MHz 1H n.m.r. In dimethyl sulphoxide solution both peptides show the presence of two strongly solvent shielded Aib NH groups, consistent with a consecutive β-turn conformation, involving the Aib(3) and Aib(4) NH groups in intramolecular 4 → I hydrogen bonds. This folded conformation is maintained for 2 in chloroform solution. Nuclear Overhauser effect studies provide evidence for a Type II Phe-Aib β-turn. An X-ray diffraction study of Boc-(d,l)-Phe-(Aib)3-OH establishes a single type III(III′) β-turn conformation with Aib(2)-Aib(3) as the corner residues. A single intramolecular 4 → I hydrogen bond between Phe(I) CO and Aib(4) NH groups is observed in the crystal. The solution conformation may incorporate a consecutive type II-III′ structure for the Phe(1)-Aib(2)-Aib(3) segment, with the initial type II β-turn being destabilized by intermolecular interactions in the solid state.

An infrared spectroscopic study of the phase transitions of crystalline aromatic donor-acceptor complexes involving a pseudoplastic state

Variable temperature i.r. spectroscopic studies of weak pi-donor-pi-acceptor complexes in the crystalline state indicate that the complexes undergo order-disorder transitions, the disorder being caused by molecular motion. Thermodynamic data on the phase transitions along with the spectral data suggest that the high-temperature crystalline forms of the complexes are likely to be pseudoplastic.

Lead-acid batteries for partial-state-of-charge applications

2 V/40 Ah valve-regulated lead-acid (VRLA) cells have been constructed with negative plates employing carbon black as well as an admixture of carbon black fumed silica as additives in negative active material for partial-state-of-charge (PSoC) applications. Electrical performance of such cells is compared with conventional 2 V/40 Ah VRLA cells for PSoC operation. Active material utilization has been found to be higher for carbon-black fumed-silica mixed negative plates while formation is faster for cells with carbon-black mixed negative plates. Both faradaic efficiency and percentage capacity delivered have been found to be higher for cells with carbon-black + fumed-silica mixed negative plates. However, a high self-discharge rate is observed for cells with carbon-black + fumed-silica mixed negative plates.

Spatial model of site index based on Y-ray spectrometry and a digital elevation model for two Pinus species in Tuan Toolara State Forest, Queensland, Australia

Site index prediction models are an important aid for forest management and planning activities. This paper introduces a multiple regression model for spatially mapping and comparing site indices for two Pinus species (Pinus elliottii Engelm. and Queensland hybrid, a P. elliottii x Pinus caribaea Morelet hybrid) based on independent variables derived from two major sources: g-ray spectrometry (potassium (K), thorium (Th), and uranium (U)) and a digital elevation model (elevation, slope, curvature, hillshade, flow accumulation, and distance to streams). In addition, interpolated rainfall was tested. Species were coded as a dichotomous dummy variable; interaction effects between species and the g-ray spectrometric and geomorphologic variables were considered. The model explained up to 60% of the variance of site index and the standard error of estimate was 1.9 m. Uranium, elevation, distance to streams, thorium, and flow accumulation significantly correlate to the spatial variation of the site index of both species, and hillshade, curvature, elevation and slope accounted for the extra variability of one species over the other. The predicted site indices varied between 20.0 and 27.3 m for P. elliottii, and between 23.1 and 33.1 m for Queensland hybrid; the advantage of Queensland hybrid over P. elliottii ranged from 1.8 to 6.8 m, with the mean at 4.0 m. This compartment-based prediction and comparison study provides not only an overview of forest productivity of the whole plantation area studied but also a management tool at compartment scale.

Electricity pricing in New Zealand and the Australian State of Queensland: Accounting for the impact of sector restructuring

The electricity industries of New Zealand (NZ) and the Australian state of Queensland have undergone substantial structural and regulatory reform with the common intent to improve economic efficiency. Deregulation and privatisation have been key elements of the reform but have been approached differently by each jurisdiction. This study traces the link between structural and regulatory regimes and asset valuation, profits and, ultimately, pricing. The study finds that key drivers in recent price increases are the government-owned generation and retail sector in NZ and the government-owned distribution sector in Queensland. It is concluded that, contrary to the rationale for the imposition of regulatory controls in a nonmarket environment, the regulatory regimes appear to have contributed to higher rather than lower pricing structures.

Cyclic Peptide Disulfides - Solution And Solid-State Conformation Of Boc-Cys-Pro-Aib-Cys-S-S-Bridge-Nhme,A Disulfide-Bridged Peptide Helix

The solution and solid-state conformations of the peptide disulfide Boc-Cys-Pro-Aib-Cys-NHMe have been determined by NMR spectroscopy and X-ray diffraction. The Cys(4) and methylamide NH groups are solvent shielded in CDCI3 and (CD,),SO, suggesting their involvement in intramolecular hydrogen bonding. On the basis of known stereochemical preferences of Pro and Aib residues, a consecutive @-turn structure is favored in solution. X-ray diffraction analysis reveals a highly folded 310 helical conformation for the peptide, with the S-S bridge lying approximately parallel to the helix axis, linking residues 1 and 4. The backbone conformational angles are Cys(1) 4 = -121.1', $ = 65.6"; Pro(2) 4 = -58.9', 4 = -34.0'; Aib(3) 4 = -61.8', $ = -17.9'; Cys(4) 4 = -70.5', $ = -18.6'. Two intramolecular hydrogen bonds are observed between Cys(1) CO--HN Cys(4) and Pro(2) CO--HNMe. The disulfide bond has a right-handed chirality, with a dihedral angle (xss) of 82'.

A Magnetic Susceptibility Study of Spin-state Transitions in Rare-earth TrioxocobaItates( III)

Rare-earth trioxocobaltates(lll), Ln[CoO,], with Ln = Pr, Nd, Tb, Dy. and Yb exhibit low-spin to high-spin transitions of cobalt characterised by a maximum in the Ax-l against temperature plots where Ax is the cobalt contribution to the magnetic susceptibility. The susceptibility behaviour is distinct from that of La[CoO,] which shows a plateau in the x-I-T curve accompanied by a structural transition. The temperature at which the AX- I-T curve shows a maximum increases with the decrease in the size of the rare-earth ion. The susceptibility behavior of solid solutions of La,,Nd,CoO, has been investigated to see how the behaviour characteristic of Nd[CoO,] changes to that of La[CoO,].

State Estimates of Employment Rates for Persons with Disabilities: Report Summary

Statistics on the states’ employment rates for persons with disabilities relative to their non-disabled peers may be of assistance to providers of employment services for persons with disabilities. Such information can help service providers, policy makers, and disability advocacy leaders to assess whether the employment rate of people with disabilities is improving over time, given policy, regulatory, and service intervention strategies. A recent report from the Cornell University Rehabilitation Research and Training Center (RRTC) for Economic Research on Employment Policy for Persons with Disabilities uses data from the March Current Population Survey to estimate employment rates for persons with and without a disability in the non-institutionalized working-age (aged 25 through 61) civilian population in the United States, and for each state and the District of Columbia for the years 1980 through 1998. The employment rate of persons with a disability relative to that of persons without disabilities are found to vary greatly across states. Over the last 20 years the relative employment rate of those with a disability dramatically declined overall and in most states.

Steady-State Response of Thick Rectangular Plates

The classical theory of plates neglects the effects of rotatory inertia and shear deformation, and due to this assumption it is applicable only for thin plates. Mindlin presented an improved plate theory which is fairly accurate.

Reversible photodimerization of phenylbutadienes in the solid state

Based on x-ray crystallographic studies, it is shown that crystal chemical factors govern the reversible photodimerization of phenylbutadienes in the solid state.

Roles, responsibilities and scope of practice: describing the ‘state of play’ for infection control professionals in Australia and New Zealand

Background In the past decade the policy and practice context for infection control in Australia and New Zealand has changed, with infection control professionals (ICPs) now involved in the implementation of a large number of national strategies. Little is known about the current ICP workforce and what they do in their day-to-day positions. The aim of this study was to describe the ICP workforce in Australia and New Zealand with a focus on roles, responsibilities, and scope of practice. Methods A cross-sectional design using snowball recruitment was employed. ICPs completed an anonymous web-based survey with questions on demographics; qualifications held; level of experience; workplace characteristics; and roles and responsibilities. Chi-squared tests were used to determine if any factors were associated with how often activities were undertaken. Results A total of 300 ICPs from all Australian states and territories and New Zealand participated. Most ICPs were female (94%); 53% were aged over 50, and 93% were employed in registered nursing roles. Scope of practice was diverse: all ICPs indicated they undertook a large number and variety of activities as part of their roles. Some activities were undertaken on a less frequent basis by sole practitioners and ICPs in small teams. Conclusion This survey provides useful information on the current education, experience levels and scope of practice of ICPs in Australia and New Zealand. Work is now required to establish the best mechanisms to support and potentially streamline scope of practice, so that infection-control practice is optimised.

Theory of the mixed valent state

After briefly discussing the question of a distinct mixed valent state and theoretical models for it, the area of greatest theoretical success, namely the mixed valent impurity, is reviewed. Applications to spectroscopy, energetics and Hall effect are then putlined. The independent impurity approximation is inadequate for many properties of the bulk system, which depend on lattice coherence. A recent auxiliary or slave boson approach with a simple mean field limit and fluctuation corrections is summarized. Finally the mixed valent semiconductor is discussed as an outstanding problem.

A study in Crystal engineering: Solid-state photodimerization of chloro- and methyl-coumarins

Use of chloro and methyl substitution in crystal engineering and their interchangeability in terms of mode of packing have been examined in a series of substituted coumarins. Photoreactivity in the solid state lists been correlated with the crystallograhic structures of these coumarins. The packing of chloro-substituted aromatic compounds has been investigated by analysing the arrangement of 132 compounds. Results substantiate the use of the chloro group as a steering agent and show that the chloro and methyl groups are not always interchangeable.