A note on the necessary conditions for the algebraic Riccati equation

We derive some useful and easily computable necessary conditionsfor the existence of a positive semi-definite solution to thealgebraic Ricatti equation (ARE). A motivating example is givento highlight the usefulness of the conditions for controllerand observer designs for nonlinear systems. Further, an upperbound on the trace of the solution to the ARE is also derived.     

Mechanism of DNA-drug interactions

Over the last two decades many strategies have been planned to design specific drugs for rare diseases to target their action at the DNA level. Advancements in our understanding of the interactions of small nonpeptide molecules with DNA have opened the doors for “rational” drug design. Special methods have now been developed to give accurate account of the precise location of ligand-DNA adducts on target DNA. We are now in a position to think of designing ligands that recognize particular sequences of base pairs. This work will allow us to enter into a new era of gene therapy for diseases like Cystic fibrosis, Alzheimer’s disease and many related disorders at genetic level. These ligands can also be employed in the treatment of various types of cancers. They may also be useful as highly specific probes to locate particular sequences in the genomic DNA.     

A modified apparatus for determination of carbon in metals by the low pressure method

The low pressure method of determination of carbon in metals and alloys was modified to include certain new techniques. An isopentane slush bath dispensed with the use of liquid oxygen and the usual McLeod gauge was replaced by a differential oil manometer, which increased the sensitivity. As little as 5 μg of carbon in CaCO₃-quartz standards could be determined with a coefficient of variation of 16.0% which improved to 3.3% at the 100-μg level. The apparatus was used for the determination of carbon in metals such as uranium, zirconium and iron and in steels and cupronickel alloy.     

Thermal decompositions of sulphosalicylates of MG(II), CA(II) and ZN(II)

The thermal decompositions of the sulphosalicylates of Mg(II), Ca(II) and Zn(II) have been investigated by means of TG and DTA. The preparation and analysis of these compounds are included. The possible decomposition reactions in the various stages and the final decomposition products are discussed.     

First example of the C-alkylation of indoles with Baylis-Hillman acetates

Baylis-Hillman acetates undergo S_N2′ allylic substitution with indoles in the presence of 20 mol % of indium tribromide under mild conditions to afford a new class of substituted indoles in high yields with (E)-stereoselectivity. The stereochemistry of the products was assigned by various NMR experiments.     

Organoboranes—34 : General synthesis of chiral boronic and borinic esters via asymmetric hydroboration-displacement. carbenoidation of chiral borinic esters to acyclic ketones of high enantiomeric purities

Asymmetric hydroboration of appropriate alkenes with diisopinocampheylborane (Ipc₂BH) or monoisopinocampheylborane (IpcBH₂) produces intermediates that readily eliminate α-pinene on treat- ment with acetaldehyde, providing a direct, convenient route to chiral boronic esters of high enantiomeric purities. Mixed chiral trialkylboranes, readily prepared by stepwise hydroboration of appropriate alkenes with IpcBH₂, eliminate α-pinene on treatment with acetaldehyde under very mild conditions. The procedure makes readily available chiral borinic esters of high enantiomeric purities. The synthetic utility of chiral borinic esters is demonstrated by converting them into acyclic ketones including an alarm pheromone of the ant Monica mutica.     

A comparative study of various computational approaches in calculating the structure of pyridoxal 5'-phosphate (PLP)-dependent beta-lyase protein. The importance of protein environment

Various computational approaches, using molecular mechanics (Amber), semiempirical (AM1), density functional (B3LYP), and various ONIOM methods, have been comparatively investigated for the structure of Escherichia coli NifS CsdB protein. The structure of the entire monomer containing 407 amino acid residues and 579 surrounding water molecules has been optimized. The full geometry optimization in the "active site-only" approach (including only active site atoms) has been found to give the largest root-mean-square (RMS) deviation from the X-ray structure; a much better agreement has been achieved by keeping the atoms leading to the backbones of some amino acids frozen in their positions in the X-ray structure. The best agreement has been attained by including the surrounding protein in the calculations using the two-layer ONIOM (B3LYP:Amber) approach. The results presented in this study conclusively demonstrate the importance of the protein/active-site interaction on the active-site structure of the enzyme. The present theoretical study represents the largest system studied at the ONIOM level to date, containing 7992 atoms, including 84 atoms in the QM region and rest in the MM region.     

A comparison of the mechanism for the reductive half-reaction between pea seedling and other copper amine oxidases (CAOs)

In a previous DFT study a mechanism for the reductive half-reaction of pea seedling amine oxidase (PSAO) was suggested. In many of the suggested steps a lysine at the active site plays an important role. However, this lysine is not found in other amine oxidases. The primary aim of the present DFT study is therefore to investigate alternative mechanisms for those amine oxidases (CAO) where the lysine residue is not present. One of the most important roles suggested for the lysine in PSAO was to protonate the O2-site of TPQ before the critical Cbond;H bond cleavage of the substrate. In the absence of lysine the O2-site of TPQ is now suggested to be protonated by a water ligand on the copper metal complex, in line with experimental suggestions. In other steps the role of lysine is taken over by an asparagine. All results are compared with experimental observations and good agreement is generally found.