Studies on the equilibrium uptake of some metal ions on a mixed and doped hydrous oxide using radiotracers

A highly sensitive and rapid method has been developed for the extraction-spectrophotometric determination of ultra trace amounts of americium. Americium(III) is selectively extracted from 1–10M HNO₃ medium with a mixture of (0.3M HDEHP+0.1M P₂O₅), both dissolved in xylene, and finally estimated in the organic phase itself absorptiometrically employing Arsenazo-III as the chromogenic reagent. A 60% dioxaneethanol mixture was used for optium colour development. Beer's law is obeyed in the concentration range 0.1–0.7 g Am cm^–3 and as little as 0.11 g Am cm^–3 could be determined with a precision better than ±2%. The molar absorptivity based on Am content is (3.599±0.049)·10⁵ dm³·mol^–1·cm^–1 at 648 nm which is incidentally the highest value reported as yet for its determination. The optimum concentration range, evaluated by Ringbom's method is 0.1–0.6 ppm Am. Common contaminants such as Al³⁺, Co²⁺, Cr³⁺, Fe³⁺, Ni²⁺, Zr⁴⁺, F^–, NO₃ ^–, and SO ₄ ^2- in fairly large quantities and moderate amounts of Pu⁴⁺, Th⁴⁺ and UO ₂ ²⁺ cause no interference in the final assay. Colour development is almost instantaneous and its intensity remains virtually constant for at least 48 hours.     

Simple Markov‐chain algorithms for generating bipartite graphs and tournaments

We consider two problems: randomly generating labeled bipartite graphs with a given degree sequence and randomly generating labeled tournaments with a given score sequence. We analyze simple Markov chains for both problems. For the first problem, we cannot prove that our chain is rapidly mixing in general, but in the near‐regular case, i.e., when all the degrees are almost equal, we give a proof of rapid mixing. Our methods also apply to the corresponding problem for general (nonbipartite) regular graphs, which was studied earlier by several researchers. One significant difference in our approach is that our chain has one state for every graph (or bipartite graph) with the given degree sequence; in particular, there are no auxiliary states as in the chain used by Jerrum and Sinclair. For the problem of generating tournaments, we are able to prove that our Markov chain on tournaments is rapidly mixing, if the score sequence is near‐regular. The proof techniques we use for the two problems are similar. ©1999 John Wiley & Sons, Inc. Random Struct. Alg., 14: 293–308, 1999     

Conformational structure of peptides containing dehydroalanine: Formation of β‐bend ribbon structure

α,β‐Unsaturated amino acids (dehydroamino acids) have been found in naturally occurring antibiotics of microbial origin and in some proteins. Due to the presence of the C_αC_β double bond, the dehydroamino acids influence the main‐chain and the side‐chain conformations. The lowest‐energy conformational state of the model tripeptides, Ac–X–ΔAla–NHMe, (X=Ala, Val, Leu, Abu, or Phe) corresponds to ϕ₁=−30°, ψ₁=120° and ϕ₂=ψ₂=30°. This structure is stabilized by the hydrogen bond between CO of the acetyl group and the NH of the amide group, resulting in the formation of a 10‐membered ring. In the model heptapeptide containing ΔAla at alternate position with Ala, Abu, and Leu, the lowest‐energy conformation corresponds to ϕ=−30° and ψ=120° for all the Ala, Abu, and Leu residues and ϕ=ψ=30° for all ΔAla residues. A graphical view of the molecule in this conformation reveals the formation of three hydrogen bonds involving the CO moiety of the ith residue and the NH moiety of the i+3th residue, resulting in a 10‐membered ring formation. In this structure, only alternate peptide bonds are involved in the intramolecular hydrogen‐bond formation unlike the helices and it has been named the β‐bend ribbon structure. The helical structures were predicted to be the most stable structures in the heptapeptide Ac–(Aib–ΔAla)₃–NHMe with ϕ=±30°, ψ=±60° for Aib residues and ϕ=ψ=±30° for ΔAla residues. The computational results reveal that the ΔAla residue does not induce an inverse γ‐turn in the preceding residue. It is the competitive interaction of small solvent molecules with the hydrogen‐bonding sites of the peptide which gives rise to the formation of an inverse γ‐turn (ϕ₁=−54°, ψ₁=82°; ϕ₂=44°, ψ₂=3°) in the preceding residue to ΔAla. The computational studies for the positional preference of ΔAla in the peptide containing one ΔAla and nine Ala residues reveals the formation of a 3₁₀ helical structure in all the cases with the terminal preferences for ΔAla, consistent with the position of ΔAla in the natural antibiotics. The extended structures is found to be the most stable for poly‐ΔAla. ©1999 John Wiley & Sons, Inc. Int J Quant Chem 72: 15–23, 1999     

Polyimide-epoxy alloys prepared via micro-modification: Water sorption and diffusion

A novel polyimide-epoxy or PI-EP alloys are prepared by the modification of polyamic acid in the concentration range of 1.54×10⁻⁶ to 1.54×10⁻² mol/L. The methanol sorption for these alloys at 24 hrs and at equilibrium conditions are determined and the residual solvent in fully cyclized polyimides were calculated. The presence of the residual solvent is visualized in fully imidized polymer and a structure containing partly imidized amic acid moiety is proposed and their concentration (in percentage) is calculated. The water sorption for these alloys at 24 hrs and at equilibrium conditions and the values of the water diffusion coefficient are determined from absorption isotherms. The PI-EP alloys have shown comparatively lower water sorption and higher diffusion coefficient than the unmodified polyimide. The mechanistic aspects of water sorption and diffusion are discussed.     

Random walks and an O*(n5) volume algorithm for convex bodies

Given a high dimensional convex body K⊆ℝⁿ by a separation oracle, we can approximate its volume with relative error ε, using O*(n⁵) oracle calls. Our algorithm also brings the body into isotropic position. As all previous randomized volume algorithms, we use “rounding” followed by a multiphase Monte-Carlo (product estimator) technique. Both parts rely on sampling (generating random points in K), which is done by random walk. Our algorithm introduces three new ideas: the use of the isotropic position (or at least an approximation of it) for rounding; the separation of global obstructions (diameter) and local obstructions (boundary problems) for fast mixing; and a stepwise interlacing of rounding and sampling. © 1997 John Wiley & Sons, Inc. Random Struct. Alg., 11 , 1–50, 1997     

Tilianin: A Potential Natural Lead Molecule for New Drug Design and Development for the Treatment of Cardiovascular Disorders

Cardiovascular disorders (CVDs) are the leading risk factor for death worldwide, and research into the processes and treatment regimens has received a lot of attention. Tilianin is a flavonoid glycoside that can be found in a wide range of medicinal plants and is most commonly obtained from Dracocephalum moldavica. Due to its extensive range of biological actions, it has become a well-known molecule in recent years. In particular, numerous studies have shown that tilianin has cardioprotective properties against CVDs. Hence, this review summarises tilianin’s preclinical research in CVDs, as well as its mechanism of action and opportunities in future drug development. The physicochemical and drug-likeness properties, as well as the toxicity profile, were also highlighted. Tilianin can be a natural lead molecule in the therapy of CVDs such as coronary heart disease, angina pectoris, hypertension, and myocardial ischemia, according to scientific evidence. Free radical scavenging, inflammation control, mitochondrial function regulation, and related signalling pathways are all thought to play a role in tilianin’s cardioprotective actions. Finally, we discuss tilianin-derived compounds, as well as the limitations and opportunities of using tilianin as a lead molecule in drug development for CVDs. Overall, the scientific evidence presented in this review supports that tilianin and its derivatives could be used as a lead molecule in CVD drug development initiatives.     

MODIFIED POLYVINYL ALCOHOL-BENZOPORPHYRIN DERIVATIVE CONJUGATES AS PHOTOTOXIC AGENTS

Abstract— Photosensitizing and biodistribution characteristics of a photosensitizer(benzoporphyrin derivative, monoacid ring A; BPD) conjugated to a macromolecule (modified polyvinyl alcohol; M-PVA, molecular weight=10000) were tested in vitro and in vivo . Modified PVA was loaded with BPD at molar ratios 1:12, 1:25, 1:50, 1:75 and 1:100. Most of the work was carried out with a conjugate having a 1:25 molar ratio. In vitro photosensitization was tested using A549 (human lung carcinoma), A432 (human epidermoid carcinoma) and P815 (mastocytoma of DBA/2 mice) cell lines. Photosensitization of M1 (rhabdomyosarcoma of DBA/2 mice) tumors was tested in an in vivo/in vitro assay, in which tumor-bearing mice were injected intravenously with free or conjugated ³H-BPD and 3 h later light activation of tumor cells was carrie out in vitro . Biodistribution studies were carried out using M1 tumor-bearing DBA/2 mice and ³H-BPD either free or conjugated to M-PVA. The result of there these studies showed that the conjugatin of BPD to M-PVA resulted in the formation of a macromolecular photosensitizer that retained full photosensitizing avtivity of the photosensitizer molecules and at the same time gained new charcteristics, advantageous from photodynamic treatment, especially in vivo . In vitro M-PVA-BPD conjugates were at least as efficient in photosensitization of tumor cells as an equivalent number of free BPD molecules, both in the presence and in the absence of serum. Although the biodistribution was in general comparabel to free BPD, the conjugate(1:25) reached slightly higher leves in the blood, kidney, lung and spleen, and lower levels in the liver, brain, skin and muscle in comparison with free BPD. Although the level of M-PVA-BPD in tumor tissue was lower than tht of free BPD under comparable conditions, the conjugate was bound more tightly to the tumor cells and effected higher tumor cell kill when activated by light     

Crystal and Molecular structure of 3,3-Diethyl–2,4,6–[1 H,3 H,5 H] Pyrimidine Trione

C₈H₁₂O₃N₂, M_r = 184.19, Trigonal, R3 (hexagonal axes) a = b = 26.800(1) Å, c = 6.828(3) Å, α = β = 90°, γ = 120°, V = 4247.11 ų, Z = 18, D_m = 1.297 Mg m⁻³, D_c = 1.296 Mg m⁻³, mu = 0.79 mm⁻¹, F(000) = 1764, T = 293 K, final R = 0.080 for 1205 observed reflections. There are two crystallographically independent molecules in the unit cell of the title compound.     

Hydrogel Nanocomposite as a Synthetic Intra-Ocular Lens Capable of Accommodation

A hydrogel nanocomposite was designed, synthesized, and evaluated for use as an auto-focusing intra-ocular lens. The hydrogel scaffold was composed of a monomer-free, thiol that contained polyacrylamide (5%), which was allowed to gel in the presence of nanoparticles at pH 7.4, 25°C. The nanoparticles consisted of a proteo-mimetic polyacrylamide nanogel (∼42 nm), bovine serum albumin (BSA) (∼6 nm), and hydrophilized silica (∼3 nm). The extent of nanoparticle loading increased with decreasing particle size. The elastic modulus increased with increasing loading of the proteo-mimetic nanogels and BSA, and it decreased with hydrophilized silica. In this investigation, the hydrogel that contained silica was the most promising class of nanocomposite hydrogels with properties comparable to that of a young porcine lens. A nanocomposite that consisted of 10% hydrogel scaffold and 24% hydrophilized silica (elastic [E] modulus of ∼1.0 kPa and refractive index [RI] of 1.42) was injected into a pre-evacuated porcine lens capsular bag. The composite lens was evaluated in a custom-designed four-arm radial stretcher, and its force-time spectrum was characterized by time constants of 60 ± 8.9 and 800 ± 32 ms. These results were comparable to a young porcine lens (E Modulus of 1.2 kPa; RI of 1.4105; time constants of 48.3 ± 0.58 and 668 ± 24.6 ms, respectively)