The Ups and Downs of Percent (and Some Interesting Connections)

Percent is a standardized ratio comparison that is often used to describe relative amounts of increase and decrease. In this paper, the nonsymmetric relationship between percent of increase and percent of decrease is explored in several ways. Beginning with a simple graphical representation of the relationship, the functional relationship is developed, with relative decrease expressed as a function of relative increase. Once expressed in the form f(x) = 100x/(100 + x), an immediate connection is made to two other topics commonly found within the study of rates—the work problem and the harmonic mean. Finally, successive percents of increase or decrease are shown to be everyday applications of the geometric mean. This deeper look at a common mathematical concept has uncovered rich structural relationships between topics that are often isolated in the curriculum.     

Germacrene A is a product of the aristolochene synthase-mediated conversion of farnesylpyrophosphate to aristolochene

The biosynthesis of several sesquiterpenes has been proposed to proceed via germacrene A. However, to date, the production of germacrene A has not been proven directly for any of the sesquiterpene synthases for which it was postulated as an intermediate. We demonstrate here for the first time that significant amounts of germacrene A (7.5% of the total amount of products) are indeed released from wild-type aristolochene synthase (AS) from Penicillium roqueforti. Germacrene A was identified through direct GC-MS comparison to an authentic sample and through production of beta-elemene in a thermal Cope rearrangement. AS also produced a small amount of valencene through deprotonation of C6 rather than C8 in the final step of the reaction. On the basis of the X-ray structure of AS, Tyr 92 was postulated to be the active-site acid responsible for protonation of germacrene A (Caruthers, J. M.; Kang, I.; Rynkiewicz, M. J.; Cane, D. E.; Christianson, D. W. J. Biol. Chem. 2000, 275, 25533-25539). The CD spectra of a mutant protein, ASY92F, in which Tyr 92 was replaced by Phe, and of AS were very similar. ASY92F was approximately 0.1% as active as nonmutated recombinant AS. The steady-state kinetic parameters were measured as 0.138 min(-1) and 0.189 mM for k(cat) and K(M), respectively. Similar to a mutant protein of 5-epi-aristolochene (Rising, K. A.; Starks, C. M.; Noel, J. P.; Chappell, J. J. Am. Chem. Soc. 2000, 122, 1861-1866), the mutant released significant amounts of germacrene A (approximately 29%). ASY92F also produced various amounts of a further five hydrocarbons of molecular weight 204, valencene, beta-(E)-farnesene, alpha- and beta-selinene, and selina-4,11-diene.     

Comment: 2004's fastest organic and biomolecular chemistry!

In January 2003, the Royal Society of Chemistry launched Organic & Biomolecular Chemistry (OBC)--a journal promising to provide high quality research from all aspects of synthetic, physical and biomolecular organic chemistry. The journal was set to build upon the foundations laid down by its predecessor publications (J. Chem. Soc., Perkin Trans. 1 and J. Chem. Soc., Perkin Trans. 2) as well as complement the subject coverage already published in prestigious general chemistry journals such as Chemical Communications and Chemical Society Reviews. Nearly two years on, just how is the programme developing and what can the community expect to see from the Royal Society of Chemistry (RSC)?     

A review on initiatives for the management of daily medical emergencies prior to the arrival of emergency medical services

Central European Journal of Operations Research - Emergency services worldwide face increasing cost pressure that potentially limits their existing resources. In many countries, emergency services...     

Definitive identification of cysteine and glutathione complexes of bismuth by mass spectrometry: assessing the biochemical fate of bismuth pharmaceutical agents

Solutions containing BiCl3, bismuth subsalicylate or Bi(NO3)3 with L-cysteine, DL-homocysteine, D-methionine or glutathione have been examined by electrospray mass spectrometry. Prominent peaks are assigned to bismuth complexes of these biomolecules and provide insight towards understanding the bioactivity of bismuth compounds.     

Regioselectivity in palladium-catalyzed C-H activation/oxygenation reactions

[reaction: see text] Palladium-catalyzed directed C-H activation/oxygenation reactions have been explored in a series of meta-substituted aryl pyridine and aryl amide derivatives. These transformations tolerate a diverse array of electron-donating and electron-withdrawing meta-substituents and generally proceed with high levels of regioselectivity for functionalization of the less sterically hindered ortho-C-H bond.     

EFFECT OF BASE SEQUENCE ON THE ULTRAVIOLET IRRADIATION PRODUCTS OF DOUBLE-STRANDED POLYNUCLEOTIDES CONTAINING BROMOURACIL AND ADENINE

Abstract —The effects of ultraviolet irradiation of double-stranded synthetic polynucleotides containing BrU and A have been investigated. Homopolymer pairs and alternating copolymers composed of either ribo- or deoxyribo-nucleotides were prepared and were irradiated with either 313 nm or ˜ 285 nm light. Strand separation and a modest amount of strand breakage followed irradiation of the homopolymer pairs. Changes in the ultraviolet absorption spectra of the polymers during irradiation reflected the sum of hyperchromic increases caused by progressive strand separation and loss of absorbance caused by photoproduct formation. Extensive debromination occurred. An RNase digest of irradiated poly(rA)–poly¹⁴C(rBrU), analysed by column chromatography, showed components similar to those found previously upon irradiation of single-stranded poly(rBrU). Little photoproduct was released by RNase digestion as mononucleotides. The major photoproduct was in the dinucleotide fraction, and may be 5,5'-diuracil. Base sequence had a profound effect on the sensitivity of the polynucleotides. Irradiation of alternating copolymers with doses of light comparable to those that produced major photochemical changes in the homopolymer pairs brought about little if any change in the copolymers of alternating base sequence.     

Equilibrium and kinetic aspects of the uptake of poly(ethylene oxide) by copolymer microgel particles of N-isopropylacrylamide and acrylic acid

The use of microgels for controlled uptake and release has been an area of active research for many years. In this work copolymer microgels of N-isopropylacrylamide (NIPAM) and acrylic acid (AAc), containing different concentrations of AAc and also cross-linking monomer, have been prepared and characterized. These microgels are responsive to pH and temperature. As well as monitoring the equilibrium response to changes in these variables, the rates of swelling/de-swelling of the microgel particles, on changing either the pH or the temperature, have also been investigated. It is shown that the rate of de-swelling of the microgel particles containing AAc is much faster than the rate of swelling, on changing the pH appropriately. This is explained in terms of the relative mobilities of the H(+) and Na(+) ions, in and out of the particles. It was observed that the microgels containing AAc, at pH 8, de-swelled relatively slowly on heating to 50 degrees C from 20 degrees C. This is attributed to the resistance to collapse associated with the large increase in counterion concentration inside the microgel particles. The swelling and de-swelling properties of these copolymer microgels have also been investigated in aqueous poly(ethylene oxide) (PEO) solutions, of different MW (2000-300 000). The corresponding absorbed amounts of PEO from solution onto the microgels have also been determined using a depletion method. The results, as a function of AAc content, cross-linker concentration, PEO MW, pH, and temperature, have been rationalized in terms of the ease and depth of penetration of the PEO chains into the various microgel particles and also the H-bonding associations between PEO and either the -COOH of the AAc moeities and/or the H of the amide groups (much weaker). Finally, the adsorption and desorption of the PEO molecules in to and out of the microgel particles have been shown to be extremely slow compared to normal diffusion time scales for polymer adsorption onto rigid surfaces.     

Secondary bonding interactions observed in two arsenic thiolate complexes

Treatment of N-(2-mercaptoethyl)-1,8-naphthalimide (HL) with stoichiometric amounts of AsCl(3) and base affords AsL(2)Cl and AsL(3) complexes stabilized in part by secondary As...O bonding interactions.     

Interaction of nonionic surfactants with copolymer microgel particles of NIPAM and acrylic acid

Binding of the nonionic surfactants Triton X-100 and Triton X-405 onto linear copolymers of N-isopropylacrylamide (NIPAM) and acrylic acid and to cross-linked microgel particles of similar composition but differing in their cross-link densities has been studied. The binding capacities vary for each of these polymeric systems, being smallest for the linear copolymer. The binding is also significantly less in all cases for the more hydrophilic surfactant, namely, Triton X-405. By comparing estimates of the pore or "cage" size within the microgel particles with the dimensions of the free micelles in solution, it is concluded that micelles of Triton X-100 form within the microgel particles more readily for the lower cross-linked microgel particles. However, micelles do not form as easily inside either microgel for Triton X-405. The swelling/deswelling behavior of each of the two microgels, in the presence of the surfactants, has been explained in terms of their relative binding behavior and how this contributes to the osmotic pressure difference inside and outside the microgel particles and also in terms of micelle "bridging" of the polymer network, causing shrinkage.