Determination of nitrate in pickling baths with a nitrate-selective electrode and a standard addition procedure

A reverse addition method for the determination of nitrate in pickling baths is described. Calibration solutions of nitric acid were added to the standard solution so that the slope and intercept of the electrode response function could be determined. The standard deviation of the method was better than 1 %. Nitrate in pickling baths containing hydrofluoric and nitric acids was measured and compared to measured hydrogen ion concentrations as a function of running time for the bath. The effects of iron(III) and hydrofluoric acid on the results were studied.     

Singlet Excited States and the Light-Harvesting Function of Carotenoids in Bacterial Photosynthesis

Abstract— The recent results of stationary-state and time-resolved absorption, fluorescence and Raman spectroscopies of some typical carotenoids are summarized. Theoretical analyses of carotenoid singlet states and of carotenoid-to-bacteriochlorophyll singlet-energy transfer are also included. On the bases of the energies, the lifetimes and other properties of singlet excited states of the carotenoids in solution and bound to the light-harvesting complexes, the energetics and the dynamics of the light-harvesting function in purple photosynthetic bacteria are discussed with emphasis on the 2A_g and B_u⁺ states.     

Generation and reactions of radical cations from the photolysis of aromatic compounds with tetranitromethane in 1,1,1,3,3,3-hexa-fluoropropan-2-ol

The generation and reactions of aromatic radical cations by photolysis of ArH-tetranitromethane in 1,1,1,3,3,3-hexfluoropropan-2-ol (HFP) at room temperature has been investigated. The primary radical cations (ArH^⊙?) were detectable by EPR spectroscopy in most cases where E ^o(Ar^⊙?/ArH) 1.5 V (vs. Ag/AgCl). Secondary radical cations were obtained from pentamethylbenzene and durene (1,2,3,4,5,6,7,8-octamethyl- and 1,2,4,5,6,8-hexamethyl-anthraceneradical cation), from certain naphthalenes (dehydrodimer radical cations, Ar?Ar^⊙?) and from 2,3-dimethylanisole (the radical of a nitroso derivative). The persistence of the radical cations in the presence of trinitromethanide ion is seen as a consequence of the stabilization of the nucleophile by HFP. This assumption was supported by preparative results on 1-methoxynaphthalene and 1,4-dimethylnaphthalene, where the trinitromethanide ion initiated pathway was completely eliminated in HFP, contrary to results earlier obtained in dichloromethane.     

A novel ATR-FTIR approach for characterisation and identification of ex situ immobilised species.

We demonstrate a novel method to analyse ex situ prepared protein chips by attenuated total reflection Fourier IR spectroscopy (ATR-FTIR), which circumvents tedious functionalisation steps of internal reflection elements (IREs), and simultaneously allows for complementary measurements by other analytical techniques. This concept is proven by utilising immobilised metal affinity capture (IMAC) chips containing about 10 mum thick films of copolymers coated with nitrilotriacetic acid (NTA) groups, which originally was manufactured for surface enhanced laser desorption ionisation (SELDI) spectrometry. Three immobilisation steps were analysed by ATR-FTIR spectroscopy: 1) NTA complexation with nickel(II) ions 2) binding of two histidine (His)-tagged synthetic peptides of 25 (25-His6) and 48 (48-His6) amino acids to the NTA-groups and 3) attachment of a ligand, mesyl amide, to the surface-bound 48-His6. Despite interference from H(2)O, both amide I and II were well resolved. Utilising peptide adsorption in the thick copolymer matrix yields a high saturation peptide concentration of approximately 100 mg mL(-1) and a dissociation constant of 116+/-11 muM, as determined by a detailed analysis of the Langmuir adsorption isotherm. The mesyl amide ligand was directly seen in the raw ATR-FTIR spectrum with specific peaks in the fingerprint region at 1172 and 1350 cm(-1). Several aspects of the fine structure of the amide I band of the peptide were analysed: influences from secondary structure, amino side chains and competing contamination product. We believe that this approach has great potential as a stand-alone or complementary analytical tool for determination of the chemical composition of functionalised surfaces. We emphasise further that with this approach no chemical treatment of IREs is needed; the chips can be regenerated and reused, and applied in other experimental set-ups.     

Chemically defined sialoside scaffolds for investigation of multivalent interactions with sialic acid binding proteins

Four glycodendrons and a glycocluster were synthesized from carbohydrate building blocks to form paucivalent (di- to tetravalent) structures of controlled scaffold architectures. Enzymatic sialylation of the functionalized cluster and dendrons, terminated in lactose residues, generated a library of paucivalent synthetic sialosides displaying sialic acids with different dispositions. These newly constructed bioactive sialic acid-based structures were differentially recognized by sialoadhesin, a mammalian macrophage sialic acid binding protein. The binding of the sialosides to sialoadhesin was evaluated by an enzyme-linked immunosorbant assay to investigate the complementarity of scaffold structure and binding to sialoadhesin. Modulating the interaction between sialoadhesin and its sialic acid ligands has important implications in immunobiology.     

Unbounded derivations ofC*-algebras II

It is demonstrated that a closed symmetric derivation δ of aC?-algebra \(\mathfrak{A}\) generates a strongly continuous one-parameter group of automorphisms of aC?-algebra \(\mathfrak{A}\) if and only if, it satisfies one of the following three conditions

1. (αδ+1)(D(δ))= \(\mathfrak{A}\) , α∈?\{0}.
2. δ possesses a dense set of analytic elements.
3. δ possesses a dense set of geometric elements.

Together with one of the following two conditions

1. ∥(αδ+1)(A)∥≧∥A∥, α∈IR,A∈D(δ).
2. If α∈IR andA∈D(δ) then (αδ+1)(A)≧0 impliesA≧0.

Other characterizations are given in terms of invariant states and the invariance ofD(δ) under the square root operation of positive elements.     

Positivity and monotonicity properties ofC 0-semigroups. I

If exp {?tH}, exp {?tK}, are self-adjoint, positivity preserving, contraction semigroups on a Hilbert space ?=L ²(X;dμ) we write (*) $$e^{ - tH} \succcurlyeq e^{ - tK} \succcurlyeq 0$$ whenever exp {?tH}-exp {?tK} is positivity preserving for allt≧0 and then we characterize the class of positive functions for which (*) always implies $$e^{ - tf(H)} \succcurlyeq e^{ - tf(K)} \succcurlyeq 0.$$ This class consists of thef∈C ^∞(0, ∞) with $$( - 1)^n f^{(n + 1)} (x) \geqq 0,x \in (0,\infty ),n = 0,1,2, \ldots .$$ In particular it contains the class of monotone operator functions. Furthermore if exp {?tH} isL ^p (X;dμ) contractive for allp∈[1, ∞] and allt>0 (or, equivalently, forp=∞ andt>0) then exp {?tf(H)} has the same property. Various applications to monotonicity properties of Green's functions are given.     

The influence of different parameters on the mercerisation of cellulose for viscose production

A quantitative analysis of degree of transformation from a softwood sulphite dissolving pulp to alkalised material and the yield of this transformation as a function of the simultaneous variation of the NaOH concentration, denoted [NaOH], reaction time and temperature was performed. Samples were analysed with Raman spectroscopy in combination with multivariate data analysis and these results were confirmed by X-ray diffraction. Gravimetry was used to measure the yield. The resulting data were related to the processing conditions in a Partial Least Square regression model, which made it possible to explore the relevance of the three studied variables on the responses. The detailed predictions for the interactive effects of the measured parameters made it possible to determine optimal conditions for both yield and degree of transformation in viscose manufacturing. The yield was positively correlated to the temperature from room temperature up to 45 °C, after which the relation was negative. Temperature was found to be important for the degree of transformation and yield. The time to reach a certain degree of transformation (i.e. mercerisation) depended on both temperature and [NaOH]. At low temperatures and high [NaOH], mercerisation was instantaneous. It was concluded that the size of fibre particles (mesh range 0.25–1 mm) had no influence on degree of transformation in viscose processing conditions, apparently due to the quick reaction with the excess of NaOH.