Evaluations of solid electrodes for use in voltammetric monitoring of heavy metals in samples from metallurgical nickel industry

Evaluation of different solid electrode systems for detection of zinc, lead, cobalt, and nickel in process water from metallurgical nickel industry with use of differential pulse stripping voltammetry has been performed. Zinc was detected by differential pulse anodic stripping voltammetry (DPASV) on a dental amalgam electrode as intermetallic Ni–Zn compound after dilution in ammonium buffer solution. The intermetallic compound was observed at –375 mV, and a linear response was found in the range 0.2–1.2 mg L^–1 (r²=0.98) for 60 s deposition time. Simultaneous detection of nickel and cobalt in the low g L^–1 range was successfully performed by use of adsorptive cathodic stripping voltammetry (AdCSV) of dimethylglyoxime complexes on a silver–bismuth alloy electrode, and a good correlation was found with corresponding AAS results (r²=0.999 for nickel and 0.965 for cobalt). Analyses of lead in the g L^–1 range in nickel-plating solution were performed with good sensitivity and stability by DPASV, using a working electrode of silver together with a glassy carbon counter electrode in samples diluted 1:3 with distilled water and acidified with H₂SO₄ to pH 2. A new commercial automatic at-line system was tested, and the results were found to be in agreement with an older mercury drop system. The stability of the solid electrode systems was found to be from one to several days without any maintenance needed.     

STRUCTURE-ACTIVITY STUDIES OF PHOTOACTIVATED ANTIVIRAL AND CYTOTOXIC TRICYCLIC THIOPHENES

The photoactivated antiviral and cytotoxic activities of the naturally occurring thiophene, alpha-terthienyl (1), and 15 synthetic analogues were evaluated against murine cytomegalovirus and Sindbis virus, and murine mastocytoma cells. After irradiation with near UV light, alpha-terthienyl and most of its analogues had significant toxicity, with minimum inhibitory concentrations in the range of 0.02-40 microM. In the absence of near UV irradiation, only one analogue had antiviral activity and five were cytotoxic. The most active analogues were those containing carboxylic acid, hydroxyl, or cyano substituents. Quantitative structure-activity relationship analysis of thiophene phototoxicity suggested that the rate of singlet oxygen production is the primary determinant of antiviral and cytotoxic activities. For phototoxicity against murine cytomegalovirus, a significant role for hydrophobicity was also demonstrated. Tricyclic thiophenes show significant potential for photochemotherapy of viral infections and cancer, and further evaluation in animal models is recommended.     

Saturated heterocycles. 251 . Determination of σ+ values of heteroaryl-substituted phenyl groups via ring-chain tautomerism

The Hammett-Brown electrophilic substituent constants σ⁺ for five heteroaryl-substituted phenyl groups were estimated via the ring-chain tautomeric equilibria of three sets of oxazolidines and 1,3-oxazines in deuteriochloroform solution. For oxazolidines derived from norephedrine and norpseudoephedrine, the σ⁺ values were also determined via the gas-phase ring-chain equilibria, by means of mass spectrometry. The results show that the heteroaromatic substituents studied have a slight electron-withdrawing character, with σ⁺ in the range -0.03 to 0.59. The gas-phase σ⁺ values are significantly higher than the solution values.     

Assignments of the Pfr-Pr FTIR difference spectrum of cyanobacterial phytochrome Cph1 using 15N and 13C isotopically labeled phycocyanobilin chromophore

The reversible red and far-red light-induced transitions of cyanobacterial phytochrome Cph1 from Synechocystis PCC 6803 were investigated by Fourier transform infrared (FTIR) difference spectroscopy. High-quality light-induced Pfr-Pr difference FTIR spectra were recorded for the 58 kDa N-terminal domain of Cph1 by repetitive photochemical cycling and signal averaging. The Pfr-Pr difference spectra in H(2)O and D(2)O were very similar to those previously reported for full-length 85 kDa Cph1.(1) Published assignments were extended by analysis of the effects of (13)C and (15)N isotope substitutions at selected sites in the phycocyanobilin chromophore and by (15)N global labeling of the protein. The Pfr-Pr difference spectra were dominated by an amide I peak/trough at 1653 cm(-1)(+)/1631 cm(-1)(-) and a smaller amide II band at 1554 cm(-1). Labeling effects allowed specific chromophore assignments for the C(1)=O (1736 cm(-1)(-)/1724 cm(-1)(+)) and C(19)=O (1704 cm(-1)(-)) carbonyl vibrations, C=C vibrations at 1589 cm(-1)(+), and bands at 1537(-), 1512(+), 1491(-), 1163(+), 1151(-), 1134(+), 1109(-), and 1072(-) cm(-1) that must involve chromophore C-N bonds. A variety of additional changes were insensitive to isotope labeling of the chromophore. Effects of (15)N labeling of the protein were used to tentatively assign some of these to specific amino acid changes. Those insensitive to (15)N labeling included a protonated aspartic or glutamic acid at 1734 cm(-1)(-)/1722 cm(-1)(+) and a cysteine at 2575 cm(-1)(+)/2557 cm(-1)(-). Bands sensitive to (15)N protein labeling at 1487 cm(-1)(+)/1502 cm(-1)(-) might arise from trytophan and bands at 1261 cm(-1)(+)/1244 cm(-1)(-) and 1107 cm(-1)(-)/1095 cm(-1)(+) might arise from a histidine environment or protonation change. These assignments are discussed in light of the 15Z-E photoisomerization model of phototransformation and the associated protein conformational changes.     

Quality control and evaluation of mass spectra

Over 1400 electron ionization mass spectra of selected organic compounds have been measured under carefully defined conditions. In this paper, the variables such as sample purity and spectrometer calibration that are controlled are described. The quality of the resulting spectra as well as the cost of the measurements is reported.     

Effect of finite extensibility on the viscoelastic properties of a styrene–butadiene rubber vulcanizate in simple tensile deformations up to rupture

Stress–strain and rupture data were determined on an unfilled styrene–butadiene vulcanizate at temperatures from ?45 to 35°C and at extension rates from 0.0096 to 9.6 min^?1. The data were represented by four functions: (1) the well-known temperature function (shift factor) a_T; (2) the constant strain rate modulus, F(t,T), reduced to temperature T₀ and time t/a_T, i.e., T₀F(t/a_T)/T; (3) the time-dependent maximum extensibility, λ_m(t/a_T); and (4) a function Ω(χ) where χ = (λ ? 1)λ_m⁰/λ_m, in which λ is the extension ratio and λ_m⁰ is the maximum extensibility under equilibrium conditions. The constant strain rate modulus characterizes the stress–time response to a constant extension rate at small strains, within the range of linear response; λ_m is a material parameter needed to represent the response at large λ; and Ω(χ) represents the stress–strain curve of the material in a reference state of unit modulus and λ_m = λ_m. The shift factor a_T was found to be sensibly independent of extension. At all values of t/a_T for which the maximum extensibility is time-independent, the relaxation rate was also found to be independent of λ. These observations indicate that the monomeric friction coefficient is strain-independent over the ranges of T and λ covered in the present study. It was found that λ_m⁰ = 8.6 and that the largest extension ratio at break, (λ_b)_max, is 7.3. Thus, rupture always occurs before the network is fully extended.     

Probabilistic Predictions with Federated Learning

Probabilistic predictions with machine learning are important in many applications. These are commonly done with Bayesian learning algorithms. However, Bayesian learning methods are computationally expensive in comparison with non-Bayesian methods. Furthermore, the data used to train these algorithms are often distributed over a large group of end devices. Federated learning can be applied in this setting in a communication-efficient and privacy-preserving manner but does not include predictive uncertainty. To represent predictive uncertainty in federated learning, our suggestion is to introduce uncertainty in the aggregation step of the algorithm by treating the set of local weights as a posterior distribution for the weights of the global model. We compare our approach to state-of-the-art Bayesian and non-Bayesian probabilistic learning algorithms. By applying proper scoring rules to evaluate the predictive distributions, we show that our approach can achieve similar performance as the benchmark would achieve in a non-distributed setting.     

On H-Linked Graphs

For a fixed multigraph H, possibly containing loops, with V(H)={h₁, . . . , h_k}, we say a graph G is H-linked if for every choice of k vertices v₁, . . . , v_k in G, there exists a subdivision of H in G such that v_i represents h_i (for all i). This notion clearly generalizes the concept of k-linked graphs (as well as other properties). In this paper we determine, for a connected multigraph H and for any sufficiently large graph G, a sharp lower bound on δ(G) (depending upon H) such that G is H-linked.     

Subdivision Extendibility

Let H be a multigraph and G a graph containing a subgraph isomorphic to a subdivision of H, with S ⊂ V(G) (the ground set) the image of V(H) under the isomorphism. We consider connectivity and minimum degree or degree sum conditions sufficient to imply there is a spanning subgraph of G isomorphic to a subdivision of H on the same ground set S. These results generalize a number of theorems in the literature.     

Studies of hydrogen bonding: Part XXIX. An experimental and theoretical approach to the structure of nitriles and of hydrogen-bonded complexes with phenol

Dipole moments, μ_a, of four nitriles, have been determined experimentally and calculated by the CNDO/2 method. The results obtained can be accounted for in terms of a planar trimer parallel-antiparallel model held together in clusters. Experimental and CNDO/2 calculated dipole moments of hydrogen-bonded complexes between nitriles and phenol indicate strongly that the O-H proton in phenol is located perpendicular to the triple bond.