Nitrate and Nitrite Ultraviolet Actinometers

Abstract We developed nitrate and nitrite actinometers to determine radiant fluxes from 290 to 410 nm. These actinometers are based on the reaction of the photochemically generated OH radical with benzoic acid to form salicylic acid (SA) and p-hydroxybenzoic acid (pHBA). Actinom-eter development included determination of the temperature and wavelength dependence of the quantum yield for formation of SA and pHBA from nitrate and nitrite photolysis in air-saturated solutions. Quantum yields (at 25°C) for SA production from nitrate photolysis ranged from 0.00146 to 0.00418 between 290 and 350 nm, and from 0.00185 to 0.00633 for nitrite photolysis between 290 and 405 nm. The quantum yields for SA production were approximately 50–60% greater than quantum yields for pHBA production from nitrate and nitrite photolysis. For both actinometers, SA and pHBA formation was temperature dependent, increasing by approximately a factor of 2.2 from 0 to 35°C. Activation energies for SA formation varied with wavelength, ranging from 14.7 to 16.5 kj mol -¹ between 290 and 330 nm for the nitrate actinometer and 12.3 to 17.8 kj mol-¹ between 310 and 390 nm for the nitrite actinometer. Activation energies for pHBA formation were 2–11% higher. Wavelength-dependent changes in the quantum yield and activation energy for SA and pHBA formation from nitrate photolysis suggest multiple electronic transitions for nitrate from 290 to 350 nm. Quantum yields for OH radical formation from nitrate and nitrite photolyses were estimated from SA and pHBA quantum yields at 25°C. Wavelength-dependent OH quantum yields ranged from 0.007 to 0.014 for nitrate photolysis between 290 and 330 nm and from 0.024 to 0.078 for nitrite photolysis between 298 and 390 nm. The nitrate and nitrite actinometers can maintain initial rate conditions for hours, are insensitive to laboratory lighting, easy to use and extremely sensitive; the minimum radiant energy that can be detected in our irradiation system is approximately 10^-9 einsteins.     

Private Weakly-Random Sequences from Human Heart Rate for Quantum Amplification

We investigate whether the heart rate can be treated as a semi-random source with the aim of amplification by quantum devices. We use a semi-random source model called ε-Santha–Vazirani source, which can be amplified via quantum protocols to obtain a fully private random sequence. We analyze time intervals between consecutive heartbeats obtained from Holter electrocardiogram (ECG) recordings of people of different sex and age. We propose several transformations of the original time series into binary sequences. We have performed different statistical randomness tests and estimated quality parameters. We find that the heart can be treated as a good enough, and private by its nature, source of randomness that every human possesses. As such, in principle, it can be used as input to quantum device-independent randomness amplification protocols. The properly interpreted ε parameter can potentially serve as a new characteristic of the human heart from the perspective of medicine.     

Synthesis and Preliminary Evaluation of the Cytotoxicity of Potential Metabolites of Quinoline Glycoconjugates

The design of prodrugs is one of the important strategies for selective anti-cancer therapies. When designing prodrugs, attention is paid to the possibility of their targeting tumor-specific markers such as proteins responsible for glucose uptake. That is why glycoconjugation of biologically active compounds is a frequently used strategy. Glycoconjugates consisting of three basic building blocks: a sugar unit, a linker containing a 1,2,3-triazole ring, and an 8-hydroxyquinoline fragment was described earlier. It is not known whether their cytotoxicity is due to whole glycoconjugates action or their metabolites. To check the biological activity of products that can be released from glycoconjugates under the action of hydrolytic enzymes, the synthetically obtained potential metabolites were tested in vitro for the inhibition of proliferation of HCT-116, MCF-7, and NHDF-Neo cell lines using the MTT assay. Research shows that for the full activity of glycoconjugates, the presence of all three building blocks in the structure of a potential drug is necessary. For selected derivatives, additional tests of targeted drug delivery to tumor cells were carried out using polymer nanocarriers in which they are encapsulated. This approach significantly lowered the determined IC₅₀ values of the tested compounds and improved their selectivity and effectiveness.     

Regioselective formation of a 2,3‐oxaphosphabicyclo[2.2.2]octene 3‐oxide in Baeyer–Villiger type oxidation; a dual pathway for its fragmentation

The O‐insertion reaction of a 7‐phos‐ phanorbornene ( 3 ) unsubstituted on the double‐ bond gave the corresponding 2,3‐oxaphosphabicyclo‐ [2.2.2]octene oxide ( 4a ) in a regioselective manner that was useful in the fragmentation‐related phosphonylation of alcohols. Both the UV‐light mediated and the thermoinduced phosponylation accomplished on the bridged P‐heterocycle ( 4a ) were found to be sensitive toward steric factors, suggesting that beside the well‐known elimination–addition reaction path taking place via metaphosphonate ( 11 ), a competitive novel addition‐‐elimination route involving an intermediate with a pentacoordinated P‐atom ( 12 ) is also present. This was confirmed by the kinetic consideration of our experimental data. © 2006 Wiley Periodicals, Inc. Heteroatom Chem 17:369–375, 2006; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20213     

The physical and NMR characterizations of allyl‐ and crotylcelluloses

Tri‐O‐allylcellulose (degree of polymerization, DP ∼112) was prepared in ∼91% yield, and tri‐O‐crotylcellulose (DP ∼138) was prepared in ∼56% yield from microcrystalline cellulose (DP ∼172, and polydispersity index, PDI ∼1.95) using modified literature methods. Number‐average molecular weight (M_n = 31,600), weight‐average molecular weight (M_w = 191,800), and PDI = 6.07 data suggested that tri‐O‐allylcellulose may be crosslinking in air to generate branched chains. The polymer was stabilized with 100 ppm butylated hydroxy toluene (BHT). The material without BHT experienced glass transition (T_g, differential‐scanning calorimetry, DSC) between −2 and +3 °C, crosslinked beyond 100 °C, and degraded at 298.6 °C (by thermogravimetric analysis, TGA). M_n (45,100), M_w (118,200), PDI (2.62), and thermal data (T_g − 5 to +3 °C, melting point 185.8 °C, recrystallization 168.9 °C, and degradation 343.6 °C) on tri‐O‐crotylcellulose suggested that the polymer was formed with about the same polydispersity as the starting material and is heat stable. While allylcellulose generated continuous flexible yellow films by solution casting, crotylcellulose precipitated from solution as brittle white flakes. Dynamic mechanical analysis (DMA) data on allylcellulose films (T_g − 29.1 °C, Young's modulus 5.81 × 10⁸ Pa) suggest that the material is tough and flexible at room temperature. All ¹H and ¹³C resonances in the NMR spectra were identified and assigned using the following methods: Double‐quantum filter correlation spectroscopy (DQF COSY) was used to assign the network of seven protons in the anhydroglucose portion of the repeat unit. The proton assignments were verified and confirmed by total correlation spectroscopy (TOCSY). A combination of heteronuclear single‐quantum coherence (HSQC) and ¹³C spectroscopies were used to identify all bonded carbon–hydrogen pairs in the anhydroglucose portion of the repeat unit, and assign the carbon nuclei chemical shift values. Heteronuclear multiple bond correlation (HMBC) spectroscopy was used to connect the resonances of methines and methylenes at positions 2, 3, and 6 to the methylene resonances of the allyl ethers. TOCSY was used again to identify the fifteen ¹H resonances in the three pendant allyl groups. Finally, a combination of HSQC, HMBC, and ¹³C spectroscopies were used to identify each carbon in the allyl pendants at 2, 3, and 6. Because of line broadening and signal overlap, we were unable to identify the conformational arrangement about the C5 and C6 bond in tri‐O‐allyl‐ and tri‐O‐crotylcelluloses. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1889–1902, 2000     

NMR shielding in helium-3 atoms modified by gaseous nitrogen and oxygen

Helium-3 nuclear magnetic resonance (³He NMR) measurements were carried out for the gaseous mixtures of helium-3 with pure nitrogen and synthetic air as the solvents. It was found that ³He shielding is linearly dependent on solvent density up to approx. 6 mol/L. At higher density of the gaseous solvent, the change of ³He shielding is nonlinear and especially distinct when helium-3 atoms can interact with two O₂ molecules. The interaction with paramagnetic oxygen molecules can induce two kinds of ³He shielding changes: (1) due to the isotropic Fermi contact interaction and (2) from the dipolar magnetic interaction between unpaired O₂ electrons and ³He nuclear magnetic dipole moment. The two paramagnetic effects in helium-3 shielding cannot be experimentally separated, although for such small molecular objects, they could be presumably modeled by advanced theoretical calculations.     

Estimation of asymmetric responses of U.S. retail fuel prices to changes in input prices based on a linear exponential adjustment cost approach

Central European Journal of Operations Research - Numerous studies have indicated that retail fuel prices respond more quickly when crude oil prices rise than when they fall. We suggest that the...     

Moisture adsorption of glucomannan and xylan hemicelluloses

Wood and wood materials are highly sensitive to moisture in the environment. To a large extent this relates to the hygroscopicity of wood hemicelluloses. In order to increase our understanding of the effects of moisture sorption of the major wood hemicelluloses, glucomannan and xylan, model experiments using films of amorphous konjak glucomannan and rye arabinoxylan were conducted. Moisture-induced expansion and stiffness softening were characterized using dynamic mechanical testing. Both hemicelluloses showed a threshold around 5 % of moisture content above which swelling increased whereas the modulus decreased by more than 70 %. FTIR spectra, using H₂O and D₂O, indicated that even at high RH about 15 % of the hydroxyl groups were not accessible to hydrogen exchange by D₂O. For xylan both hydroxyl groups were found to exchange in the same manner while for the glucomannan the O(6)H group seemed to be the most accessible.