Recent Advances and Applications of “Successive Self-Nucleation and Annealing” (SSA) High Speed Thermal Fractionation

The Successive Self-nucleation and Annealing (SSA) thermal fractionation technique is briefly reviewed to highlight recent advances such as the use of high speed DSC concepts to perform faster fractionation. Additionally, recent applications of SSA to characterize confined semi-crystalline model polyethylenes in block copolymer nanophases and in situ prepared nanocomposites with carbon nanotubes are also reviewed. A novel result presented here deals with the use of a macromolecular plasticizer to improve the quality of SSA thermal fractionation.     

A practical paramagnetic relaxation reagent for aqueous solutions

While there is a useable paramagnetic relaxation reagent (PARR) for use in nonpolar or low polarity solvents, there has not been a practical PARR for use in highly polar solvents. A reagent, Gd(NO₃)₃-inositol, is described which appears to satisfy this need. The performance of the reagent is given in terms of its effect on the T₁, NOE and line width values of N,N-dimethylformamide. In addition, the application of this reagent to adenosine is also reported.     

On the validity of the Avrami theorem in the case of decelerating growth

It is argued that the use of the Avrami theorem, S(t) = 1−e^−S_x(t), is in principle not allowed when applied to overlapping diffusion zones or, more generally, in all cases where the phantom nuclei overtake the front of their parent nuclei. Via computer simulations the overtake effect is shown to exist and is found to be surprisingly small. The use of a modified Avrami equation, S(t) = FS_x(t)·[1 −e^−S_x(t)], is suggested for such cases and the function F[S_x(t)] pertaining to diffusion-controlled growth is reported.     

Study of the transition state in the isomerization of trans-N2F2 to cis-N2F2 by extended Hückel theory

Conclusion The quantitative agreement with experimental barrier height and the extra stabilization energy of cis-N₂F₂ over trans-N₂F₂ may not be considered to be very good, but this is only to be expected as small differences between large quantities are being calculated. It appears from our present calculations that the use of Cusachs relation for evaluating the off-diagonal matrix elements in this system is open to question since the experimentally observed planarity of N₂F₂ is not correctly predicted by the use of this relation. We therefore prefer the use of the Wolfsberg-Helmholz relation in this system. A value of K= 1.75 appears to be preferable. The results of all the E.H.T. calculations made here for difluorodiazine clearly show that a twisted transition state is more probable than a linear one (LT or LC) in the isomerization of trans-N₂F₂ to cis-N₂F₂. This conclusion also receives further support from a consideration of the high preexponential factor in the rate equation [1] and the multiplicity of the transition state.     

Nuclear medicine and radiochemistry

Nuclear-medical diagnostic methods are widely used at present, examples being localization diagnosis e.g. of the thyroid, the kidney, and the spleen and function tests, e.g. on the thyroid and on the liver. For these tests it is essential to have organ-specific vehicle substances that can be labeled with suitable radionuclides. For in-vivo investigations, the exposure of the patient to radiation should be kept as small as possible, but the radiation must nevertheless be sufficient to allow the detection of the nuclide. Today, the therapeutic use of radionuclides is only small in comparison with their use in diagnosis.     

Synthesis,characterization, and investigation of the thermal behavior of Cu(II) pyrazolyl complexes

In the present contribution, a procedure to estimate parameters using non-isothermal data was applied. The estimation procedure is based on the use of an energy balance in DSC furnace. The approach found all kinetic parameters of autocatalytic model (E ₁, E ₂, A ₁, A ₂, m, n) besides the ultimate reaction heat and their confidence regions by using deterministic and heuristic algorithms. The application of this approach to isothermal data was done in a previous work and similar results were obtained. The results show that the use of an energy balance is a good methodology to estimate cure kinetic parameters of non-isothermal experiments.     

ATR/FTIR characterization of Steinernema glaseri and Heterorhabditis indica

The use of Fourier transform mid-infrared spectroscopy with attenuated total reflection for characterizing entomopathogenic nematodes is evaluated for the first time. The resulting spectra of Steinernema glaseri and Heterorhabditis indica were compared with the spectrum of Caenorhabditis elegans. In the absorption spectra generated by the nematodes samples, the absorption bands were assigned to the molecular species and some important components were identified including triglycerides, trehalose, glycogen and collagen. Also, the use of star diagrams for the fingerprint section of nematode spectra for separating genera is discussed.     

Negative-ion fast atom bombardment mass spectra of some bisanionic hypervalent germanium,silicon and titanium salts

Negative-ion fast atom bombardment mass spectra of hypervalent germanates silicates and titanate with the use of two matrices, glycerol and m-nitrobenzyl alcohol, were studied. In the case of germanates a complete reaction of the studied anion with glycerol is observed, so it is impossible to use such a matrix to identify these compounds. The use of m-nitrobenzyl alcohol allows spectra to be obtained that are significant with respect to the structure for all the studied compounds. However, for each compound a partial reaction of this matrix is observed. Further, in the case of doubly charged anions, the adduct ion obtained with an alkali metal cation does not show glycerol reactivity whereas such reactivity occurs from the adduct ion obtained with proton.     

Evaluation of GTO molecular integrals

Methods for evaluating the function F_m(t) occurring in molecular integrals over Gaussian-type orbitals are reviewed and extended. Formulas based on Bessel function and continued-fraction expansions are analyzed. The recommended evaluation procedures, embodied in a portable computer program, involve Padé approximations for various argument intervals and use recursion in m. The program is economical in storage requirements and faster than those in current use.     

A convenient technique for determination of reactivity ratios

A new technique to determine the reactivity ratios for monomers is described. It is based on vapor-phase chromatography and can be used for any volatile monomer. A new simplified equation was deduced which permits the direct use of the retention times to obtain the pair r₁r₂. The method is suggested for use in determination of the molar ratios of the chemical units in the polymer chain, regardless of chemical composition or constitution. The simplicity of this technique allows its use for monomer–polymer systems composed of any number of volatile monomers. The validity of this method was checked by using the pair methyl methacrylate–styrene. This technique is also being applied to the study of kinetics in polymerizations, since it allows the measurements of several samples taken from a single experiment.     

Bis(tert‐butylpyrene) Nanotweezers and Nanocalipers: Enhanced Extraction and Recognition Abilities for Single‐Walled Carbon Nanotubes

We developed a host–guest methodology for separation of single‐walled carbon nanotubes (SWNTs) according to the handedness, diameter and metallicity by the use of diporphyrin nanotweezers and nanocalipers. Although the pyrene has been frequently used to replace porphyrin, due to a similar affinity to the surface of SWNTs and better availability, the extraction and recognition abilities of dipyrene nanotweezers were not so good as those of diporphyrin ones as we reported previously. However, introduction of a tert‐butyl substituent at the 7′‐position of 2‐pyrene is found to enhance the extraction and recognition abilities of dipyrene nanotweezers and nanocalipers. That is, (6,5)‐SWNTs were obtained in high purity by use of bis(tert‐butylpyrene) nanotweezers with a phenanthrene spacer and metallic SWNTs were highly enriched by use of bis(tert‐butylpyrene) nanocalipers with a carbazole–anthracene–carbazole spacer.     

Palladium‐Catalyzed Regioselective C‐Benzylation via a Rearrangement Reaction: Access to Benzyl‐Substituted Anilines

An unprecedented C‐benzylation rearrangement reaction, catalyzed by palladium, is reported. The reaction proceeds by rearrangement leading to the direct synthesis of para or ortho benzyl‐substituted N‐methylanilines. The product is obtained in high regioselectivity, without the need to use a ligand for the catalytic process.     

The effect of topical ethanol extract of Cotinus coggygria Scop. on cutaneous wound healing in rats

The aim of this study is to determine the cutaneous wound healing effects of the ethanol extract of Cotinus coggygria leaves in rats by excision wound model to provide scientific evidence for the traditional use of C. coggygria Scop. The levels of malondialdehyde, catalase, superoxide dismutase, glutathione and hydroxyproline were investigated in wound tissues. Histopathological examination was also performed. The hydroxyproline content of the granulation tissue and the glutathione levels were both significantly higher in the treatment group than in the control group (p < 0.05 for both); while the malondialdehyde levels were significantly lower in the treatment group (p < 0.05). These results were supported with histological results. The ethanol extract of C. coggygria Scop could be considered as an effective agent in wound healing in accordance with its traditional use.     

Change of the Apparent Reaction Order with Temperature as a Consequence of the Reaction Mechanism Complexity

The theoretical isotherms (α=α(t), where α is the conversion degree and t is the time) and the theoretical thermogravimetric curves(α=α(T), where T is the temperature) were simulated for a system in which two consecutive reactions occur. A critical analysis of the use of an overall single rate reaction equation instead of the use of the true rate equations is presented. Both for isothermal and non-isothermal data and α≤0.50, the apparent reaction order depends on temperature. It is pointed out that the apparent reaction order for a given temperature can be evaluated if the parameters of the compensation effect are known. This revised version was published online in July 2006 with corrections to the Cover Date.     

Using apparent molecular weight from SEC in controlled/living polymerization and kinetics of polymerization

Apparent molecular weights from size exclusion chromatography, that is molecular weights relative to standards of a nature different to that of the polymer sample being studied, are frequently used. We use calculations corresponding to realistic cases to provide guidelines for situations when, and to what extent, apparent molecular weights (MWs) can be meaningful. In controlled polymerization, we show how, without due care, use of apparent MW, could lead to the incorrect conclusion that the reaction was not controlled, whereas the true MWs would be close to theoretical values. We show here that the quality of the eluent as a solvent for the standard and the polymer sample is a good indication of the accuracy and the significance of the apparent polydispersity index. Accurate Mark–Houwink–Sakurada parameters are of limited availability, but the data about solvent quality available in handbooks or available from static light scattering measurements. Apparent M_n is of no use in controlled polymerization if simple simulations as performed in this work do not validate their use. The determination of transfer constants by the Mayo plot can be performed using apparent M_n without introducing any significant error, contrary to apparent weight‐average molecular weight M_w or apparent ln number distribution. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 897–911, 2008     

Dose–Response and Temperature Dependence of the Mortality of Spider Mite and Predatory Mite Eggs Caused by Daily Nighttime Ultraviolet-B Irradiation

The two-spotted spider mite, Tetranychus urticae, is an economically important agricultural pest. A novel physical control method involving daily nighttime UV-B irradiation was recently developed for use in strawberry greenhouses. However, the overlapping of leaves after March prevents direct irradiation to T. urticae on the lower leaf surface, decreasing control effect. Excessive UV-B irradiation causes leaf sunscald in winter. Therefore, optimization of UV-B irradiance and a compensatory control agent are desired. Temperature may affect the survival of organisms exposed to UV-B, although the temperature dependence of UV-B damage is controversial. A phytoseiid mite, Neoseiulus californicus, is a prominent predator but vulnerable to a single UV-B irradiation. We compared dose–response and temperature dependence of UV-B damage between T. urticae and N. californicus eggs under daily nighttime UV-B irradiation. Unexpectedly, N. californicus showed greater resistance to UV-B than T. urticae, and the mortality was increased and decreased at low and high temperatures, respectively. This makes possible the application of UV-B doses that are lethal for spider mites but safe for phytoseiid mites. Overall, we concluded that combined use of phytoseiid mites with UV-B lamps is advantageous to spider mite management in strawberry greenhouses.     

Hydrocyanation of Unsaturated Imines Using Potassium Hexacyanoferrate(II) as a Cyanide Source

An efficient method for the hydrocyanation of unsaturated imines to synthesize β,γ‐unsaturated α‐aminonitriles by a one‐pot two‐step procedure using potassium hexacyanoferrate(II) as a cyanide source and benzoyl chloride as a promoter under catalyst‐free condition is described. The advantages of this protocol are the use of a nontoxic, nonvolatile and inexpensive cyanating agent, no use of transition metal catalysts, high yield and simple work‐up procedure.     

Rapid Determination of Aristolochic Acids I and II in Some Medicinal Plants by High-Performance Liquid Chromatography

Aristolochic acids (AA) are toxic components of Aristolochia plants which result in diseases of the kidney such as urothelial cancer. It is, therefore, essential to monitor the amount of aristolochic acid in herbal medicines. In this study a reversed-phase high-performance liquid-chromatographic (HPLC) method has been developed for rapid determination of aristolochic acids I and II. Baseline separation was achieved within five minutes by use of an ODS C₁₈ column with methanol–water, 60:40, as mobile phase. Two kinds of aristolochic acid were successfully determined in 31 herbal samples of Aristolochia fangchi Wu and Caulis Aristolochiae Manshuriensis. The results indicated that in most samples the aristolochic acid I content is much higher than that of aristolochic acid II. The two kinds of aristolochic acid were not detected in Aristolochia fangchi from the Guangdong region, so Aristolochia fangchi from this region is recommended for use in herbal remedies.     

Repeatability analysis of the Tetrahymena pyriformis population growth impairment assay

Assessments necessary to ensure the safety of both humans and the environment are challenged by the sheer number of chemicals in use today. Chemical legislation, such as REACH, aims to use alternative methods to reduce the reliance on in vivo animal testing. Consequently, databases such as the TETRATOX database, containing data from the Tetrahymena pyriformis population growth impairment assay, have been used extensively to develop computational models which aid in priority setting and initial hazard assessments. To use any toxicological data, an assessment of quality is required. One important aspect of quality is the repeatability of the assay. This study considered TETRATOX assay data for 85 structurally and mechanistically diverse compounds. The repeatability of replicate determinations was assessed and factors relating to repeatability are discussed. Despite the majority of compounds demonstrating excellent repeatability, it was found that the mechanism of action is likely to be a modulating factor, with compounds acting via electrophilic mechanisms being more likely to exhibit reduced repeatability than those acting via narcotic mechanisms. It is evident from this study that the TETRATOX assay is a robust and highly repeatable assay, suitable for use in toxicological modelling studies and priority setting.     

Focused microwave-assisted Soxhlet extraction of acorn oil for determination of the fatty acid profile by GC–MS. Comparison with conventional and standard methods

A study of the feasibility of focused microwave-assisted Soxhlet extraction of acorn oil and comparison of results from analysis of trans fatty acids in the oil thus obtained with those for oils obtained by use of other methods commonly used for oil extraction are reported here. The proposed method was optimized by means of a 21-experiment screening design to determine, by means of a reduced number of experiments, which factors affect both extraction efficiency and the degree of unsaturation of the fatty acids in the oil. The proposed method enables total extraction of the fatty acids in 30 min, which is much less than the time required by the Folch (4.5 h), Soxhlet (16 h), and ISO (8 h) reference methods and the stirring–extraction method (56 h). The efficiency of extraction achieved by use of the proposed method is statistically equivalent to that achieved by use of the other methods; the composition of the extracts obtained by use of the proposed method and the Folch and stirring reference methods are also statistically similar. No trans fatty acids were present in the extracts obtained by use of the Folch, stirring, and proposed methods but they were detected in the extracts obtained by use of both the Soxhlet and ISO methods.