Synthesis and Theoretical Study of New Guanylated Cyclophosphazenes and Their Use in the CO2 Fixation into Styrene Carbonate

Three new guanylated cyclophosphazenes G1–G3 have been synthesized through the catalytic guanylation of three different bi, tetra and hexa (p-aminophenoxy)-cyclophosphazenes by using N,N’-diisopropylcarbodiimide as guanylating agent, ZnEt₂ as catalyst and dry tetrahydrofuran as solvent. The resulting products have been characterized by ¹H, ¹³C{¹H} and ³¹P{¹H} NMR spectroscopy. The hexaguanylated cyclophosphazenes exhibit a deep purple colour, unusual for this type of compounds. The electronic structure of these compounds was investigated by carrying out density functional calculations at PBE-D3(BJ)/TZP level of theory. The molecular structural analysis reveals that aromatic rings are stacked and time dependent density functional calculations show that a charge transfer electronic transition occurs between the aromatic rings which absorb light around 500–700 nm. Finally, the catalytic usefulness of guanylated cyclophosphazene compounds G1–G3 has been proven by the preparation of styrene carbonate from the reaction between styrene oxide and carbon dioxide.

     

Antibacterial activity against Escherichia coli of Cu‐BTC (MOF‐199) metal‐organic framework immobilized onto cellulosic fibers

A strong antimicrobial activity against Escherichia coli of Cu‐BTC metal‐organic frameworks immobilized over cellulosic fibers is hereby reported. The in situ synthesis of Cu‐BTC metal‐organic frameworks, aka MOF‐199 or HKUST‐1, onto cellulosic substrates was carried out by exposing carboxymethylated cellulosic substrates to Cu(OAC)₂, 1,3,5‐benzenetricarboxylic acid and triethylamine solutions following a very specific order. Using an in vitro model, in accordance to ASTM E2149‐13a, we observed that the cellulose‐MOF system was able to completely eliminate the growth of E. coli on agar plates and liquid cultures. The antibacterial activity of the comprising components of MOF‐199 and the cellulosic substrate was also evaluated and determined to be negligible. Since the method used to synthesize MOF‐199 crystals provides a strong bond between the crystals and the cellulosic substrates, the crystals not detach from the anionic cellulosic fibers allowing the modified textile to be washed and reused hence opening a new avenue to fabricate antibacterial clinical fabrics. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40815.     

A rapid spectroscopic method for quantification of P57 in Hoodia gordonii raw material

The feasibility of quantifying the perceived active ingredient (P57) in Hoodia gordonii raw material using Fourier transform near- and mid-infrared spectroscopy combined with chemometric techniques was investigated. The concentration of P57 (a triterpene glycoside) was determined in 146 plant samples with liquid chromatography coupled to mass spectrometry and these values were used to develop a calibration model based on the partial least squares projections to latent structures (PLS) and orthogonal projections to latent structures (O-PLS) regression algorithms. The performance of each calibration model was evaluated according to the root mean square error of prediction (RMSEP) and correlation coefficient (R²). The PLS model with 2nd derivative pre-processing predicted P57 content based on the FT-NIR spectra with the best accuracy and a correlation coefficient (R²) value of 0.9629 and the lowest RMSEP of 0.03%. These results demonstrated that FT-NIR spectroscopy can be used to rapidly quantify P57 in H. gordonii raw material with high accuracy.     

How the free limbs are used by elite high jumpers in generating vertical velocity

The aim of this study was to quantify how elite high jumpers used their free limbs in a competitive high jump and to estimate the contribution that these made to vertical take-off velocity. This was achieved by analysing the competitive performances of six elite male high jumpers using 3D motion analysis and assessing limb function using the relative momentum method. The mean peak relative momentum of the arm nearest to the bar at take-off was 9.4 kg m s(-1), while that of the arm furthest away from the bar was 11.3 kg m s(-1) and these did not differ significantly. The free (lead) leg reached a mean peak relative momentum of 20.9 kg m s(-1). At touch-down the free leg had a large positive relative momentum that was offset by the negative relative momentum of the arms, although their combined value still remained positive. The mean combined free limbs' relative momentum at touch-down was 13.8 kg m s(-1) and reached a peak of 37.6 kg m s(-1). The difference between these two values amounted to 7.1 % of whole-body momentum, which was judged to be the amount by which the free limbs contributed to performance. The arms had a greater influence on performance than had the lead leg. This was because the lead leg increased its relative momentum little during the contact period while the arms had an initial negative value that increased markedly after touch-down. The compressive force exerted by the motion of the free limbs, estimated by the change in the combined free limbs' relative momentum, reached a mean peak of 366 N and was greatest at 37% of the contact period. It was concluded that to maximize the contribution the free limbs can make to performance, given the restraints imposed on technique by other performance requirements, the arms should have a vigorous downward motion at touch-down to make the most use of the high (but little changing) relative momentum of the lead leg.     

Specific serodiagnosis of human leishmaniasis with recombinant Leishmania P2 acidic ribosomal proteins

The Leishmania P2 proteins have been analyzed as potential tools for the immunodiagnosis of human mucocutaneous and visceral leishmaniasis. Two recombinant Leishmania infantum proteins, rLIP2a and rLip2b, were used. The analysis indicated that the rLiP2a and rLiP2b proteins are recognized by 76% (16 of 21) and 42% (9 of 21), respectively, of sera from patients with mucocutaneous leishmaniasis and by 50% (5 of 10) and 40% (4 of 10), respectively, of sera from patients with visceral leishmaniasis. The Leishmania P2 proteins were engineered to have deletions of particular amino acids from the carboxyl-terminal region in order to avoid cross-reactivity with sera from patients with systemic lupus erythematosus and Chagas' disease, since it is known that this region is the main target of the autoantibodies present in sera from these patients. The results show that while the modified recombinant proteins rLiP2a-Q and rLiP2b-Q, in which the five carboxyl-terminal amino acids had been deleted, maintain the leishmaniasis-specific epitopes, they do not react with sera from patients with autoimmune disease and Chagas' disease. For this reason, and also because the sera from patients with tuberculosis and leprosy, diseases that have to be considered in a differential clinical diagnosis of infectious diseases, do not react with the rLiP2a-Q or rLiP2b-Q protein, we think that the engineered proteins may be considered specific tools for the immunodiagnosis of mucocutaneous and visceral leishmaniasis.     

Poly(sulphopropylbetaines): 1. Synthesis and characterization

The synthesis of aromatic and aliphatic poly(sulphopropylbetaines) is described within the series of vinylpyridines and tertiary amino-methacrylates. Two complementary strategies were used: (a) preparation and free radical polymerization in aqueous solution (60°C, 4,4'-azobiscyanovaleric acid) of the monomers; (b) heterogeneous quaternization of preformed poly(vinylpyridines) and poly(tertiary amino-methacrylates) by 1,3-propanesultone in propylene carbonate or tetramethylene sulphone solution (120°C). The high molecular weight poly (zwitterions) ($\text{10}{}^5\text{<}\text{M}\text{?}{}_{\mathrm{W}}\text{< 5 × 10}{}^6$) were characterized by ultra-violet and ¹H nuclear magnetic resonance spectroscopy, and their water affinity at 20°C was estimated by water vapour absorption measurements.     

Olive oil consumption and reduced incidence of hypertension: The SUN study

Olive oil, a major component of the Mediterranean diet, has been associated in some small clinical trials and cross-sectional studies with a reduction in blood pressure. The objective of this study was to assess the association of olive oil consumption with the incidence of hypertension in an epidemiologic cohort, the Seguimiento Universidad de Navarra (SUN) study. The SUN Project is a prospective cohort study whose members are all university graduates. The recruitment and follow-up of participants is made using mailed questionnaires. Diet was assessed using a semiquantitative food frequency questionnaire previously validated in Spain, with 136 items. Outcomes of interest were newly diagnosed cases of hypertension, as reported by participants in the follow-up questionnaires. Logistic regression models were fit to assess the risk of hypertension associated with olive oil consumption. For the present analysis, we have taken in consideration the first 6,863 participants, with at least 2 yr of follow-up. After a median follow-up time of 28.5 mon, the cumulative incidence of hypereension was 4.7% in men and 1.7% in women. A lower risk of hypertension was observed among participants with a higher olive oil consumption at baseline, but the results were not statistically significant (P=0.13 for the linear trend test in the multivariate model). However, among men, the adjusted odds ratios (OR) (95% confidence intervals) of hypertension for the second to fifth quintiles of olive oil consumption, compared with the first quintile, were 0.55 (0.28–1.10), 0.75 (0.39–1.43), 0.32 (0.15–0.70), and 0.46 (0.23–0.94), respectively (P=0.02 for linear trend). No association was found between olive oil consumption and the risk of hypertension among women. In conclusion, in a Mediterranean population, we found olive oil consumption to be associated with a reduced risk of hypertension only among men. The lack of association observed among women might be attributed to the overall lower incidence of hypertension found among females and the resulting lower statistical power.     

Initial in-orbit results from a low-cost atmospheric ozone monitor operating on board the FASat-Bravo microsatellite

In 1994, a collaborative programme was set up between the University of Surrey and the Chilean Air Force to design and build a low-cost 50 kg microsatellite with instrumentation capable of monitoring the distribution and concentration of stratospheric ozone, particularly over Chilean territory. This resulted in the joint design and development of the ozone-layer monitoring experiment (OLME), which was flown on board the resultant FASat-Bravo microsatellite, launched in July 1998 into an 820 km altitude Sun-synchronous orbit. The nadir-pointing OLME measures the solar ultraviolet light backscattered from the atmosphere in four spectral bands. From these raw radiometric data, total column ozone concentrations can be deduced. Since the launch, a series of high-spatial-resolution measurements have been made over Chilean scientific stations, while continuous low-spatial-resolution measurements have been used to provide global coverage. To date, the University of Surrey has concentrated on these global measurements, and has used a simplified ozone retrieval algorithm to check the results qualitatively against ozone maps produced by NASA's Earth Probe Total Ozone Mapping Spectrometer (TOMS) payload. These initial results look promising, with apparently good correlation between the two datasets. A novel, more-complex retrieval algorithm has been applied to the high-resolution data, and early results have shown agreement with the TOMS.     

Density-driven flow and solute transport problems. A 2-D numerical model based on the network simulation method

The network simulation method, based on the formal equivalence between physical systems and electrical networks, solves numerical problems of relatively mathematical complexity in a versatile, efficient and computationally fast way. In this paper, the method is applied for the first time to the design of a general purpose model for simulating two-dimensional transient density-driven flow and solute transport through porous media, a mathematical model made up by coupled, nonlinear differential equations. Using the Boussinesq approximation and the stream function formulation, the model is used to solve two typical problems related with groundwater flows. Isochlor concentration and stream function curves are presented and successfully compared with those of other authors. Simulation is carried out using the digital computer program Pspice with relatively low computing times.