Degradation of poly(vinyl alcohol)‐graft‐lactic acid copolymers by Trichotecium roseum fungus

The biodegradation of poly(vinyl alcohol) and poly(vinyl alcohol)‐graft‐lactic acid copolymers was analyzed, using Trichotecium roseum fungus. The samples were examined during biodegradation at different periods of exposure. Structural modifications of the biodegraded samples were investigated by Fourier transform infrared‐attenuated total reflectance spectroscopy, and the surface morphology was investigated by scanning electron microscopy. The static light scattering results concluded that the weight average molecular mass (M_w) of the copolymers increased after biodegradation, because the fractions with low molecular weight of the copolymers were destroyed. The thermal behavior and stability of the samples before and after the biodegradation period were investigated by differential scanning calorimetry (DSC) and thermogravimetric analyses. The thermogravimetric analyses and their derivatives (TG‐DTG) showed that the thermal stability of the biodegraded samples was more raised comparatively to the unbiodegraded ones. The DSC results demonstrated that biodegradation took place in the amorphous domains of the investigated polymer samples and the crystallinity degree increased after 24 biodegradation days. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41777.     

Preparation and swelling properties of homopolymeric alginic acid fractions/poly(N‐isopropyl acrylamide) graft copolymers

Graft copolymers of crosslinked poly(N‐isopropyl acrylamide) (PNIPAAm) and homopolyguluronic acid (GG) and homopolymannuronic acid (MM) fractions of alginic acid were synthesized. MM and GG block fractions were obtained by partial acid hydrolysis of the alkaline extract from the brown seaweed Macrocystis pyrifera. The conjugation of these block fractions with the synthetic polymer was achieved by amidation with crosslinked PNIPAAm functionalized with an amino group at the end of the polymer chain. The structure of conjugates was determined by Fourier transform infrared and NMR spectroscopy. Atomic force microscopy of the graft copolymer GG‐g‐PNIPAAm showed a regular porous pattern, whereas the MM‐g‐PNIPAAm graft copolymer showed a regular netlike structure. Aqueous solutions of the synthesized graft copolymers afforded hydrogels by stirring with 0.1M CaCl₂. The hydrogels showed a well‐defined stimulus–response to temperature and pH. The swelling, thermal, and pH characterizations demonstrated the superior properties of the GG‐g‐PNIPAAm hydrogel over the MM‐g‐PNIPAAm hydrogel. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42398.     

Multidimensional modeling of biofilm development and fluid dynamics in a hydrogen-based,membrane biofilm reactor (MBfR)

A two-dimensional, particle-based biofilm model coupled with mass transport and computational fluid dynamics was developed to simulate autotrophic denitrification in a spiral-wound membrane biofilm reactor (MBfR), where hydrogen is supplied via hollow-fiber membrane fabric. The spiral-wound configuration consists of alternating layers of plastic spacer net and membrane fabric that create rows of flow channels, with the top and bottom walls comprised of membranes. The transversal filaments of the spacer partially obstruct the channel flow, producing complex mixing and shear patterns that require multidimensional representation. This study investigated the effect of hydrogen and nitrate concentrations, as well as spacer configuration, on biofilm development and denitrification fluxes. The model results indicate that the cavity spacer filaments, which rest on the bottom membranes, cause uneven biofilm growth. Most biofilm resided on the bottom membranes, only in the wake of the filaments where low shear zones formed. In this way, filament configuration may help achieve a desired biofilm thickness. For the conditions tested in this study, the highest nitrate fluxes were attained by minimizing the filament diameter and maximizing the filament spacing. This lowered the shear stress at the top membranes, allowing for more biofilm growth. For the scenarios studied, biomass limitation at the top membranes hindered performance more significantly than diffusion limitation in the thick biofilms at the bottom membranes. The results also highlighted the importance of two-dimensional modeling to capture uneven biofilm growth on a substratum with geometrical complexity.     

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.     

Molecularly imprinted poly(acrylonitrile‐co‐acrylic acid) matrix with sclareol

There are presented results regarding a new set of molecularly imprinted polymers (MIPs) based on acrylonitrile:acrylic acid (AN:AA) copolymer matrix. As template, it was used sclareol, an important anticancer bioactive compound, never used before for molecular imprinting. An emerging and insufficient studied MIP preparation method, namely the phase inversion, was used to prepare 0.8 mm spherical sclareol MIPs (S‐MIPs). Three AN:AA copolymers, having the initial monomer ratios 90:10, 80:20, and 70:30, were synthesized by radical copolymerization in emulsion, without emulsifier. After that, each copolymer was dissolved in the presence of the template (sclareol) in dimethylformamide. The imprinting and the morphology of these new materials were analyzed by rheology, elemental analysis, infrared spectroscopy, size exclusion chromatography, thermogravimetric analysis, differential scanning calorimetry, batch rebinding tests, and Scatchard analysis. The conclusion was that the AN:AA‐80:20 matrix proved to be the optimized solution between high rigidity (given by the AN segments) and high affinity for the template (given by AA segments), the average imprinting factor for this system being 2.67. POLYM. ENG. SCI., 54:1484–1494, 2014. © 2013 Society of Plastics Engineers     

Senescent CD4+CD28− T Lymphocytes as a Potential Driver of Th17/Treg Imbalance and Alveolar Bone Resorption during Periodontitis

Senescent cells express a senescence-associated secretory phenotype (SASP) with a pro-inflammatory bias, which contributes to the chronicity of inflammation. During chronic inflammatory diseases, infiltrating CD4⁺ T lymphocytes can undergo cellular senescence and arrest the surface expression of CD28, have a response biased towards T-helper type-17 (Th17) of immunity, and show a remarkable ability to induce osteoclastogenesis. As a cellular counterpart, T regulatory lymphocytes (Tregs) can also undergo cellular senescence, and CD28⁻ Tregs are able to express an SASP secretome, thus severely altering their immunosuppressive capacities. During periodontitis, the persistent microbial challenge and chronic inflammation favor the induction of cellular senescence. Therefore, senescence of Th17 and Treg lymphocytes could contribute to Th17/Treg imbalance and favor the tooth-supporting alveolar bone loss characteristic of the disease. In the present review, we describe the concept of cellular senescence; particularly, the one produced during chronic inflammation and persistent microbial antigen challenge. In addition, we detail the different markers used to identify senescent cells, proposing those specific to senescent T lymphocytes that can be used for periodontal research purposes. Finally, we discuss the existing literature that allows us to suggest the potential pathogenic role of senescent CD4⁺CD28⁻ T lymphocytes in periodontitis.     

Physical Reasoning to Synchronize Electrical Signals and Related Diagnostics in Plasma Focus Devices

Plasma Focus (PF) devices as well as other similar pulsed discharge devices requires a variety of diagnostics for their proper control and optimization, including the voltage between electrodes, the time derivative of the discharge current, detection of X-rays and neutron emissions, and pulsed laser images (Shadow, Schlieren, interferograms). This article discusses the problem of the time reference of all these outputs and proposes specific techniques for synchronizing them based on sound physical grounds. The foundations of synchronization criterion are verified in several experiments on PF devices.