RESUMO
To overcome the recalcitrance of para-aramid textiles against dyeing, this study demonstrated that increasing the functionalities of soybean oil applied to the surface of para-aramids followed by a nonthermal plasma (NTP) treatment improved the dyeing color strength compared with the use of soybean oil alone, and that dyeing occurred through covalent bonding. Particularly, compared with the pretreatment using soybean oil that obtained the highest color strength of 3.89 (as K/S value determined from spectral analysis of the sample reflectance in the visible range), the present pretreatments with either acrylated epoxidized soybean oil (AESO) or a mixture of acrylic acid and soybean oil (AA/Soy) achieved K/S values higher than nine (>9.00). The NTP treatment, after the AESO or AA/Soy pretreatment, was essential in inducing the formation of a polymerized network on the surface of para-aramids that bonded the dye molecules and generating covalent bonds that anchored the polymerized network to the para-aramids, which is difficult to achieve given the high crystallinity and chemical inertness of para-aramids. As an important economic consideration, the sequential experimentation method demonstrated that a simple mixture of AA/Soy could replace the expensive AESO reagent and render a comparable performance in dyeing para-aramids. Among the auxiliary additives tested with the AESO and AA/Soy pretreatments followed by NPT treatment in this study, Polysorbate 80 as a surfactant negatively affected the dyeing, benzyl alcohol as a swelling agent had minimal effect, and NaCl as an electrolyte showed a positive effect. The dyeing method developed in this study did not compromise the strength of para-aramids.
RESUMO
The increasing use of functional aramids in a wide array of applications and the inert nature of aramids against conventional dye and print methods requires developing new dyeing methods. This study aims to use environmentally friendly method with a cationic dye as an alternative for dyeing para-aramid fabrics. Experiments used a multi-factorial design with functions of pretreatment, dye solvent (water and/or glycerol) and auxiliary chemical additives (swelling agent and surfactant) and a sequential experimentation methodology. The most effective dyeing procedures involved the following steps: (i) pretreatments of the fabrics with soybean oil and nonthermal plasma (NTP), (ii) using water at T = 100 °C as the dye solvent, and (iii) omitting other chemical additives. With a commercial cationic dye, these conditions achieved a color strength in K/S value of 2.28, compared to ~1 for untreated samples. FTIR analysis revealed that a functional network formed on the fibers and yarns of the fabrics by chemical reactions of excited plasma species with double bonds in the soybean oil molecules was responsible for significantly improving the color strength. These results extend the potential uses of a renewable material (soybean oil) and an environmentally friendly technology (NTP) to improve the dyeing of para-aramid textiles and reduce the use of harsh dye chemicals.
RESUMO
BACKGROUND: To utilize the potential of non-thermal plasma technologies for food safety control and sanitation, the inactivation mechanisms of Bacillus amyloliquefaciens spores by non-thermal plasma of ambient air (NTP-AA) were investigated using scanning electron microscopy, atomic force microscopy, attenuated total reflectance Fourier transform infrared spectroscopy with chemometric analysis and proton nuclear magnetic resonance spectroscopy, aiming to probe both the morphological and biochemical changes occurring in spores during the kinetic inactivation process. RESULTS: Kinetic analysis indicates that there is no intrinsic D-value (i.e. time required to inactivate 90% of the spores) in spore inactivation by NTP-AA because we observed non-linear (biphasic) inactivation kinetics and, in addition, the inactivation rate depended on the initial spore concentration and how the spores were exposed to the reactive species in the NTP-AA. The presence of suitable amount of water in the NTP-AA field accelerates spore inactivation. CONCLUSION: Progressive erosion of spore surface by NTP-AA with ensuing or concomitant biochemical damage, which includes the alteration of structural proteins, internal lipids and the loss of dipicolinic acid content from the spore core, represent the main mechanisms of inactivation, and there is evidence that reactive NTP-AA species could penetrate the cortex and reach the core of spores to cause damage. © 2018 Society of Chemical Industry.
Assuntos
Bacillus amyloliquefaciens/crescimento & desenvolvimento , Viabilidade Microbiana/efeitos dos fármacos , Gases em Plasma/farmacologia , Esporos Fúngicos/efeitos dos fármacos , Ar/análise , Bacillus amyloliquefaciens/química , Bacillus amyloliquefaciens/efeitos dos fármacos , Cinética , Esporos Fúngicos/química , Esporos Fúngicos/crescimento & desenvolvimentoRESUMO
The effect of water activity (aw), as lowered by different dietary humectants, on the germination of Bacillus subtilis, Bacillus megaterium and Bacillus cereus spores with germinants that act by different mechanisms has been investigated and compared. Germination of spores of these species by all of the germinants investigated was inhibited as aw decreased, with the general order of efficacy for these non-ionic humectants being sucrose > trehalose > glycerol. The effect of lowering aw on germination by germinant receptor (GR)-dependent germinants was not appreciably altered by varying germinant concentrations, was generally not much more effective with spores lacking coats or an outer membrane, and was less pronounced with heat-activated spores. Analysis of the effect of aw on spore germination via different mechanisms showed that GR-dependent germination was least sensitive to aw, while germination via activation of spore cortex peptidoglycan hydrolysis or dipicolinic acid release was more sensitive. However, germination by high hydrostatic pressure was less sensitive to inhibition by low aw, than was germination by other germinants. Examination of the GR-dependent germination of individual spores indicated that aw acted most strongly in inhibiting the commitment step of germination, while exerting smaller effects on dipicolinic acid release or cortex peptidoglycan hydrolysis.
Assuntos
Bacillus cereus/efeitos dos fármacos , Bacillus megaterium/efeitos dos fármacos , Bacillus subtilis/efeitos dos fármacos , Higroscópicos/farmacologia , Esporos Bacterianos/crescimento & desenvolvimento , Água/metabolismo , Bacillus cereus/crescimento & desenvolvimento , Bacillus cereus/metabolismo , Bacillus megaterium/crescimento & desenvolvimento , Bacillus megaterium/metabolismo , Bacillus subtilis/crescimento & desenvolvimento , Bacillus subtilis/metabolismo , Glicerol/farmacologia , Peptidoglicano/metabolismo , Esporos Bacterianos/efeitos dos fármacos , Esporos Bacterianos/metabolismo , Sacarose/farmacologia , Trealose/farmacologia , Água/análiseRESUMO
UNLABELLED: Raman spectroscopy and phase-contrast microscopy were used to examine calcium dipicolinate (CaDPA) levels and rates of nutrient and nonnutrient germination of multiple individual Bacillus subtilis spores treated with cold atmospheric plasma (CAP). Major results for this work include the following: (i) >5 logs of spores deposited on glass surfaces were inactivated by CAP treatment for 3 min, while deposited spores placed inside an impermeable plastic bag were inactivated only â¼2 logs in 30 min; (ii) >80% of the spores treated for 1 to 3 min with CAP were nonculturable and retained CaDPA in their core, while >95% of spores treated with CAP for 5 to 10 min lost all CaDPA; (iii) Raman measurements of individual CAP-treated spores without CaDPA showed differences from spores that germinated with l-valine in terms of nucleic acids, lipids, and proteins; and (iv) 1 to 2 min of CAP treatment killed 99% of spores, but these spores still germinated with nutrients or exogenous CaDPA, albeit more slowly and to a lesser extent than untreated spores, while spores CAP treated for >3 min that retained CaDPA did not germinate via nutrients or CaDPA. However, even after 1 to 3 min of CAP treatment, spores germinated normally with dodecylamine. These results suggest that exposure to the present CAP configuration severely damages a spore's inner membrane and key germination proteins, such that the treated spores either lose CaDPA or can neither initiate nor complete germination with nutrients or CaDPA. Analysis of the various CAP components indicated that UV photons contributed minimally to spore inactivation, while charged particles and reactive oxygen species contributed significantly. IMPORTANCE: Much research has shown that cold atmospheric plasma (CAP) is a promising tool for the inactivation of spores in the medical and food industries. However, knowledge about the effects of plasma treatment on spore properties is limited, especially at the single-cell level. In this study, Raman spectroscopy and phase-contrast microscopy were used to analyze CaDPA levels and kinetics of nutrient- and non-nutrient-germinant-induced germination of multiple individual spores of Bacillus subtilis that were treated by a planar CAP device. The roles of different plasma species involved in spore inactivation were also investigated. The knowledge obtained in this study will aid in understanding the mechanism(s) of spore inactivation by CAP and potentially facilitate the development of more effective and efficient plasma sterilization techniques in various applications.
Assuntos
Bacillus subtilis/fisiologia , Técnicas Bacteriológicas/métodos , Viabilidade Microbiana , Microscopia de Contraste de Fase , Ácidos Picolínicos/metabolismo , Gases em Plasma/farmacologia , Análise Espectral Raman , Esporos Bacterianos/fisiologia , Esporos Bacterianos/químicaRESUMO
UNLABELLED: This work analyzes the high-pressure (HP) germination of spores of the food-borne pathogen Clostridium perfringens (with inner membrane [IM] germinant receptors [GRs]) and the opportunistic pathogen Clostridium difficile (with no IM GRs), which has growing implications as an emerging food safety threat. In contrast to those of spores of Bacillus species, mechanisms of HP germination of clostridial spores have not been well studied. HP treatments trigger Bacillus spore germination through spores' IM GRs at â¼150 MPa or through SpoVA channels for release of spores' dipicolinic acid (DPA) at ≥400 MPa, and DPA-less spores have lower wet heat resistance than dormant spores. We found that C. difficile spores exhibited no germination events upon 150-MPa treatment and were not heat sensitized. In contrast, 150-MPa-treated unactivated C. perfringens spores released DPA and became heat sensitive, although most spores did not complete germination by fully rehydrating the spore core, but this treatment of heat-activated spores led to almost complete germination and greater heat sensitization. Spores of both clostridial organisms released DPA during 550-MPa treatment, but C. difficile spores did not complete germination and remained heat resistant. Heat-activated 550-MPa-HP-treated C. perfringens spores germinated almost completely and became heat sensitive. However, unactivated 550-MPa-treated C. perfringens spores did not germinate completely and were less heat sensitive than spores that completed germination. Since C. difficile and C. perfringens spores use different mechanisms for sensing germinants, our results may allow refinement of HP methods for their inactivation in foods and other applications and may guide the development of commercially sterile low-acid foods. IMPORTANCE: Spores of various clostridial organisms cause human disease, sometimes due to food contamination by spores. Because of these spores' resistance to normal decontamination regimens, there is continued interest in ways to kill spores without compromising food quality. High hydrostatic pressure (HP) under appropriate conditions can inactivate bacterial spores. With growing use of HP for food pasteurization, advancement of HP for commercial production of sterile low-acid foods requires understanding of mechanisms of spores' interactions with HP. While much is known about HP germination and inactivation of spores of Bacillus species, how HP germinates and inactivates clostridial spores is less well understood. In this work we have tried to remedy this information deficit by examining germination of spores of Clostridium difficile and Clostridium perfringens by several HP and temperature levels. The results may give insight that could facilitate more efficient methods for spore eradication in food sterilization or pasteurization, biodecontamination, and health care.
Assuntos
Clostridium/crescimento & desenvolvimento , Desinfecção/métodos , Esporos Bacterianos/química , Proteínas de Bactérias/genética , Proteínas de Bactérias/metabolismo , Clostridium/química , Clostridium/genética , Clostridium/metabolismo , Pressão , Esporos Bacterianos/crescimento & desenvolvimento , Esporos Bacterianos/metabolismo , TemperaturaRESUMO
Recently, global public health organizations such as Doctors without Borders (MSF), the World Health Organization (WHO), Public Health Canada, National Institutes of Health (NIH), and the U.S. government developed and deployed Field Decontamination Kits (FDKs), a novel, lightweight, compact, reusable decontamination technology to sterilize Ebola-contaminated medical devices at remote clinical sites lacking infra-structure in crisis-stricken regions of West Africa (medical waste materials are placed in bags and burned). The basis for effectuating sterilization with FDKs is chlorine dioxide (ClO2) produced from a patented invention developed by researchers at the US Army Natick Soldier RD&E Center (NSRDEC) and commercialized as a dry mixed-chemical for bacterial spore decontamination. In fact, the NSRDEC research scientists developed an ensemble of ClO2 technologies designed for different applications in decontaminating fresh produce; food contact and handling surfaces; personal protective equipment; textiles used in clothing, uniforms, tents, and shelters; graywater recycling; airplanes; surgical instruments; and hard surfaces in latrines, laundries, and deployable medical facilities. These examples demonstrate the far-reaching impact, adaptability, and versatility of these innovative technologies. We present herein the unique attributes of NSRDEC's novel decontamination technologies and a Case Study of the development of FDKs that were deployed in West Africa by international public health organizations to sterilize Ebola-contaminated medical equipment. FDKs use bacterial spores as indicators of sterility. We review the properties and structures of spores and the mechanisms of bacterial spore inactivation by ClO2. We also review mechanisms of bacterial spore inactivation by novel, emerging, and established non-thermal technologies for food preservation, such as high pressure processing, irradiation, cold plasma, and chemical sanitizers, using an array of Bacillus subtilis mutants to probe mechanisms of spore germination and inactivation. We employ techniques of high-resolution atomic force microscopy and phase contrast microscopy to examine the effects of γ-irradiation on bacterial spores of Bacillus anthracis, Bacillus thuringiensis, and Bacillus atrophaeus spp. and of ClO2 on B. subtilis spores, and present in detail assays using spore bio-indicators to ensure sterility when decontaminating with ClO2.
RESUMO
Nutrient germination of spores of Bacillus species occurs through germinant receptors (GRs) in spores' inner membrane (IM) in a process stimulated by sublethal heat activation. Bacillus subtilis spores maximum germination rates via different GRs required different 75 °C heat activation times: 15 min for l-valine germination via the GerA GR and 4 h for germination with the L-asparagine-glucose-fructose-K(+) mixture via the GerB and GerK GRs, with GerK requiring the most heat activation. In some cases, optimal heat activation decreased nutrient concentrations for half-maximal germination rates. Germination of spores via various GRs by high pressure (HP) of 150 MPa exhibited heat activation requirements similar to those of nutrient germination, and the loss of the GerD protein, required for optimal GR function, did not eliminate heat activation requirements for maximal germination rates. These results are consistent with heat activation acting primarily on GRs. However, (i) heat activation had no effects on GR or GerD protein conformation, as probed by biotinylation by an external reagent; (ii) spores prepared at low and high temperatures that affect spores' IM properties exhibited large differences in heat activation requirements for nutrient germination; and (iii) spore germination by 550 MPa of HP was also affected by heat activation, but the effects were relatively GR independent. The last results are consistent with heat activation affecting spores' IM and only indirectly affecting GRs. The 150- and 550-MPa HP germinations of Bacillus amyloliquefaciens spores, a potential surrogate for Clostridium botulinum spores in HP treatments of foods, were also stimulated by heat activation.
Assuntos
Bacillus subtilis/crescimento & desenvolvimento , Bacillus subtilis/genética , Proteínas de Bactérias/genética , Temperatura Alta , Pressão , Esporos Bacterianos/crescimento & desenvolvimento , Bacillus , Bacillus subtilis/metabolismo , Proteínas de Bactérias/metabolismo , Metabolismo dos Lipídeos , TemperaturaRESUMO
Moisture transport in a food system involving two different materials of unequal moisture content was modeled with water activity as the driving force using a porous media framework. This model was applied to a bread-barbecue chicken pocket sandwich stored in isothermal conditions. The model successfully predicted the equilibrium condition, where the two materials, bread and chicken, reached the same water activity, but not the same water content. The transient changes in the moisture content in the bread and chicken were predicted and shown to be significantly affected by air gap between the bread and chicken. The prediction process was also sensitive to the Darcy permeability values for the materials. The modeling framework presented for a sandwich system is very general and can easily be extended to other multicomponent food systems.
RESUMO
There is a stated Army need for a field-portable, non-steam sterilizer technology that can be used by Forward Surgical Teams, Dental Companies, Veterinary Service Support Detachments, Combat Support Hospitals, and Area Medical Laboratories to sterilize surgical instruments and to sterilize pathological specimens prior to disposal in operating rooms, emergency treatment areas, and intensive care units. The following ensemble of novel, 'clean and green' chlorine dioxide technologies are versatile and flexible to adapt to meet a number of critical military needs for decontamination(6,15). Specifically, the Portable Chemical Sterilizer (PCS) was invented to meet urgent battlefield needs and close critical capability gaps for energy-independence, lightweight portability, rapid mobility, and rugged durability in high intensity forward deployments(3). As a revolutionary technological breakthrough in surgical sterilization technology, the PCS is a Modern Field Autoclave that relies on on-site, point-of-use, at-will generation of chlorine dioxide instead of steam. Two (2) PCS units sterilize 4 surgical trays in 1 hr, which is the equivalent throughput of one large steam autoclave (nicknamed "Bertha" in deployments because of its cumbersome size, bulky dimensions, and weight). However, the PCS operates using 100% less electricity (0 vs. 9 kW) and 98% less water (10 vs. 640 oz.), significantly reduces weight by 95% (20 vs. 450 lbs, a 4-man lift) and cube by 96% (2.1 vs. 60.2 ft(3)), and virtually eliminates the difficult challenges in forward deployments of repairs and maintaining reliable operation, lifting and transporting, and electrical power required for steam autoclaves.
Assuntos
Compostos Clorados/química , Desinfetantes/química , Hospitais Militares , Higiene Militar/instrumentação , Higiene Militar/métodos , Óxidos/química , Esterilização/instrumentação , Esterilização/métodosRESUMO
The Bacillus subtilis spoVAEa and spoVAF genes are expressed in developing spores as members of the spoVA operon, which encodes proteins essential for the uptake and release of dipicolinic acid (DPA) during spore formation and germination. SpoVAF is likely an integral inner spore membrane protein and exhibits sequence identity to A subunits of the spore's nutrient germinant receptors (GRs), while SpoVAEa is a soluble protein with no obvious signals to allow its passage across a membrane. However, like SpoVAD, SpoVAEa is present on the outer surface of the spore's inner membrane, as SpoVAEa was accessible to an external biotinylation agent in spores and SpoVAEa disappeared in parallel with SpoVAD during proteinase K treatment of germinated spores. SpoVAEa and SpoVAD were also distributed similarly in fractions of disrupted dormant spores. Unlike spoVAD, spoVAEa is absent from the genomes of some spore-forming members of the Bacillales and Clostridiales orders, although SpoVAEa's amino acid sequence is conserved in species containing spoVAEa. B. subtilis strains lacking SpoVAF or SpoVAEa and SpoVAF sporulated normally, and the spores had normal DPA levels. Spores lacking SpoVAF or SpoVAEa and SpoVAF also germinated normally with non-GR-dependent germinants but more slowly than wild-type spores with GR-dependent germinants, and this germination defect was complemented by ectopic expression of the missing proteins.
Assuntos
Bacillus subtilis/fisiologia , Proteínas de Bactérias/metabolismo , Regulação Bacteriana da Expressão Gênica/fisiologia , Esporos Bacterianos/fisiologia , Proteínas de Bactérias/genética , Teste de Complementação Genética , Genótipo , MutaçãoRESUMO
Germination of Bacillus spores with a high pressure (HP) of â¼150 MPa is via activation of spores' germinant receptors (GRs). The HP germination of multiple individual Bacillus subtilis spores in a diamond anvil cell (DAC) was monitored with phase-contrast microscopy. Major conclusions were that (i) >95% of wild-type spores germinated in 40 min in a DAC at â¼150 MPa and 37°C but individual spores' germination kinetics were heterogeneous; (ii) individual spores' HP germination kinetic parameters were similar to those of nutrient-triggered germination with a variable lag time (Tlag) prior to a period of the rapid release (ΔTrelease) of the spores' dipicolinic acid in a 1:1 chelate with Ca(2+) (CaDPA); (iii) spore germination at 50 MPa had longer average Tlag values than that at â¼150 MPa, but the ΔTrelease values at the two pressures were identical and HPs of <10 MPa did not induce germination; (iv) B. subtilis spores that lacked the cortex-lytic enzyme CwlJ and that were germinated with an HP of 150 MPa exhibited average ΔTrelease values â¼15-fold longer than those for wild-type spores, but the two types of spores exhibited similar average Tlag values; and (v) the germination of wild-type spores given a ≥30-s 140-MPa HP pulse followed by a constant pressure of 1 MPa was the same as that of spores exposed to a constant pressure of 140 MPa that was continued for ≥35 min; (vi) however, after short 150-MPa HP pulses and incubation at 0.1 MPa (ambient pressure), spore germination stopped 5 to 10 min after the HP was released. These results suggest that an HP of â¼150 MPa for ≤30 s is sufficient to fully activate spores' GRs, which remain activated at 1 MPa but can deactivate at ambient pressure.
Assuntos
Bacillus subtilis/crescimento & desenvolvimento , Pressão Hidrostática , Esporos Bacterianos/crescimento & desenvolvimento , Microscopia de Contraste de FaseRESUMO
As previously reported, gerP Bacillus subtilis spores were defective in nutrient germination triggered via various germinant receptors (GRs), and the defect was eliminated by severe spore coat defects. The gerP spores' GR-dependent germination had a longer lag time between addition of germinants and initiation of rapid release of spores' dipicolinic acid (DPA), but times for release of >90% of DPA from individual spores were identical for wild-type and gerP spores. The gerP spores were also defective in GR-independent germination by DPA with its associated Ca(2+) divalent cation (CaDPA) but germinated better than wild-type spores with the GR-independent germinant dodecylamine. The gerP spores exhibited no increased sensitivity to hypochlorite, suggesting that these spores have no significant coat defect. Overexpression of GRs in gerP spores did lead to faster germination via the overexpressed GR, but this was still slower than germination of comparable gerP(+) spores. Unlike wild-type spores, for which maximal nutrient germinant concentrations were between 500 µM and 2 mM for l-alanine and ≤10 mM for l-valine, rates of gerP spore germination increased up to between 200 mM and 1 M l-alanine and 100 mM l-valine, and at 1 M l-alanine, the rates of germination of wild-type and gerP spores with or without all alanine racemases were almost identical. A high pressure of 150 MPa that triggers spore germination by activating GRs also triggered germination of wild-type and gerP spores identically. All these results support the suggestion that GerP proteins facilitate access of nutrient germinants to their cognate GRs in spores' inner membrane.
Assuntos
Bacillus subtilis/crescimento & desenvolvimento , Bacillus subtilis/genética , Proteínas de Bactérias/genética , Proteínas de Bactérias/metabolismo , Mutação , Esporos Bacterianos/crescimento & desenvolvimento , Esporos Bacterianos/genética , Alanina/metabolismo , Cálcio/metabolismo , Cátions Bivalentes/metabolismo , Pressão Hidrostática , Ácidos Picolínicos/metabolismo , Fatores de Tempo , Valina/metabolismoRESUMO
UNLABELLED: The enhanced quasi-chemical kinetics (EQCK) model is presented as a methodology to evaluate the nonlinear inactivation kinetics of baro-resistant Listeria monocytogenes in a surrogate protein food system by high-pressure processing (HPP) for various combinations of pressure (P= 207 to 414 MPa) and temperature (T= 20 to 50 °C). The EQCK model is based on ordinary differential equations derived from 6 "quasi-chemical reaction" steps. The EQCK model continuously fits the conventional stages of the microbial lifecycle: lag, growth, stationary phase, and death; and tailing. Depending on the conditions, the inactivation kinetics of L. monocytogenes by HPP show a lag, inactivation, and tailing. Accordingly, we developed a customized, 4-step subset version of the EQCK model sufficient to evaluate the HPP inactivation kinetics of L. monocytogenes and obtain values for the model parameters of lag (λ), inactivation rate (µ), rate constants (k), and "processing time" (tp). This latter parameter was developed uniquely to evaluate kinetics data showing tailing. Secondary models are developed by interrelating the fitting parameters with experimental parameters, and Monte Carlo simulations are used to evaluate parameter reproducibility. This 4-step model is also compared with the empirical Weibull and Polylog models. The success of the EQCK model (as its 4-step subset) for the HPP inactivation kinetics of baro-resistant L. monocytogenes showing tailing establishes several advantages of the EQCK modeling approach for investigating nonlinear microbial inactivation kinetics, and it has implications for determining mechanisms of bacterial spore inactivation by HPP. PRACTICAL APPLICATION: Results of this study will be useful to the many segments of the food processing industry (ready-to-eat meats, fresh produce, seafood, dairy) concerned with ensuring the safety of consumers from the health hazards of Listeria monocytogenes, particularly through the use of emerging food preservation technologies such as high-pressure processing.
Assuntos
Microbiologia de Alimentos , Conservação de Alimentos , Listeria monocytogenes/crescimento & desenvolvimento , Pressão , Temperatura , Contagem de Colônia Microbiana , Qualidade de Produtos para o Consumidor , Contaminação de Alimentos/prevenção & controle , Manipulação de Alimentos/métodos , CinéticaRESUMO
The water dynamics and retrogradation kinetics behavior of gelatinized wheat starch by either ultrahigh pressure (UHP) processing or heat are investigated. Wheat starch completely gelatinized in the condition of 90, 000 psi at 25 degrees C for 30 min (pressurized gel) or 100 degrees C for 30 min (heated gel). The physical properties of the wheat starches were characterized in terms of proton relaxation times (T2 times) measured using time-domain nuclear magnetic resonance spectroscopy and evaluated using commercially available continuous distribution modeling software. Different T2 distributions in both micro- and millisecond ranges between pressurized and heated wheat starch gels suggest distinctively different water dynamics between pressurized and heated wheat starch gels. Smaller water self-diffusion coefficients were observed for pressurized wheat starch gels and are indicative of more restricted translational proton mobility than is observed with heated wheat starch gels. The physical characteristics associated with changes taking place during retrogradation were evaluated using melting curves obtained with differential scanning calorimetry. Less retrogradation was observed in pressurized wheat starch, and it may be related to a smaller quantity of freezable water in pressurized wheat starch. Starches comprise a major constituent of many foods proposed for commercial potential using UHP, and the present results furnish insight into the effect of UHP on starch gelatinization and the mechanism of retrogradation during storage.
Assuntos
Manipulação de Alimentos/métodos , Amido/química , Triticum/química , Água/química , Varredura Diferencial de Calorimetria , Géis/química , Temperatura Alta , Espectroscopia de Ressonância Magnética , PressãoRESUMO
Predictive microbial models generally rely on the growth of bacteria in laboratory broth to approximate the microbial growth kinetics expected to take place in actual foods under identical environmental conditions. Sigmoidal functions such as the Gompertz or logistics equation accurately model the typical microbial growth curve from the lag to the stationary phase and provide the mathematical basis for estimating parameters such as the maximum growth rate (MGR). Stationary phase data can begin to show a decline and make it difficult to discern which data to include in the analysis of the growth curve, a factor that influences the calculated values of the growth parameters. In contradistinction, the quasi-chemical kinetics model provides additional capabilities in microbial modelling and fits growth-death kinetics (all four phases of the microbial lifecycle continuously) for a general set of microorganisms in a variety of actual food substrates. The quasi-chemical model is differential equations (ODEs) that derives from a hypothetical four-step chemical mechanism involving an antagonistic metabolite (quorum sensing) and successfully fits the kinetics of pathogens (Staphylococcus aureus, Escherichia coli and Listeria monocytogenes) in various foods (bread, turkey meat, ham and cheese) as functions of different hurdles (a(w), pH, temperature and anti-microbial lactate). The calculated value of the MGR depends on whether growth-death data or only growth data are used in the fitting procedure. The quasi-chemical kinetics model is also exploited for use with the novel food processing technology of high-pressure processing. The high-pressure inactivation kinetics of E. coli are explored in a model food system over the pressure (P) range of 207-345 MPa (30,000-50,000 psi) and the temperature (T) range of 30-50 degrees C. In relatively low combinations of P and T, the inactivation curves are non-linear and exhibit a shoulder prior to a more rapid rate of microbial destruction. In the higher P, T regime, the inactivation plots tend to be linear. In all cases, the quasi-chemical model successfully fit the linear and curvi-linear inactivation plots for E. coli in model food systems. The experimental data and the quasi-chemical mathematical model described herein are candidates for inclusion in ComBase, the developing database that combines data and models from the USDA Pathogen Modeling Program and the UK Food MicroModel.
Assuntos
Bactérias/crescimento & desenvolvimento , Manipulação de Alimentos/métodos , Microbiologia de Alimentos , Modelos Biológicos , Pressão , Temperatura , Pão/microbiologia , Queijo/microbiologia , Contagem de Colônia Microbiana , Escherichia coli/crescimento & desenvolvimento , Escherichia coli O157/crescimento & desenvolvimento , Tecnologia de Alimentos , Cinética , Listeria monocytogenes/crescimento & desenvolvimento , Carne/microbiologia , Modelos Teóricos , Staphylococcus aureus/crescimento & desenvolvimentoRESUMO
Stopped-flow spectrophotometric measurements identify and determine equilibrium data for thiourea (tu) complexes of copper(II) formed in aqueous solution. In excess Cu(II), the complex ion [Cu(tu)](2+) has a stability constant beta(1) = 2.3 +/- 0.1 M(-)(1) and molar absorptivity at 340 nm of epsilon(1) = (4.0 +/- 0.2) x 10(3) M(-)(1) cm(-)(1) at 25.0 degrees C, 2.48 mM HClO(4), and &mgr; = 464 mM (NaClO(4)). The fast reduction of Cu(II) by excess tu obeys the rate law -d[Cu(II)]/dt = k'[Cu(II)](2)[tu](7) with a value for the ninth-order rate constant k' = (1.60 +/- 0.18) x 10(14) M(-)(8) s(-)(1), which derives from a rate-determining step involving the bimolecular decomposition of two complexed Cu(II) species. Copper(II) catalyzes the reduction of hexachloroiridate(IV) by tu according to the rate law -d[IrCl(6)(2)(-)]/dt = (k(2,unc)[tu](2) + k(1,cat) [tu](5)[Cu(II)])[IrCl(6)(2)(-)]. Least-squares analysis yields values of k(2,unc) and k(1,cat) equaling 385 +/- 4 M(-)(2) s(-)(1) and (3.7 +/- 0.1) x 10(13) M(-)(6) s(-)(1), respectively, at &mgr; = 115 mM (NaClO(4)). The corresponding mechanism has a rate-determining step that involves the oxidation of [Cu(II)(tu)(5)](2+) by [IrCl(6)](2)(-) rather than the bimolecular reaction of two cupric-tu complexes.