Coupling of Modes in Step-Index Plastic Optical Fibers by Using D-Shape Technique.

This article presents a technique for reducing the stabilization length of steady-state modes in step-index plastic optical fibers (POFs), which is significant for sensor networks, Internet of Things, signal processing, and data fusion in sensor systems. The results obtained with the com- putational tool developed suggest that the D-shape created in the POF effectively reduces the stabi- lization length of the modes and, by extension, minimizes the dispersion effects of the modes by filtering out high-order modes. Applying the analysis to commercial POFs, the authors experimen- tally verified a reduction in the stabilization length of modes from 27 to 10 m and from 20 m to 5 m. Reducing the mode stabilization length minimizes the bit error rate (BER) in short-length SI-POF- based optical links operating at 250 Mbp/s. A reduction from 7.6 × 10-7 to 3.7 × 10-10 was achieved.

Visualizing Street Pavement Anomalies through Fog Computing V2I Networks and Machine Learning.

Analyzing data related to the conditions of city streets and avenues could help to make better decisions about public spending on mobility. Generally, streets and avenues are fixed as soon as they have a citizen report or when a major incident occurs. However, it is uncommon for cities to have real-time reactive systems that detect the different problems they have to fix on the pavement. This work proposes a solution to detect anomalies in streets through state analysis using sensors within the vehicles that travel daily and connecting them to a fog-computing architecture on a V2I network. The system detects and classifies the main road problems or abnormal conditions in streets and avenues using Machine Learning Algorithms (MLA), comparing roughness against a flat reference. An instrumented vehicle obtained the reference through accelerometry sensors and then sent the data through a mid-range communication system. With these data, the system compared an Artificial Neural Network (supervised MLA) and a K-Nearest Neighbor (Supervised MLA) to select the best option to handle the acquired data. This system makes it desirable to visualize the streets' quality and map the areas with the most significant anomalies.

X-ray Characterization of Conformational Changes of Human Apo- and Holo-Transferrin.

Human serum transferrin (Tf) is a bilobed glycoprotein whose function is to transport iron through receptor-mediated endocytosis. The mechanism for iron release is pH-dependent and involves conformational changes in the protein, thus making it an attractive system for possible biomedical applications. In this contribution, two powerful X-ray techniques, namely Macromolecular X-ray Crystallography (MX) and Small Angle X-ray Scattering (SAXS), were used to study the conformational changes of iron-free (apo) and iron-loaded (holo) transferrin in crystal and solution states, respectively, at three different pH values of physiological relevance. A crystallographic model of glycosylated apo-Tf was obtained at 3.0 Å resolution, which did not resolve further despite many efforts to improve crystal quality. In the solution, apo-Tf remained mostly globular in all the pH conditions tested; however, the co-existence of closed, partially open, and open conformations was observed for holo-Tf, which showed a more elongated and flexible shape overall.

Combination of Cymbopogon citratus and Allium cepa essential oils increased antibacterial activity in leafy vegetables.

BACKGROUND: Cymbopogon citratus and Allium cepa essential oils (EOs) are rich in terpenes and sulfur compounds respectively, both with antibacterial activity and different cell targets, supporting the idea that their combination can increase their efficacy. RESULTS: Major constituents of C. citratus were geranial and neral, while A. cepa presented dipropyl disulfide and dipropyl trisulfide. Cymbopogon citratus and A. cepa EOs inhibited the in vitro growth of Escherichia coli O157:H7 (minimal inhibitory concentrations of 2.21 and 5.13 g L-1 respectively), Salmonella Choleraesuis (3.04 and 1.28 g L-1 ), Listeria monocytogenes (1.33 and 2.56 g L-1 ) and Staphylococcus aureus (0.44 and 5.26 g L-1 ). Application of the EO combination to spinach caused a greater reduction in E. coli (2.34 log colony-forming units (CFU) g-1 ), S. Choleraesuis (2.94 log CFU g-1 ), L. monocytogenes (2.06 log CFU g-1 ) and S. aureus (1.37 log CFU g-1 ) compared with higher doses of individual EOs; a similar effect was observed for romaine lettuce. Individual and combined EOs caused a reduction in flavor acceptability level; however, no significant differences were found among odor acceptability of control vegetables and those treated with the EO combination and C. citratus EO. CONCLUSION: Leafy vegetables treated with the EO combination showed higher antibacterial protection and odor acceptability compared with individual EO treatments. © 2016 Society of Chemical Industry.

Oregano (Lippia graveolens) essential oil added within pectin edible coatings prevents fungal decay and increases the antioxidant capacity of treated tomatoes.

BACKGROUND: Tomato is a fruit widely consumed due to its flavor and nutritional value; however, it is susceptible to fungi contamination. Oregano essential oil (OEO) is a fungicide whose constituents are volatile; therefore, their incorporation within edible coatings can protect them and maintain their efficacy. In this context, this study evaluated the effect of OEO applied within pectin coatings on the inhibition of Alternaria alternata growth, antioxidant content and sensorial acceptability of tomatoes. RESULTS: The major volatile compounds of OEO were carvacrol (47.41%), p-cymene (26.44%) and thymol (3.02%). All the applied OEO concentrations (15.7, 25.9 and 36.1 g L(-1) ) inhibited the in vitro growth of A. alternata, whereas the in vivo effective concentrations were 25.9 and 36.1 g L(-1) . Additionally, there was an increment of total phenols and antioxidant activity in coated tomatoes compared to controls. Aroma acceptability of tomatoes was not affected by the pectin-OEO coating; additionally, the pectin, pectin-OEO 15.7 g L(-1) treatments and control tomatoes showed higher flavor acceptability than those coated with pectin-OEO 25.9 and 36.1 g L(-1) . CONCLUSION: Pectin-OEO coatings showed antifungal effect and increased the antioxidant activity without negative effects on the sensorial acceptability of tomatoes. © 2015 Society of Chemical Industry.

A vertebrate-conserved cis-regulatory module for targeted expression in the main hypothalamic regulatory region for the stress response.

BACKGROUND: The homeodomain transcription factor orthopedia (Otp) is an evolutionarily conserved regulator of neuronal fates. In vertebrates, Otp is necessary for the proper development of different regions of the brain and is required in the diencephalon to specify several hypothalamic cell types, including the cells that control the stress response. To understand how this widely expressed transcription factor accomplishes hypothalamus-specific functions, we performed a comprehensive screening of otp cis-regulatory regions in zebrafish. RESULTS: Here, we report the identification of an evolutionarily conserved vertebrate enhancer module with activity in a restricted area of the forebrain, which includes the region of the hypothalamus that controls the stress response. This region includes neurosecretory cells producing Corticotropin-releasing hormone (Crh), Oxytocin (Oxt) and Arginine vasopressin (Avp), which are key components of the stress axis. Lastly, expression of the bacterial nitroreductase gene under this specific enhancer allowed pharmacological attenuation of the stress response in zebrafish larvae. CONCLUSION: Vertebrates share many cellular and molecular components of the stress response and our work identified a striking conservation at the cis-regulatory level of a key hypothalamic developmental gene. In addition, this enhancer provides a useful tool to manipulate and visualize stress-regulatory hypothalamic cells in vivo with the long-term goal of understanding the ontogeny of the stress axis in vertebrates.

Optimizing industrial transport with a connected automated vehicle demonstrator for assembly systems and end-of-line production.

In recent years, the automotive industry has witnessed significant progress in the development of automated driving technologies. The integration of advanced sensors and systems in vehicles has led to the emergence of various functionalities, such as driving assistance and autonomous driving. Applying these technologies on the assembly line can enhance the efficiency, safety, and speed of transportation, especially at end-of-line production. This work presents a connected automated vehicle (CAV) demonstrator for generating autonomous driving systems and services for the automotive industry. Our prototype electric vehicle is equipped with state-of-the-art sensors and systems for perception, localization, navigation, and control. We tested various algorithms and tools for transforming the vehicle into a self-driving platform, and the prototype was simulated and tested in an industrial environment as proof of concept for integration into assembly systems and end-of-line transport. Our results show the successful integration of self-driving vehicle platforms in the automotive industry, particularly in factory halls. We demonstrate the localization, navigation, and communication capabilities of our prototype in a demo area. This work anticipates a significant increase in efficiency and operating cost reduction in vehicle manufacturing, despite challenges such as current low traveling speeds and high equipment costs. Ongoing research aims to enhance safety for higher vehicle speeds, making it a more viable business case for manufacturers, considering the increasing standardization of automated driving equipment in cars. The main contribution of this paper lies in introducing the general concept architecture of the integration of automated driving functionalities in end-of-line assembly and production systems. Showing a case study of the effective development and implementation of such functionalities with a CAV demonstrator in a more standardized industrial operational design domain.

Forcing vine regrowth under different irrigation strategies: effect on polyphenolic composition and chromatic characteristics of cv. Tempranillo wines grown in a semiarid climate.

One of the effects of climate change in warm areas is the asynchrony between the dates of the technological and the phenolic maturity of grapes. This is important because the quality and color stability of red wines are directly related to the content and distribution of phenolic compounds. A novel alternative that has been proposed to delay grape ripening and make it coincide with a seasonal period more favorable for the formation of phenolic compounds is crop forcing. This consists of severe green pruning after flowering, when the buds of the following year have already differentiated. In this way, the buds formed during the same season are forced to sprout, initiating a new delayed cycle. The aim of the present work is to study the effect on the phenolic composition and color of wines elaborated from vines fully irrigated (C), grown using conventional non-forcing (NF) and forcing (F) techniques (C-NF and C-F), and wines from vines subjected to regulated irrigation (RI), grown using NF and F techniques (RI-NF and RI-F). The trial was carried out in an experimental vineyard of the Tempranillo variety located in a semi-arid area (Badajoz, Spain) in the 2017-2019 seasons. The wines (four by treatment) were elaborated and stabilized according to the classic methodologies for red wine. All wines had the same alcohol content, and malolactic fermentation was not carried out in any of them. Anthocyanin profiles were analyzed by HPLC, and total polyphenolic content, anthocyanin content, catechin content, the contribution to color due to co-pigmented anthocyanins, and various chromatic parameters were also determined. Although a significant effect of year was found for almost all the parameters analyzed, a general increasing trend in F wines was found for most of them. The anthocyanin profile of F wines was found to differ from that of C wines, especially in delphinidin, cyanidin, petunidin, and peonidin content. These results indicate that by using the forcing technique it was possible to increase the polyphenolic content by ensuring that the synthesis and accumulation of these substances occurred at more suitable temperatures.

Investigations on the Role of Iron (III) and Silica-Iron (III) for DNA Protection Against Highly Intense UV Radiation: Tracking the Connection of Prebiotic Chemistry to Biology.

The mineral reaction pathways that yield organic compounds of increasing complexity would have required a means of protective screening against strong ultraviolet radiation for macromolecular assembly on early Earth. In this study, a bacterial chromosomal plasmid DNA was used as a model biomolecule that represents a complex polymeric nucleic acid containing genetic information. The plasmid DNA was exposed to UV radiation through a medium containing air, water, iron (Fe3+), or silica-iron rich aqueous solutions. Our results demonstrate that the plasmid DNA underwent covalent breakage in an aqueous solution when exposed to UV radiation but was shielded against damage due to the presence of iron and silica. It is demonstrated that a suspension of ca. 40 nm colloidal particles of silica gel embedded with Fe3+ ions adsorbed on silanol groups that formed nanoclusters of noncrystalline iron hydroxide is an extremely efficient shelter against intense UV radiation. The implications for our understanding of primitive Earth and Earth-like planets, moons, and asteroids are discussed. The stability of a chromosomal DNA molecule against UV radiation in the presence of iron and silica may provide support on how macromolecules endured early Earth environments and brought forth important implications on early molecular survival against UV radiation.

Methanolysis of Poly(lactic Acid) Using Catalyst Mixtures and the Kinetics of Methyl Lactate Production.

Polylactic acid (PLA) is a leading bioplastic of which the market share is predicted to increase in the future; its growing production capacity means its end-of-life treatment is becoming increasingly important. One beneficial disposal route for PLA is its chemical recycling via alcoholysis. The alcoholysis of PLA leads to the generation of value-added products alkyl lactates; this route also has potential for a circular economy. In this work, PLA was chemically recycled via methanolysis to generate methyl lactate (MeLa). Four commercially available catalysts were investigated: zinc acetate dihydrate (Zn(OAc)2), magnesium acetate tetrahydrate (Mg(OAc)2), 4-(dimethylamino)pyridine (DMAP), and triazabicyclodecene (TBD). Dual catalyst experiments displayed an increase in reactivity when Zn(OAc)2 was paired with TBD or DMAP, or when Mg(OAc)2 was paired with TBD. Zn(OAc)2 coupled with TBD displayed the greatest reactivity. Out of the single catalyst reactions, Zn(OAc)2 exhibited the highest activity: a higher mol% was found to increase reaction rate but plateaued at 4 mol%, and a higher equivalent of methanol was found to increase the reaction rate, but plateaued at 17 equivalents. PLA methanolysis was modelled as a two-step reversible reaction; the activation energies were estimated at: Ea1 = 25.23 kJ∙mol-1, Ea2 = 34.16 kJ∙mol-1 and Ea-2 = 47.93 kJ∙mol-1.

Experimental data of cathodes manufactured in a convective dryer at the pilot-plant scale, and charge and discharge capacities of half-coin lithium-ion cells.

Megtec Systems pilot-plant scale continuous convective coater. The data was generated as part of an experimental design involving the following coating-drying process variables and ranges: comma bar gap, 80-140 µm; web speed, 0.5-1.5 m/min; coating ratio, 110-150%; drying temperature, 85-110 °C and drying air speed, 5-15 m/s. The manufacturing data include pre-calendered coating thickness, mass loading dry and wet, pre-calendered porosity, spatial autocorrelation and join counting (SAJC) Z-score for carbon and for fluorine, cell thickness, coating weight and porosity of 15 different electrode coatings and 45 half-coin cells. The electrochemical data was obtained at 25 °C in a Maccor 4000 series battery cycler and consists of charge and discharge capacities at C/20, C/5, C/2, 1C, 2C, 5C and 10C C-rates. Discharge gravimetric and volumetric capacities, rate performance (at 5C:0.2C) and first cycle loss data is also reported. Details of the experimental design and a comprehensive analysis of the data can be found in the co-submitted manuscript (Román-Ramírez et al., 2021). Additional collected data not used in Román-Ramírez et al. (2021) is reported in the present manuscript and include visual observations of coating defects, rheological properties of the electrode slurries (solid content, viscosity, coating shear rate and viscosity at coating shear rate), room temperature and room humidity during the coatings and first cycle loss of the coin cells. Raw and analyzed data is made available. The reported data can be used to extend the analysis reported in Román-Ramírez et al. (2021), and for the comparison of relevant data obtained at different manufacturing scales.

Predictors of Septic Shock or Bacteremia in Children Experiencing Febrile Neutropenia Post-Chemotherapy.

BACKGROUND: Febrile neutropenia (FN) is an early indicator of infection in oncology patients post-chemotherapy. We aimed to determine clinical predictors of septic shock and/or bacteremia in pediatric cancer patients experiencing FN and to create a model that classifies patients as low-risk for these outcomes. METHODS: This is a retrospective analysis with clinical data of a cohort of pediatric oncology patients admitted during July 2015 to September 2017 with FN. One FN episode per patient was randomly selected. Statistical analyses include distribution analysis, hypothesis testing, and multivariate logistic regression to determine clinical feature association with outcomes. RESULTS: A total of 865 episodes of FN occurred in 429 subjects. In the 404 sampled episodes that were analyzed, 20.8% experienced outcomes of septic shock and/or bacteremia. Gram-negative bacteria count for 70% of bacteremias. Features with statistically significant influence in predicting these outcomes were hematological malignancy (P < .001), cancer relapse (P = .011), platelet count (P = .004), and age (P = .023). The multivariate logistic regression model achieves AUROC = 0.66 (95% CI 0.56-0.76). The optimal classification threshold achieves sensitivity = 0.96, specificity = 0.33, PPV = 0.40, and NPV = 0.95. CONCLUSIONS: This model, based on simple clinical variables, can be used to identify patients at low-risk of septic shock and/or bacteremia. The model's NPV of 95% satisfies the priority to avoid discharging patients at high-risk for adverse infection outcomes. The model will require further validation on a prospective population.

A dominant function of LynB kinase in preventing autoimmunity.

Here, we report that the LynB splice variant of the Src-family kinase Lyn exerts a dominant immunosuppressive function in vivo, whereas the LynA isoform is uniquely required to restrain autoimmunity in female mice. We used CRISPR-Cas9 gene editing to constrain lyn splicing and expression, generating single-isoform LynA knockout (LynAKO) or LynBKO mice. Autoimmune disease in total LynKO mice is characterized by production of antinuclear antibodies, glomerulonephritis, impaired B cell development, and overabundance of activated B cells and proinflammatory myeloid cells. Expression of LynA or LynB alone uncoupled the developmental phenotype from the autoimmune disease: B cell transitional populations were restored, but myeloid cells and differentiated B cells were dysregulated. These changes were isoform-specific, sexually dimorphic, and distinct from the complete LynKO. Despite the apparent differences in disease etiology and penetrance, loss of either LynA or LynB had the potential to induce severe autoimmune disease with parallels to human systemic lupus erythematosus (SLE).

Antibiofilm Action of Plant Terpenes in Salmonella Strains: Potential Inhibitors of the Synthesis of Extracellular Polymeric Substances.

Salmonella can form biofilms that contribute to its resistance in food processing environments. Biofilms are a dense population of cells that adhere to the surface, creating a matrix composed of extracellular polymeric substances (EPS) consisting mainly of polysaccharides, proteins, and eDNA. Remarkably, the secreted substances, including cellulose, curli, and colanic acid, act as protective barriers for Salmonella and contribute to its resistance and persistence when exposed to disinfectants. Conventional treatments are mostly ineffective in controlling this problem; therefore, exploring anti-biofilm molecules that minimize and eradicate Salmonella biofilms is required. The evidence indicated that terpenes effectively reduce biofilms and affect their three-dimensional structure due to the decrease in the content of EPS. Specifically, in the case of Salmonella, cellulose is an essential component in their biofilms, and its control could be through the inhibition of glycosyltransferase, the enzyme that synthesizes this polymer. The inhibition of polymeric substances secreted by Salmonella during biofilm development could be considered a target to reduce its resistance to disinfectants, and terpenes can be regarded as inhibitors of this process. However, more studies are needed to evaluate the effectiveness of these compounds against Salmonella enzymes that produce extracellular polymeric substances.

Antimalarial treatment may have a time-dependent effect on lupus survival: data from a multinational Latin American inception cohort.

OBJECTIVE: To evaluate the beneficial effect of antimalarial treatment on lupus survival in a large, multiethnic, international longitudinal inception cohort. METHODS: Socioeconomic and demographic characteristics, clinical manifestations, classification criteria, laboratory findings, and treatment variables were examined in patients with systemic lupus erythematosus (SLE) from the Grupo Latino Americano de Estudio del Lupus Eritematoso (GLADEL) cohort. The diagnosis of SLE, according to the American College of Rheumatology criteria, was assessed within 2 years of cohort entry. Cause of death was classified as active disease, infection, cardiovascular complications, thrombosis, malignancy, or other cause. Patients were subdivided by antimalarial use, grouped according to those who had received antimalarial drugs for at least 6 consecutive months (user) and those who had received antimalarial drugs for <6 consecutive months or who had never received antimalarial drugs (nonuser). RESULTS: Of the 1,480 patients included in the GLADEL cohort, 1,141 (77%) were considered antimalarial users, with a mean duration of drug exposure of 48.5 months (range 6-98 months). Death occurred in 89 patients (6.0%). A lower mortality rate was observed in antimalarial users compared with nonusers (4.4% versus 11.5%; P< 0.001). Seventy patients (6.1%) had received antimalarial drugs for 6-11 months, 146 (12.8%) for 1-2 years, and 925 (81.1%) for >2 years. Mortality rates among users by duration of antimalarial treatment (per 1,000 person-months of followup) were 3.85 (95% confidence interval [95% CI] 1.41-8.37), 2.7 (95% CI 1.41-4.76), and 0.54 (95% CI 0.37-0.77), respectively, while for nonusers, the mortality rate was 3.07 (95% CI 2.18-4.20) (P for trend < 0.001). After adjustment for potential confounders in a Cox regression model, antimalarial use was associated with a 38% reduction in the mortality rate (hazard ratio 0.62, 95% CI 0.39-0.99). CONCLUSION: Antimalarial drugs were shown to have a protective effect, possibly in a time-dependent manner, on SLE survival. These results suggest that the use of antimalarial treatment should be recommended for patients with lupus.

Comparative Study on the Hydrogenation of Naphthalene over Both Al2O3-Supported Pd and NiMo Catalysts against a Novel LDH-Derived Ni-MMO-Supported Mo Catalyst.

Naphthalene hydrogenation was studied over a novel Ni-Al-layered double hydroxide-derived Mo-doped mixed metal oxide (Mo-MMO), contrasted against bifunctional NiMo/Al2O3, and Pd-doped Al2O3 catalysts, the latter of which with Pd loadings of 1, 2, and 5 wt %. Reaction rate constants were derived from a pseudo-first-order kinetic pathway describing a two-step hydrogenation pathway to tetralin (k 1) and decalin (k 2). The Mo-MMO catalyst achieved comparable reaction rates to Pd2%/Al2O3 at double concentration. When using Pd5%/Al2O3, tetralin hydrogenation was favored over naphthalene hydrogenation culminating in a k 2 value of 0.224 compared to a k 1 value of 0.069. Ni- and Mo-based catalysts produced the most significant cis-decalin production, with Mo-MMO culminating at a cis/trans ratio of 0.62 as well as providing enhanced activity in naphthalene hydrogenation compared to NiMo/Al2O3. Consequently, Mo-MMO presents an opportunity to generate more alkyl naphthenes in subsequent hydrodecyclization reactions and therefore a higher cetane number in transport fuels. This is contrasted by a preferential production of trans-decalin observed when using all of the Al2O3-supported Pd catalysts, as a result of octalin intermediate orientations on the catalyst surface as a function of the electronic properties of Pd catalysts.

Monocyte activation by apoptotic cells removal in systemic lupus erythematosus patients.

Decreased apoptotic cells (ACs) removal has been described as relevant in systemic lupus erythematosus (SLE) pathogenesis. Binding/phagocytosis of ACs was decreased in SLE patients. Blocking experiments suggested a role for CD36 in ACs clearance in healthy controls, not observed in SLE patients. Binding/phagocytosis of ACs induced the production of IL-6, CXCL8 and CCL22 in patients and controls and IL-1ß, TNF-α and CCL3 only in healthy controls. ACs clearance induced an increase in CD80 and a decrease in CD86 expression in healthy controls and atherosclerotic patients. However, SLE patients did not up-regulate CD80 expression. The number and expression of CD36 and CD163 in monocytes was not different between the groups. ACs removal induced a down-regulation of CD36 expression in adherent HLA-DR(+) cells in SLE patients but not healthy controls. The decreased binding/phagocytosis of ACs observed in SLE patients, induces a distinct immune response compared with healthy controls.

Two-step counterdiffusion protocol for the crystallization of haemoglobin II from Lucina pectinata in the pH range 4-9.

Lucina pectinata haemoglobin II (HbII) transports oxygen in the presence of H(2)S to the symbiotic system in this bivalve mollusc. The composition of the haem pocket at the distal site includes TyrB10 and GlnE7, which are very common in other haem proteins. Obtaining crystals of oxyHbII at various pH values is required in order to elucidate the changes in the conformations of TyrB10 and GlnE7 and structural scenarios induced by changes in pH. Here, the growth of crystals of oxyHbII using the capillary counterdiffusion (CCD) technique at various pH values using a two-step protocol is reported. In the first step, a mini-screen was used to validate sodium formate as the best precipitating reagent for the growth of oxyHbII crystals. The second step, a pH screen typically used for optimization, was used to produce crystals in the pH range 4-9. Very well faceted prismatic ruby-red crystals were obtained at all pH values. X-ray data sets were acquired using synchrotron radiation of wavelength 0.886 A (for the crystals obtained at pH 5) and 0.908 A (for those obtained at pH 4, 8 and 9) to maximum resolutions of 3.30, 1.95, 1.85 and 2.00 A for the crystals obtained at pH 4, 5, 8 and 9, respectively. All of the crystals were isomorphous and belonged to space group P4(2)2(1)2.

Kinetics of Methyl Lactate Formation from the Transesterification of Polylactic Acid Catalyzed by Zn(II) Complexes.

The kinetics of the transesterification of polylactic acid (PLA) with methanol to form methyl lactate catalyzed by Zn(II) complexes was studied experimentally and numerically. The complexes, Zn(1 Et )2 and Zn(2 Pr )2, were synthesized from ethylenediamine and propylenediamine Schiff bases, respectively. The temperature range covered was 313.2-383.2 K. An increase in the reaction rate with the increase in temperature was observed for the Zn(1 Et )2-catalyzed reaction. The temperature relationship of the rate coefficients can be explained by a linear Arrhenius dependency with constant activation energy. The kinetics of Zn(2 Pr )2, on the other hand, is only explained by non-Arrhenius kinetics with convex variable activation energy, resulting in faster methyl lactate production rates at 323.2 and 343.2 K. The formation of a new catalyst species, likely through reaction with protic reagents, appears to promote the formation of intermediate complexes, resulting in the nonlinear behavior. Stirring speed induced the stability of the intermediate complexes. Contrary to Zn(1 Et )2, Zn(2 Pr )2 was susceptible to the presence of air/moisture in solution. The kinetic parameters were obtained by fitting the experimental data to the mass and energy balance of a consecutive second step reversible reaction taking place in a jacketed stirred batch reactor. For the case of Zn(2 Pr )2, the activation energy was fitted to a four-parameter equation. The kinetic parameters presented in this work are valuable for the design of processes involving the chemical recycling of PLA into green solvents.

Chemical Degradation of End-of-Life Poly(lactic acid) into Methyl Lactate by a Zn(II) Complex.

The catalyzed methanolysis of end-of-life poly(lactic acid) (PLA) products by an ethylenediamine Zn(II) complex to form biodegradable methyl lactate was studied experimentally at 70, 90, and 110 °C. The PLA samples consisted of typical consumer waste materials, including a cup, a toy, and a three-dimensional (3D) printing material. High selectivities and yields (>94%) were possible depending on temperature and reaction time. Additionally, and to develop a predictive kinetic model, kinetic parameters (pre-exponential factor and activation energies) of the PLA transesterification reaction were first obtained from virgin PLA. These parameters were subsequently used to estimate the conversion of PLA, selectivity, and yield of methyl lactate after 1 and 4 h of the reaction, and the results were compared with the experimental values of the end-of-life PLA. Despite the presence of unknown additives in the PLA waste material and uncontrolled particle size, the model was able to predict the overall conversion, selectivity, and yield to an average deviation of 5, 7, and 12%, respectively. A greater agreement between the model and experimental values is observed for the higher temperatures and the longer reaction time. Larger deviations were observed for the PLA toy, which we attribute to the presence of additives, since despite its lower molecular weight, it possessed a higher structural strength.