RESUMO
The enzyme PETase fromIdeonella sakaiensis (IsPETase) strain 201-F6 can catalyze the hydrolysis of polyethylene terephthalate (PET), mainly converting it into mono(2-hydroxyethyl) terephthalic acid (MHET). In this study, we used quantum mechanics/molecular mechanics (QM/MM) simulations to explore the molecular details of the catalytic reaction mechanism of IsPETase in the formation of MHET. The QM region was described with AM1d/PhoT and M06-2X/6-31+G(d,p) potential. QM/MM simulations unveil the complete enzymatic PET hydrolysis mechanism and identify two possible reaction pathways for acylation and deacylation steps. The barrier obtained at M06-2X/6-31+G(d,p)/MM potential for the deacylation step corresponds to 20.4 kcal/mol, aligning with the experimental value of 18 kcal/mol. Our findings indicate that deacylation is the rate-limiting step of the process. Furthermore, per-residue interaction energy contributions revealed unfavorable contributions to the transition state of amino acids located at positions 200-230, suggesting potential sites for targeted mutations. These results can contribute to the development of more active and selective enzymes for PET depolymerization.
Assuntos
Polietilenotereftalatos , Teoria Quântica , Polietilenotereftalatos/química , Polietilenotereftalatos/metabolismo , Simulação de Dinâmica Molecular , Burkholderiales/enzimologia , Burkholderiales/metabolismo , Hidrólise , Biodegradação Ambiental , Biocatálise , AcilaçãoRESUMO
Carboxylesterases comprise a major class of α/ß-fold hydrolases responsible for the cleavage and formation of ester bonds. Found ubiquitously in nature, these enzymes are crucial for the metabolism of both endogenous and exogenous carboxyl esters in animals, plants and microorganisms. Beyond their essential physiological roles, carboxylesterases stand out as one of the important classes of biocatalysts for biotechnology. BlEst2, an enzyme previously classified as Bacillus licheniformis esterase, remains largely uncharacterized. In the present study, we elucidate the structural biology, molecular dynamics and biochemical features of BlEst2. Our findings reveal a canonical α/ß-hydrolase fold similar to the ESTHER block L of lipases, further augmented by two additional accessory C-terminal domains. Notably, the catalytic domain demonstrates two insertions, which occupy conserved locations in α/ß-hydrolase proteins and commonly form the lid domain in lipase structures. Intriguingly, our in vitro cleavage of C-terminal domains revealed the structure of the active form of BlEst2. Upon activation, BlEst2 showed a markedly elevated hydrolytic activity. This observation implies that the intramolecular C-terminal domain serves as a regulatory intramolecular inhibitor. Interestingly, despite exhibiting esterase-like activity, BlEst2 structural characteristics align more closely with lipases. This suggests that BlEst2 could potentially represent a previously unrecognized subgroup within the realm of carboxyl ester hydrolases.
RESUMO
Using machine learning, molecular dynamics simulations, and density functional theory calculations we gain insight into the selectivity patterns of substrate activation by the cytochromes P450. In nature, the reactions catalyzed by the P450s lead to the biodegradation of xenobiotics, but recent work has shown that fungi utilize P450s for the activation of lignin fragments, such as monomer and dimer units. These fragments often are the building blocks of valuable materials, including drug molecules and fragrances, hence a highly selective biocatalyst that can produce these compounds in good yield with high selectivity would be an important step in biotechnology. In this work a detailed computational study is reported on two reaction channels of two P450 isozymes, namely the O-deethylation of guaethol by CYP255A and the O-demethylation versus aromatic hydroxylation of p-anisic acid by CYP199A4. The studies show that the second-coordination sphere plays a major role in substrate binding and positioning, heme access, and in the selectivity patterns. Moreover, the local environment affects the kinetics of the reaction through lowering or raising barrier heights. Furthermore, we predict a site-selective mutation for highly specific reaction channels for CYP199A4.
Assuntos
Sistema Enzimático do Citocromo P-450 , Lignina , Aprendizado de Máquina , Simulação de Dinâmica Molecular , Sistema Enzimático do Citocromo P-450/metabolismo , Sistema Enzimático do Citocromo P-450/química , Lignina/química , Lignina/metabolismo , Engenharia de Proteínas , Teoria da Densidade FuncionalRESUMO
The metrological quality of a measurement is characterised by evaluating the uncertainty in the measurement. In this paper, uncertainty in personal dose measured using individual monitoring CaSO4:Dy-based thermoluminescence dosimeter badge is evaluated by application of the guide to the expression of uncertainty in measurement method. The present dose reporting quantity, whole body dose (WBD) and the proposed quantity, personal dose equivalent, Hp(10) has been used as measurands. The influence of various input quantities on the measurement were analyzed through tests that conform to the requirements of the International Electrotechnical Commission IEC 62387. The study found that the expanded uncertainties for WBD and Hp(10) measurements were 63.4% and 41.4%, respectively, corresponding to a 95% coverage probability for workplace fields covering a wide photon energy range (33-1250 keV). However, the uncertainty estimates were quite lower for the type of workplaces that are identified using the dose evaluation algorithm. The input quantities, namely, the response to a mixture of photon beam qualities and photon energy and angular dependence contribute the most to the total uncertainty.
Assuntos
Exposição Ocupacional , Doses de Radiação , Dosimetria Termoluminescente , Local de Trabalho , Dosimetria Termoluminescente/instrumentação , Dosimetria Termoluminescente/métodos , Humanos , Exposição Ocupacional/análise , Incerteza , Monitoramento de Radiação/métodos , Algoritmos , Disprósio/química , Fótons , Proteção Radiológica/métodos , Proteção Radiológica/normas , Dosímetros de RadiaçãoRESUMO
Reversible crosslinkers can enable several desirable mechanical properties, such as improved toughness and self-healing, when incorporated in polymer networks for bioengineering and structural applications. In this work, we performed coarse-grained molecular dynamics to investigate the effect of the energy landscape of reversible crosslinkers on the dynamic mechanical properties of crosslinked polymer network hydrogels. We report that, for an ideal network, the energy potential of the crosslinker interaction drives the viscosity of the network, where a stronger potential results in a higher viscosity. Additional topographical analyses reveal a mechanistic understanding of the structural rearrangement of the network as it deforms and indicate that as the number of defects increases in the network, the viscosity of the network increases. As an important validation for the relationship between the energy landscape of a crosslinker chemistry and the resulting dynamic mechanical properties of a crosslinked ideal network hydrogel, this work enhances our understanding of deformation mechanisms in polymer networks that cannot easily be revealed by experiment and reveals design ideas that can lead to better performance of the polymer network at the macroscale.
RESUMO
Chikungunya virus (CHIKV) is a mosquito-borne alphavirus that causes acute, subacute, and chronic human arthritogenic diseases and, in rare instances, can lead to neurological complications and death. Here, we combined epidemiological, virological, histopathological, cytokine, molecular dynamics, metabolomic, proteomic, and genomic analyses to investigate viral and host factors that contribute to chikungunya-associated (CHIK) death. Our results indicate that CHIK deaths are associated with multi-organ infection, central nervous system damage, and elevated serum levels of pro-inflammatory cytokines and chemokines compared with survivors. The histopathologic, metabolite, and proteomic signatures of CHIK deaths reveal hemodynamic disorders and dysregulated immune responses. The CHIKV East-Central-South-African lineage infecting our study population causes both fatal and survival cases. Additionally, CHIKV infection impairs the integrity of the blood-brain barrier, as evidenced by an increase in permeability and altered tight junction protein expression. Overall, our findings improve the understanding of CHIK pathophysiology and the causes of fatal infections.
Assuntos
Febre de Chikungunya , Vírus Chikungunya , Animais , Humanos , Febre de Chikungunya/complicações , Proteômica , Vírus Chikungunya/genética , Citocinas/metabolismoRESUMO
GH 62 arabinofuranosidases are known for their excellent specificity for arabinoxylan of agroindustrial residues and their synergism with endoxylanases and other hemicellulases. However, the low thermostability of some GH enzymes hampers potential industrial applications. Protein engineering research highly desires mutations that can enhance thermostability. Therefore, we employed directed evolution using one round of error-prone PCR and site-saturation mutagenesis for thermostability enhancement of GH 62 arabinofuranosidase from Aspergillus fumigatus. Single mutants with enhanced thermostability showed significant ΔΔG changes (<-2.5 kcal/mol) and improvements in perplexity scores from evolutionary scale modeling inverse folding. The best mutant, G205K, increased the melting temperature by 5 °C and the energy of denaturation by 41.3%. We discussed the functional mechanisms for improved stability. Analyzing the adjustments in α-helices, ß-sheets, and loops resulting from point mutations, we have obtained significant knowledge regarding the potential impacts on protein stability, folding, and overall structural integrity.
Assuntos
Glicosídeo Hidrolases , Engenharia de Proteínas , Estabilidade Enzimática , Temperatura , MutagêneseRESUMO
Abstract Bacteria were isolated from samples of Fresh Apple juices from shops of three different localities of Lahore. Analysis of samples from Liberty, Anarkali and Yateem khana Markets show different levels of contamination. There were pathogenic and non-pathogenic bacteria in all samples and were identified by the morphological and biochemical tests. Most of the plasmids of pathogenic bacteria were 4kb in their molecular size. Ribotyping of 16S ribosomal RNA gene sequencing was done to confirm Helicobacter pylori strain and Gluconobacter oxydans. The highest sensitivity of 210mm was shown by Enterobacter sp. against Aztheromysine disk (15µg) while Micrococcus sp. was highly resistant against all of the Antibiotics applied. The antibiotic resistance of pathogenic bacteria was also checked against Ricinus communis plant's extracts, all isolated bacterial pathogens were resistant but only, E.coli was inhibited at 300µl of the extracts. Presence of pathogenic bacteria in Apple juice samples was due to contamination of sewage water in drinking water while some of these pathogenic bacteria came from Apple's tree and other from store houses of fruits.
Resumo As bactérias foram isoladas de amostras de suco de maçã fresco de lojas de três diferentes localidades de Lahore. A análise de amostras dos mercados Liberty, Anarkali e Yateem khana mostram diferentes níveis de contaminação. Havia bactérias patogênicas e não patogênicas em todas as amostras e foram identificadas pelos testes morfológicos e bioquímicos. A maioria dos plasmídeos de bactérias patogênicas tinha 4 kb em seu tamanho molecular. A ribotipagem do sequenciamento do gene do RNA ribossômico 16S foi realizada para confirmar a cepa de Helicobacter pylori e Gluconobacter oxydans. A maior sensibilidade de 210 mm foi mostrada por Enterobacter sp. contra disco de azteromisina (15µg) enquanto Micrococcus sp. foi altamente resistente a todos os antibióticos aplicados. A resistência a antibióticos de bactérias patogênicas também foi verificada contra extratos de plantas de Ricinus communis, todos os patógenos bacterianos isolados foram resistentes, mas apenas E. coli foi inibida em 300µl dos extratos. A presença de bactérias patogênicas nas amostras de suco de maçã deveu-se à contaminação da água de esgoto na água potável, enquanto algumas dessas bactérias patogênicas vieram da árvore da maçã e outras de armazéns de frutas.
RESUMO
The number of primary care physicians in the United States is dwindling rapidly, and osteopathic medical schools are embracing the challenge of leading students toward a career in primary care to meet this need. In recent years, the Problem-Based Learning (PBL) curriculum in medical education has emerged as a patient-centered, social-justice-focused methodology. The unique format of PBL centered around patient cases allows learning through community-based medicine, promoting medical graduates' entry into primary care. Through exploring the literature on this topic, the research question posed for this review is as follows: How have the skills gained in PBL been effectively preparing medical students to become community service-oriented primary care physicians, and how can we qualitatively and quantitatively assess a learner's preparedness to engage in primary care work? The variables studied were board licensing examination scores, clinical competence, and interpersonal skills, all of which emerged as common ways to assess learners' preparedness to work in primary care. The methodology of this literature review was organized using a Preferred Reporting Items for Systematic Reviews and Meta-Analyses flowchart to describe how articles were selected and synthesized to evaluate the variables. The results revealed the variables to be consistent strengths of PBL students, particularly clinical competence, and interpersonal skills, both of which are key in working in primary care and any clinical specialty. Since early in its implementation, literature has demonstrated the tendencies of PBL students to be interested in and later work in primary care, though little follow-up has been done recently. The question of why this phenomenon exists was largely answered by our literature review. In conclusion, through our analysis of the existing literature, the authors demonstrated that the PBL curriculum helps foster students' desire to serve patients. Limitations of the literature included small sample sizes, heterogeneous analysis methods, limited inclusion of qualitative assessment of student progress, and limited existing data on the prevalence of PBL in medical schools, as well as the entrance of PBL graduates into primary care careers.
RESUMO
The study presents a novel approach to analysing the thermoluminescence (TL) glow curves (GCs) of CaSO4:Dy-based personnel monitoring dosimeters using machine learning (ML). This study demonstrates the qualitative and quantitative impact of different types of anomalies on the TL signal and trains ML algorithms to estimate correction factors (CFs) to account for these anomalies. The results show a good degree of agreement between the predicted and actual CFs, with a coefficient of determination greater than 0.95, a root mean square error less than 0.025, and a mean absolute error less than 0.015. The use of ML algorithms leads to a significant two-fold reduction in the coefficient of variation of TL counts from anomalous GCs. This study proposes a promising approach to address anomalies caused by dosimeter, reader, and handling-related factors. Furthermore, it accounts for non-radiation-induced TL at low dose levels towards improving the dosimetric accuracy in personnel monitoring.
Assuntos
Dosímetros de Radiação , Dosimetria Termoluminescente , AlgoritmosRESUMO
Ion mobility mass spectrometry (IM-MS) techniques have become highly valued as a tool for structural characterization of biomolecular systems since they yield accurate measurements of the rotationally averaged collision cross-section (CCS) against a buffer gas. Despite its enormous potential, IM-MS data interpretation is often challenging due to the conformational isomerism of metabolites, lipids, proteins, and other biomolecules in the gas phase. Therefore, reliable and fast CCS calculations are needed to help interpret IM-MS data. In this work, we present MassCCS, a parallelized open-source code for computing CCS of molecules ranging from small organic compounds to massive protein assemblies at the trajectory method level of description using atomic and molecular buffer gas particles. The performance of the code is comparable to other available software for small molecules and proteins but is significantly faster for larger macromolecular assemblies. We performed extensive tests regarding accuracy, performance, and scalability with system size and number of CPU cores. MassCCS has proven highly accurate and efficient, with execution times under a few minutes, even for large (84.87 MDa) virus capsid assemblies with very modest computational resources. MassCCS is freely available at https://github.com/cces-cepid/massccs.
Assuntos
Proteínas , Software , Espectrometria de Massas/métodos , Proteínas/química , Compostos OrgânicosRESUMO
Bisphenol A (BPA, 2,2-bis-(4-hydroxyphenyl)propane) is used as a precursor in the synthesis of polycarbonate and epoxy plastics; however, its availability in the environment is causing toxicity as an endocrine-disrupting chemical. Metabolism of BPA and their analogues (substitutes) is generally performed by liver cytochrome P450 enzymes and often leads to a mixture of products, and some of those are toxic. To understand the product distributions of P450 activation of BPA, we have performed a computational study into the mechanisms and reactivities using large model structures of a human P450 isozyme (P450 2C9) with BPA bound. Density functional theory (DFT) calculations on mechanisms of BPA activation by a P450 compound I model were investigated, leading to a number of possible products. The substrate-binding pocket is tight, and as a consequence, aliphatic hydroxylation is not feasible as the methyl substituents of BPA cannot reach compound I well due to constraints of the substrate-binding pocket. Instead, we find low-energy pathways that are initiated with phenol hydrogen atom abstraction followed by OH rebound to the phenolic ortho- or para-position. The barriers of para-rebound are well lower in energy than those for ortho-rebound, and consequently, our P450 2C9 model predicts dominant hydroxycumyl alcohol products. The reactions proceed through two-state reactivity on competing doublet and quartet spin state surfaces. The calculations show fast and efficient substrate activation on a doublet spin state surface with a rate-determining electrophilic addition step, while the quartet spin state surface has multiple high-energy barriers that can also lead to various side products including C4-aromatic hydroxylation. This work shows that product formation is more feasible on the low spin state, while the physicochemical properties of the substrate govern barrier heights of the rate-determining step of the reaction. Finally, the importance of the second-coordination sphere is highlighted that determines the product distributions and guides the bifurcation pathways.
Assuntos
Sistema Enzimático do Citocromo P-450 , Fenóis , Humanos , Biotransformação , Sistema Enzimático do Citocromo P-450/química , Teoria da Densidade Funcional , HidroxilaçãoRESUMO
Bones are responsible for body support, structure, motion, and several other functions that enable and facilitate life for many different animal species. They exhibit a complex network of distinct physical structures and mechanical properties, which ultimately depend on the fraction of their primary constituents at the molecular scale. However, the relationship between structure and mechanical properties in bones are still not fully understood. Here, we investigate structural and mechanical properties of all-atom bone molecular models composed of type-I collagen, hydroxyapatite (HA), and water by means of fully atomistic molecular dynamics simulations. Our models encompass an extrafibrillar volume (EFV) and consider mineral content in both the EFV and intrafibrillar volume (IFV), consistent with experimental observations. We investigate solvation structures and elastic properties of bone microfibril models with different degrees of mineralization, ranging from highly mineralized to weakly mineralized and nonmineralized models. We find that the local tetrahedral order of water is lost in similar ways in the EFV and IFV regions for all HA containing models, as calcium and phosphate ions are strongly coordinated with water molecules. We also subject our models to tensile loads and analyze the spatial stress distribution over the nanostructure of the material. Our results show that both mineral and water contents accumulate significantly higher stress levels, most notably in the EFV, thus revealing that this region, which has been only recently incorporated in all-atom molecular models, is fundamental for studying the mechanical properties of bones at the nanoscale. Furthermore, our results corroborate the well-established finding that high mineral content makes bone stiffer.
Assuntos
Osso e Ossos , Microfibrilas , Animais , Modelos Moleculares , Água , MineraisRESUMO
At the molecular scale, bone is mainly constituted of type-I collagen, hydroxyapatite, and water. Different fractions of these constituents compose different composite materials that exhibit different mechanical properties at the nanoscale, where the bone is characterized as a fiber, i.e., a bundle of mineralized collagen fibrils surrounded by water and hydroxyapatite in the extra-fibrillar volume. The literature presents only models that resemble mineralized collagen fibrils, including hydroxyapatite in the intra-fibrillar volume only, and lacks a detailed prescription on how to devise such models. Here, we present all-atom bone molecular models at the nanoscale, which, differently from previous bone models, include hydroxyapatite both in the intra-fibrillar volume and in the extra-fibrillar volume, resembling fibers in bones. Our main goal is to provide a detailed prescription on how to devise such models with different fractions of the constituents, and for that reason, we have made step-by-step scripts and files for reproducing these models available. To validate the models, we assessed their elastic properties by performing molecular dynamics simulations that resemble tensile tests, and compared the computed values against the literature (both experimental and computational results). Our results corroborate previous findings, as Young's Modulus values increase with higher fractions of hydroxyapatite, revealing all-atom bone models that include hydroxyapatite in both the intra-fibrillar volume and in the extra-fibrillar volume as a path towards realistic bone modeling at the nanoscale.
RESUMO
Glucuronoyl esterases (GEs) are α/ß serine hydrolases and a relatively new addition in the toolbox to reduce the recalcitrance of lignocellulose, the biggest obstacle in cost-effective utilization of this important renewable resource. While biochemical and structural characterization of GEs have progressed greatly recently, there have yet been no mechanistic studies shedding light onto the rate-limiting steps relevant for biomass conversion. The bacterial GE OtCE15A possesses a classical yet distinctive catalytic machinery, with easily identifiable catalytic Ser/His completed by two acidic residues (Glu and Asp) rather than one as in the classical triad, and an Arg side chain participating in the oxyanion hole. By QM/MM calculations, we identified deacylation as the decisive step in catalysis, and quantified the role of Asp, Glu and Arg, showing the latter to be particularly important. The results agree well with experimental and structural data. We further calculated the free-energy barrier of post-catalysis dissociation from a complex natural substrate, suggesting that in industrial settings non-catalytic processes may constitute the rate-limiting step, and pointing to future directions for enzyme engineering in biomass utilization.
Assuntos
Esterases , Hidrolases , Biomassa , Catálise , Esterases/metabolismoRESUMO
OBJECTIVES: Growing evidence has associated solid/polluted fuel (PF) burning with higher risks of acute respiratory infection (ARI) among under-five children. However, higher usage of PF contributed to upsurge communal air pollution, which may further aggravate ARI. Instead, women empowerment may mitigate the risk of ARI by shifting towards cleaner fuels. This study aimed to estimate the mitigating impact of community-level women empowerment on ARI among under-five children in Pakistan. In addition, the study also aimed to explore the mitigating impact pathway of empowered women community. STUDY DESIGN: A cross-sectional study design was used to collect data under 2018 Pakistan Demographic and Health Survey. METHODS: Retrieved data used in the analysis comprised 12,295 surviving under-five children suffering from cough coinciding with short and rapid breathing and fever from 561 communities. Because of hierarchical structure of the data, two-level mixed-effects logistic regression was used to compute unbiased odds ratios. RESULTS: Approximately 58% of total households used PF as a primary fuel, and PF usage by more than 50% of households led to 129 polluted communities. About 19% of children suffered from symptoms of ARI within 2 weeks preceding the survey. After adjusting for individual, household and communal attributes, the odds of suffering from ARI were 1.156 times higher among children from polluted households than their counterparts. The odds of ARI were aggravated to 1.333 for highly polluted communities. Women empowerment mitigated the risk of ARI by odds of 0.708 and 0.671 at individual level and communal levels, respectively. After shifting towards cleaner fuels, highly women empowered community-mitigated ARI risk by odds of 0.765. CONCLUSIONS: Under-five children of highly polluted communities were at higher risk of ARI, while highly women empowered communities mitigated the risk by shifting towards cleaner fuels. We suggest interventional efforts towards empowering poor women in mitigating ARI.
Assuntos
Poluição do Ar em Ambientes Fechados , Infecções Respiratórias , Poluição do Ar em Ambientes Fechados/efeitos adversos , Poluição do Ar em Ambientes Fechados/análise , Poluição do Ar em Ambientes Fechados/prevenção & controle , Criança , Culinária , Estudos Transversais , Feminino , Humanos , Lactente , Paquistão/epidemiologia , Infecções Respiratórias/epidemiologia , Infecções Respiratórias/prevenção & controle , Fatores de RiscoRESUMO
Bacteria were isolated from samples of Fresh Apple juices from shops of three different localities of Lahore. Analysis of samples from Liberty, Anarkali and Yateem khana Markets show different levels of contamination. There were pathogenic and non-pathogenic bacteria in all samples and were identified by the morphological and biochemical tests. Most of the plasmids of pathogenic bacteria were 4kb in their molecular size. Ribotyping of 16S ribosomal RNA gene sequencing was done to confirm Helicobacter pylori strain and Gluconobacter oxydans. The highest sensitivity of 210mm was shown by Enterobacter sp. against Aztheromysine disk (15µg) while Micrococcus sp. was highly resistant against all of the Antibiotics applied. The antibiotic resistance of pathogenic bacteria was also checked against Ricinus communis plant's extracts, all isolated bacterial pathogens were resistant but only, E.coli was inhibited at 300µl of the extracts. Presence of pathogenic bacteria in Apple juice samples was due to contamination of sewage water in drinking water while some of these pathogenic bacteria came from Apple's tree and other from store houses of fruits.
Assuntos
Antibacterianos , Gluconobacter oxydans , Helicobacter pylori , Extratos Vegetais , Ricinus/química , Antibacterianos/farmacologia , Sucos de Frutas e Vegetais/microbiologia , Gluconobacter oxydans/efeitos dos fármacos , Helicobacter pylori/efeitos dos fármacos , Malus/microbiologia , Testes de Sensibilidade Microbiana , Extratos Vegetais/farmacologiaRESUMO
With the continued surge in Lyme disease cases, post-treatment Lyme disease syndrome (PTLDS) is becoming a more pressing health concern. The aim of this review is to identify comprehensive treatment strategies for PTLDS patients. Unfortunately, universal guidelines for diagnosing and treating PTLDS do not currently exist. Consequently, physicians cannot adequately address concerns of possible PTLDS patients. Patients are left suffering and searching for answers, and their activities of daily living and quality of life are adversely impacted. This review highlights that PTLDS clinical trials have focused mainly on treatment with antibiotics, yielding challenging results that lack consistency in inclusion criteria across trials. It will remain exceedingly difficult to extrapolate the outcomes of such studies if a standard for PTLDS diagnosis is not well-established. By focusing on treatment trials rather than establishing diagnostic criteria, research in this field ignores a critical step in investigating PTLDS. The first significant step is to create comprehensive guidelines for the diagnosis of PTLDS, which can generate uniformity and validate PTLDS treatment trials.
RESUMO
Water is one of the principal constituents by mass of living plant cell walls. However, its role and interactions with secondary cell wall polysaccharides and the impact of dehydration and subsequent rehydration on the molecular architecture are still to be elucidated. This work combines multidimensional solid-state 13C magic-angle-spinning (MAS) nuclear magnetic resonance (NMR) with molecular dynamics modeling to decipher the role of water in the molecular architecture of softwood secondary cell walls. The proximities between all main polymers, their molecular conformations, and interaction energies are compared in never-dried, oven-dried, and rehydrated states. Water is shown to play a critical role at the hemicellulose-cellulose interface. After significant molecular shrinkage caused by dehydration, the original molecular conformation is not fully recovered after rehydration. The changes include xylan becoming more closely and irreversibly associated with cellulose and some mannan becoming more mobile and changing conformation. These irreversible nanostructural changes provide a basis for explaining and improving the properties of wood-based materials.
Assuntos
Nanoestruturas , Água , Parede Celular , Celulose , XilanosRESUMO
Cellulose possesses considerable potential for a wide range of sustainable applications. Nanocellulose-based material properties are primarily dependent on the structural surface characteristics of its crystalline planes. Experimental measurements of the affinity of crystalline nanocellulose surfaces with water are scarce and challenging to obtain. Therefore, the relative hydrophilicity of different cellulose allomorphs crystalline planes is often inferred from qualitative assessments of their surface and the exposition of polar groups to the solvent. This work investigates the relative hydrophilicity of cellulose surfaces using molecular dynamics simulations. The behavior of a water droplet laid on different crystal planes was used to determine their relative hydrophilicity. The water molecules fully spread onto highly hydrophilic surfaces. However, a water droplet placed on less hydrophilic surfaces equilibrates as an oblate spheroidal cap allowing the measurement of a contact angle. The results indicate that the Iα (010), Iα (11Ì 0), Iß (010), and Iß (110) faces, as well as the faces of human-made celluloses II and III_I (100), (11Ì 0), (010), and (110) are all highly hydrophilic. They all have a contact angle value inferior to 11°. Not unexpectedly, the Iα (001) and Iß (100) surfaces are less hydrophilic with contact angles of 48 and 34°, respectively. However, the Iß (11Ì 0) plane, often referred to as a hydrophilic surface, forms a contact angle of about 32°. The results are rationalized in terms of structure, exposure of hydroxyl groups to the solvent, and degree of cellulose-cellulose versus cellulose-water hydrogen bonds on each face. The simulations also show that the surface oxidation degree tunes the surface hydrophilicity in a nonlinear manner due to cooperative effects involving water-cellulose interactions. Our study helps us to understand how the degree of hydrophilicity of cellulose emerges from specific structural features of each crystalline surface.