RESUMO
Most reported artificial esterases only hydrolyze highly activated substrates. We here report synthetic catalysts that hydrolyze nonactivated aryl esters at pH 7, via cooperative action of a thiourea group that mimics the oxyanion hole of a serine protease and a nearby nucleophilic/basic pyridyl group. The molecularly imprinted active site distinguishes subtle structural changes in the substrate, including elongation of the acyl chain by two carbons or shift of a remote methyl group by one carbon.
RESUMO
Molecular recognition in water is challenging but water-soluble molecularly imprinted nanoparticle (MINP) receptors were produced readily by double cross-linking of surfactant micelles in the presence of suitable template molecules. When the micellar surface was decorated with different polyhydroxylated ligands, significant interactions could be introduced between the surface ligands and the template. Flexible surface ligands worked better than rigid ones to interact with the polar moiety of the template, especially for those template molecules whose water-exposed surface is not properly solvated by water. The importance of these hydrophilic interactions was examined in the context of different substrates, density of the surface ligands, and surface-cross-linking density of the MINP. Together with the hydrophobic interactions in the core, the surface hydrophilic interactions can be used to enhance the binding of guest molecules in water.
RESUMO
Molecularly imprinted nanoparticles (MINPs) were prepared when surfactants with a tripropargylammonium headgroup and a methacrylate-functionalized hydrophobic tail were cross-linked in the micelle form on the surface and in the core in the presence of hydrophobic template molecules. With the surfactants containing an amide bond near the headgroup, the MINPs had a layer of hydrogen-bonding groups in the interior that strongly influenced their molecular recognition. Templates/guests with strong hydrogen-bonding groups in the midsection of the molecule benefited most, especially if the hydrophobe of the template could penetrate the amide layer to reach the hydrophobic core of the cross-linked micelles. The location and the orientation of the hydrophilic groups were also important, as they determined how the template interacted with the surfactant micelles and, ultimately, with the MINP receptors.
Assuntos
Interações Hidrofóbicas e Hidrofílicas , Impressão Molecular , Nanopartículas , Sítios de Ligação , Espectroscopia de Ressonância Magnética Nuclear de Carbono-13 , Ligação de Hidrogênio , Micelas , Espectroscopia de Prótons por Ressonância Magnética , Solubilidade , Espectrometria de Massas por Ionização por Electrospray , Tensoativos/química , Água/químicaRESUMO
Myasthenia gravis (MG) is an autoimmune disorder of the neuromuscular transmission, caused by auto antibodies against the nicotinic acetylcholine receptor. These antibodies of the IgG isotype are detected in 80-90% of generalized MG and in 50-70% of ocular MG. Seronegative MG is caused by humoral factors. Prevalence of MG lies between 1 in 10.000 and 1 in 50.000, with 2/3 of affected individuals being female. In the case of maternal myasthenia gravis, both the mother and the child may develop myasthenia symptoms with varying degrees of weakness and progressive fatigability of the skeletal muscles. Data for the case report were generated by reviewing labour, delivery, and postpartal records. We present a 26 years old lady who suffered from a generalized form of myasthenia gravis since the age of 15. She got herself admitted to a neurologic clinic for a myasthenic crisis when she was two and half months pregnant. The patient was treated with anticholinesterase medication, corticosteroids and intravenous immunoglobulin. Clinically, the patient's condition improved significantly during pregnancy. Delivery and the post delivery period were also normal for the patient. Myasthenia gravis especially when associated with pregnancy is a high-risk disease. As this disease predominantly occurs in women of reproductive age, it is important to be aware of this condition in obstetrics and its interdisciplinary diagnostic and therapeutic management is required.
Assuntos
Miastenia Gravis/diagnóstico , Miastenia Gravis/terapia , Complicações na Gravidez/diagnóstico , Complicações na Gravidez/terapia , Adulto , Feminino , Humanos , GravidezRESUMO
Natural esterases hydrolyze esters under physiological pHs but chemists often have to use strongly acidic or basic conditions for the same hydrolysis. We report synthetic nanoparticle catalysts that hydrolyze nonactivated alkyl esters at room temperature and neutral pH, with enzyme-like catalytic mechanisms and exquisite substrate selectivity. Unlike natural enzymes that denature easily at elevated temperatures, the synthetic catalysts become more active at higher temperatures.
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As rice is an important staple food globally, research for development and enhancement of its nutritional value it is an imperative task. Identification of nutrient enriched rice germplasm and exploiting them for breeding programme is the easiest way to develop better quality rice. In this study, we analyzed 113 aromatic rice germplasm in order to identify quantitative trait loci (QTL) underpinning nutrition components and determined by measuring the normal frequency distribution for Fe, Zn, amylose, and protein content in those rice germplasm. Comparatively, the germplasm Radhuni pagal, Kalobakri, Thakurbhog (26.6 ppm) and Hatisail exhibited the highest mean values for Fe (16.9 ppm), Zn (34.1 ppm), amylose (26.6 ppm) and protein content (11.0 ppm), respectively. Moreover, a significant linear relationship (R2 = 0.693) was observed between Fe and Zn contents. Cluster analysis based on Mahalanobis D2 distances revealed four major clusters of 113 rice germplasm, with cluster III containing a maximum 37 germplasm and a maximum inter-cluster distance between clusters III and IV. The 45 polymorphic SSRs and four trait associations exhibited eight significant quantitative trait loci (QTL) located on eight different chromosomes using composite interval mapping (CIM). The highly significant QTL (variance 7.89%, LOD 2.02) for protein content (QTL.pro.1) was observed on chromosome 1 at 94.9cM position. Also, four QTLs for amylose content were observed with the highly significant QTL.amy.8 located on chromosome 8 exhibiting 7.2% variance with LOD 1.83. Only one QTL (QTL.Fe.9) for Fe content was located on chromosome 9 (LOD 1.24), and two (QTL.Zn.4 and QTL.Zn.5) for Zn on chromosome 4 (LOD 1.71) and 5 (LOD 1.18), respectively. Overall, germplasm from clusters III and IV might offer higher heterotic response with the identified QTLs playing a significant role in any rice biofortification breeding program and released with development of new varieties.
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Oryza/genética , Locos de Características Quantitativas , Amilose/análise , Biofortificação/métodos , Produtos Agrícolas/química , Produtos Agrícolas/classificação , Produtos Agrícolas/genética , Alimentos Fortificados/análise , Genes de Plantas , Marcadores Genéticos , Ferro/análise , Valor Nutritivo , Oryza/química , Oryza/classificação , Fenótipo , Melhoramento Vegetal/métodos , Proteínas de Vegetais Comestíveis/análise , Análise de Regressão , Sementes/química , Sementes/genética , Zinco/análiseRESUMO
This paper measures the adhesion/cohesion force among asphalt molecules at nanoscale level using an Atomic Force Microscopy (AFM) and models the moisture damage by applying state-of-the-art Computational Intelligence (CI) techniques (e.g., artificial neural network (ANN), support vector regression (SVR), and an Adaptive Neuro Fuzzy Inference System (ANFIS)). Various combinations of lime and chemicals as well as dry and wet environments are used to produce different asphalt samples. The parameters that were varied to generate different asphalt samples and measure the corresponding adhesion/cohesion forces are percentage of antistripping agents (e.g., Lime and Unichem), AFM tips K values, and AFM tip types. The CI methods are trained to model the adhesion/cohesion forces given the variation in values of the above parameters. To achieve enhanced performance, the statistical methods such as average, weighted average, and regression of the outputs generated by the CI techniques are used. The experimental results show that, of the three individual CI methods, ANN can model moisture damage to lime- and chemically modified asphalt better than the other two CI techniques for both wet and dry conditions. Moreover, the ensemble of CI along with statistical measurement provides better accuracy than any of the individual CI techniques.
Assuntos
Inteligência Artificial , Compostos de Cálcio/química , Hidrocarbonetos/química , Microscopia de Força Atômica , Óxidos/química , Água/química , Fenômenos Mecânicos , Microscopia de Força Atômica/instrumentação , Microscopia de Força Atômica/métodos , Análise de Regressão , Processamento de Sinais Assistido por ComputadorRESUMO
High-energy tibial plateau fractures associated with severe soft tissue injury are difficult to manage. The risk of wound complications following open reduction and internal fixation is notably high owing to extensive soft tissue dissection. Alternatively, application of Ilizarov ring fixator minimizes soft tissue dissection and provides adequate fracture stabilization to allow early range of motion and correction of any mal-alignment. With this technique, soft tissue complications particularly surgical site infections are expected to be significantly reduced. This prospective interventional study was conducted from January 2012 to December 2013 at National Institute of Traumatology and Orthopaedic Rehabilitation (NITOR), Dhaka, Bangladesh. Ten patients with tibial plateau fracture Schatzker type VI were treated with Ilizarov ring fixator. Patients were visited routinely and final outcome evaluation done according to Rasmussen's functional grading system and radiological evaluation. Among the 10 patients of type-VI Schatzker tibial plateau fractures, the mean range of knee movement was 95.5°. The mean Rasmussen functional score was 23.6 (range, 16-28): excellent in 3 patients, good in 5 and fair in 2.
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Fixação Interna de Fraturas , Fraturas da Tíbia , Bangladesh , Humanos , Estudos Prospectivos , Radiografia , Fraturas da Tíbia/diagnóstico por imagem , Fraturas da Tíbia/cirurgia , Resultado do TratamentoRESUMO
A shortcoming of currently available oral cholera vaccines is their induction of relatively short-term protection against cholera compared to that afforded by wild-type disease. We were interested in whether transcutaneous or subcutaneous boosting using a neoglycoconjugate vaccine made from a synthetic terminal hexasaccharide of the O-specific polysaccharide of Vibrio cholerae O1 (Ogawa) coupled to bovine serum albumin as a carrier (CHO-BSA) could boost lipopolysaccharide (LPS)-specific and vibriocidal antibody responses and result in protective immunity following oral priming immunization with whole-cell cholera vaccine. We found that boosting with CHO-BSA with immunoadjuvantative cholera toxin (CT) or Escherichia coli heat-labile toxin (LT) following oral priming with attenuated V. cholerae O1 vaccine strain O395-NT resulted in significant increases in serum anti-V. cholerae LPS IgG, IgM, and IgA (P < 0.01) responses as well as in anti-Ogawa (P < 0.01) and anti-Inaba (P < 0.05) vibriocidal titers in mice. The LPS-specific IgA responses in stool were induced by transcutaneous (P < 0.01) but not subcutaneous immunization. Immune responses following use of CT or LT as an adjuvant were comparable. In a neonatal mouse challenge assay, immune serum from boosted mice was associated with 79% protective efficacy against death. Our results suggest that transcutaneous and subcutaneous boosting with a neoglycoconjugate following oral cholera vaccination may be an effective strategy to prolong protective immune responses against V. cholerae.