scholarly journals Effect of Active Site Modification towards Performance Enhancement in Biopolymer κ-Carrageenan Derivatives

Polymers ◽  
2020 ◽  
Vol 12 (9) ◽  
pp. 2040
Author(s):  
Mohd Hafiz Abu Bakar ◽  
Nur Hidayah Azeman ◽  
Nadhratun Naiim Mobarak ◽  
Mohd Hadri Hafiz Mokhtar ◽  
Ahmad Ashrif A Bakar

This research demonstrates a one-step modification process of biopolymer carrageenan active sites through functional group substitution in κ-carrageenan structures. The modification process improves the electronegative properties of κ-carrageenan derivatives, leading to enhancement of the material’s performance. Synthesized succinyl κ-carrageenan with a high degree of substitution provides more active sites for interaction with analytes. The FTIR analysis of succinyl κ-carrageenan showed the presence of new peaks at 1068 cm−1, 1218 cm−1, and 1626 cm−1 that corresponded to the vibrations of C–O and C=O from the carbonyl group. A new peak at 2.86 ppm in 1H NMR represented the methyl proton neighboring with C=O. The appearance of new peaks at 177.05 and 177.15 ppm in 13C NMR proves the substitution of the succinyl group in the κ-carrageenan structure. The elemental analysis was carried out to calculate the degree of substitution with the highest value of 1.78 at 24 h of reaction. The XRD diffractogram of derivatives exhibited a higher degree of crystallinity compared to pristine κ-carrageenan at 23.8% and 9.2%, respectively. Modification of κ-carrageenan with a succinyl group improved its interaction with ions and the conductivity of the salt solution compared to its pristine form. This work has a high potential to be applied in various applications such as sensors, drug delivery, and polymer electrolytes.

2019 ◽  
Author(s):  
Mark Workentin ◽  
François Lagugné-Labarthet ◽  
Sidney Legge

In this work we present a clean one-step process for modifying headgroups of self-assembled monolayers (SAMs) on gold using photo-enabled click chemistry. A thiolated, cyclopropenone-caged strained alkyne precursor was first functionalized onto a flat gold substrate through self-assembly. Exposure of the cyclopropenone SAM to UV-A light initiated the efficient photochemical decarbonylation of the cyclopropenone moiety, revealing the strained alkyne capable of undergoing the interfacial strain-promoted alkyne-azide cycloaddition (SPAAC). Irradiated SAMs were derivatized with a series of model azides with varied hydrophobicity to demonstrate the generality of this chemical system for the modification and fine-tuning of the surface chemistry on gold substrates. SAMs were characterized at each step with polarization-modulation infrared reflection-absorption spectroscopy (PM-IRRAS) to confirm successful functionalization and reactivity. Furthermore, to showcase the compatibility of this approach with biochemical applications, cyclopropenone SAMs were irradiated and modified with azide-bearing cell adhesion peptides to promote human fibroblast cell adhesion, then imaged by live cell fluorescence microscopy. Thus, the “photoclick” methodology reported here represents an improved, versatile, catalyst-free protocol that allows for a high degree of control over the modification of material surfaces, with applicability in materials science as well as biochemistry.<br>


2020 ◽  
Author(s):  
Baojian Xiong ◽  
Yue Li ◽  
Yin Wei ◽  
Søren Kramer ◽  
Zhong Lian

Cross-coupling between substrates that can be easily derived from phenols is highly attractive due to the abundance and low cost of phenols. Here, we report a dual nickel/palladium-catalyzed reductive cross-coupling between aryl tosylates and aryl triflates; both substrates can be accessed in just one step from readily available phenols. The reaction has a broad functional group tolerance and substrate scope (>60 examples). Furthermore, it displays low sensitivity to steric effects demonstrated by the synthesis of a 2,2’disubstituted biaryl and a fully substituted aryl product. The widespread presence of phenols in natural products and pharmaceuticals allow for straightforward late-stage functionalization, illustrated with examples such as Ezetimibe and tyrosine. NMR spectroscopy and DFT calculations indicate that the nickel catalyst is responsible for activating the aryl triflate, while the palladium catalyst preferentially reacts with the aryl tosylate.


Nanomaterials ◽  
2021 ◽  
Vol 11 (1) ◽  
pp. 202
Author(s):  
Yexin Dai ◽  
Jie Ding ◽  
Jingyu Li ◽  
Yang Li ◽  
Yanping Zong ◽  
...  

In this work, reduced graphene oxide (rGO) nanocomposites doped with nitrogen (N), sulfur (S) and transitional metal (Ni, Co, Fe) were synthesized by using a simple one-step in-situ hydrothermal approach. Electrochemical characterization showed that rGO-NS-Ni was the most prominent catalyst for glucose oxidation. The current density of the direct glucose alkaline fuel cell (DGAFC) with rGO-NS-Ni as the anode catalyst reached 148.0 mA/cm2, which was 40.82% higher than the blank group. The DGAFC exhibited a maximum power density of 48 W/m2, which was more than 2.08 folds than that of blank group. The catalyst was further characterized by SEM, XPS and Raman. It was speculated that the boosted performance was due to the synergistic effect of N, S-doped rGO and the metallic redox couples, (Ni2+/Ni3+, Co2+/Co3+ and Fe2+/Fe3+), which created more active sites and accelerated electron transfer. This research can provide insights for the development of environmental benign catalysts and promote the application of the DGAFCs.


Pharmaceutics ◽  
2021 ◽  
Vol 13 (2) ◽  
pp. 277 ◽  
Author(s):  
Ala’ Salem ◽  
Anna Takácsi-Nagy ◽  
Sándor Nagy ◽  
Alexandra Hagymási ◽  
Fruzsina Gősi ◽  
...  

Drug–drug cocrystals are formulated to produce combined medication, not just to modulate active pharmaceutical ingredient (API) properties. Nano-crystals adjust the pharmacokinetic properties and enhance the dissolution of APIs. Nano-cocrystals seem to enhance API properties by combining the benefits of both technologies. Despite the promising opportunities of nano-sized cocrystals, the research at the interface of nano-technology and cocrystals has, however, been described to be in its infancy. In this study, high-pressure homogenization (HPH) and high-power ultrasound were used to prepare nano-sized cocrystals of 4-aminosalysilic acid and sulfamethazine in order to establish differences between the two methods in terms of cocrystal size, morphology, polymorphic form, and dissolution rate enhancement. It was found that both methods resulted in the formation of form I cocrystals with a high degree of crystallinity. HPH yielded nano-sized cocrystals, while those prepared by high-power ultrasound were in the micro-size range. Furthermore, HPH produced smaller-size cocrystals with a narrow size distribution when a higher pressure was used. Cocrystals appeared to be needle-like when prepared by HPH compared to those prepared by high-power ultrasound, which had a different morphology. The highest dissolution enhancement was observed in cocrystals prepared by HPH; however, both micro- and nano-sized cocrystals enhanced the dissolution of sulfamethazine.


Materials ◽  
2021 ◽  
Vol 14 (14) ◽  
pp. 3783
Author(s):  
Jian-Qing Qiu ◽  
Huan-Qing Xie ◽  
Ya-Hao Wang ◽  
Lan Yu ◽  
Fang-Yuan Wang ◽  
...  

The removal of organic pollutants using green environmental photocatalytic degradation techniques urgently need high-performance catalysts. In this work, a facile one-step hydrothermal technique has been successfully applied to synthesize a Nb2O5 photocatalyst with uniform micro-flower structure for the degradation of methyl orange (MO) under UV irradiation. These nanocatalysts are characterized by transmission and scanning electron microscopies (TEM and SEM), X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET) method, and UV-Vis diffuse reflectance spectroscopy (DRS). It is found that the prepared Nb2O5 micro-flowers presents a good crystal phases and consist of 3D hierarchical nanosheets with 400–500 nm in diameter. The surface area is as large as 48.6 m2 g−1. Importantly, the Nb2O5 micro-flowers exhibit superior catalytic activity up to 99.9% for the photodegradation of MO within 20 mins, which is about 60-fold and 4-fold larger than that of without catalysts (W/O) and commercial TiO2 (P25) sample, respectively. This excellent performance may be attributed to 3D porous structure with abundant catalytic active sites.


Author(s):  
Francisco G. Cirujano ◽  
Nuria Martin ◽  
Neyvis Almora-Barrios ◽  
Carlos Martí-Gastaldo

Room temperature one-step synthesis of the peptide-based porous material with a periodic distribution of pockets decorated with lysine side chain active sites behaves as a heterogeneous organocatalyst. The pockets are...


2016 ◽  
Vol 397 (2) ◽  
pp. 135-145 ◽  
Author(s):  
Miriam Olombrada ◽  
Lucía García-Ortega ◽  
Javier Lacadena ◽  
Mercedes Oñaderra ◽  
José G. Gavilanes ◽  
...  

Abstract Ribotoxins are cytotoxic members of the family of fungal extracellular ribonucleases best represented by RNase T1. They share a high degree of sequence identity and a common structural fold, including the geometric arrangement of their active sites. However, ribotoxins are larger, with a well-defined N-terminal β-hairpin, and display longer and positively charged unstructured loops. These structural differences account for their cytotoxic properties. Unexpectedly, the discovery of hirsutellin A (HtA), a ribotoxin produced by the invertebrate pathogen Hirsutella thompsonii, showed how it was possible to accommodate these features into a shorter amino acid sequence. Examination of HtA N-terminal β-hairpin reveals differences in terms of length, charge, and spatial distribution. Consequently, four different HtA mutants were prepared and characterized. One of them was the result of deleting this hairpin [Δ(8-15)] while the other three affected single Lys residues in its close spatial proximity (K115E, K118E, and K123E). The results obtained support the general conclusion that HtA active site would show a high degree of plasticity, being able to accommodate electrostatic and structural changes not suitable for the other previously known larger ribotoxins, as the variants described here only presented small differences in terms of ribonucleolytic activity and cytotoxicity against cultured insect cells.


Catalysts ◽  
2018 ◽  
Vol 8 (10) ◽  
pp. 418 ◽  
Author(s):  
Muhammad Abdus Salam ◽  
Derek Creaser ◽  
Prakhar Arora ◽  
Stefanie Tamm ◽  
Eva Lind Grennfelt ◽  
...  

Hydrodeoxygenation (HDO) activity of a typical hydrotreating catalyst, sulfided NiMo/γ-Al2O3 for deoxygenation of a fatty acid has been explored in a batch reactor at 54 bar and 320 °C in the presence of contaminants, like phospholipids, which are known to be present in renewable feeds. Oleic acid was used for the investigation. Freshly sulfided catalyst showed a high degree of deoxygenation activity; products were predominantly composed of alkanes (C17 and C18). Experiments with a major phospholipid showed that activity for C17 was greatly reduced while activity to C18 was not altered significantly in the studied conditions. Characterization of the spent catalyst revealed the formation of aluminum phosphate (AlPO4), which affects the active phase dispersion, blocks the active sites, and causes pore blockage. In addition, choline, formed from the decomposition of phospholipid, partially contributes to the observed deactivation. Furthermore, a direct correlation was observed in the accumulation of coke on the catalyst and the amount of phospholipid introduced in the feed. We therefore propose that the reason for the increased deactivation is due to the dual effects of an irreversible change in phase to aluminum phosphate and the formation of choline.


1959 ◽  
Vol 37 (1) ◽  
pp. 1293-1299 ◽  
Author(s):  
J. M. McLaughlan ◽  
C. G. Rogers ◽  
D. G. Chapman ◽  
J. A. Campbell

Available evidence has shown that most common foods are deficient in lysine, methionine, or in methionine and cystine. Based on the determination of these amino acids, a simplified chemical score was developed and compared with protein efficiency ratio (P.E.R.) values determined with the same samples. Each of 43 foods was assigned to either of two categories: (a) foods apparently deficient in lysine or (b) in methionine (+ cystine). With 16 foods in the former group there was a high degree of correlation between lysine concentration and P.E.R. With 27 foods in the latter group, a good correlation was found between the methionine (+ cystine) concentration and P.E.R. Since the regression lines for the two groups were different, a factor was added to the methionine (+ cystine) values to simplify the relationship. That foods deficient in lysine or in methionine (+ cystine) fell into two distinct groups appeared to be substantiated by data available in the literature. Because the simplified method is relatively rapid, yields reproducible results, and correlates with animal assays, it is proposed as a rapid screening procedure for the evaluation of protein in foods, but is not intended to replace the rat bio-assay method.


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