Reversible Deacidification and Preventive Conservation of Paper-Based Cultural Relics by Mineralized Bacterial Cellulose.

Paper-based cultural relics experience irreversible aging and deterioration during long-term preservation. The most common process of paper degradation is the acid-catalyzed hydrolysis of cellulose. Nowadays, deacidification has been considered as a practical way to protect acidified literature; however, two important criteria of minimal intervention and reversibility should be considered. Inspired by the superior properties of bacterial cellulose (BC) and its structural similarity to paper, herein, the mineralized BC membranes are applied to deacidification and conservation of paper-based materials for the first time. Based on the enzyme-induced mineralization process, the homogeneous and high-loaded calcifications of hydroxyapatite (HAP) and calcium carbonate (CaCO3) nanoparticles onto the nanofibers of BC networks have been achieved, respectively. The size, morphology, structure of minerals, as well as the alkalinity and alkali reserve of BC membranes are well controlled by regulating enzyme concentration and mineralization time. Compared with HAP/CaCO3-immersed method, HAP/CaCO3-BC membranes show more efficient and sustained deacidification performance on paper. The weak alkalinity of mineralized BC membranes avoids the negative effect of alkali on paper, and the high alkali reserve implies a good sustained-release effect of alkali to neutralize the future generated acid. The multiscale nanochannels of the BC membrane provide ion exchange and acid/alkali neutralization channels between paper and the BC membrane, and the final pH of protected paper can be well stabilized in a certain range. Most importantly, this BC-deacidified method is reversible since the BC membrane can be removed without causing any damage to paper and the original structure and fiber morphology of paper are well preserved. In addition, the mineralized BC membrane provides excellent flame-retardant performance on paper thanks to its unique organic-inorganic composite structure. All of these advantages of the mineralized BC membrane indicate its potential use as an effective protection material for the reversible deacidification and preventive conservation of paper-based cultural relics.

Direct conversion of C6 sugars to methyl glycerate and glycolate in methanol.

The present work deals with the one-pot conversion of C6 sugars to methyl glycerate and glycolate via a cascade of retro-aldol condensation and oxidation processes catalyzed by using MoO3 as the Lewis acid catalyst and Au/TiO2 as the oxidation catalyst in methanol. Methyl glycerate (MGLY) is the product of C6 ketose (fructose), while methyl glycolate (MG) is produced from C6 aldose (mannose, glucose). It is found that a good one-pot match between two reactive processes is the key to the production of MGLY and MG with high yield (27.6% MGLY and 39.2% MG). A separated retro-aldol condensation and oxidation process greatly decreases their yields, and even no MGLY can be obtained in this separated process. We attribute this to high instability of glyceraldehyde/glycolaldehyde and their different reaction pathways which mainly depend on whether acetalization of retro-aldol products (glyceraldehyde and glycolaldehyde) occurs with methanol or not. This result opens a new prospect on the accumulation of C3 products other than lactate from biomass-derived carbohydrates.

Direct Transformation of HMF into 2,5-Diformylfuran and 2,5-Dihydroxymethylfuran without an External Oxidant or Reductant.

The selective transformation of 5-hydroxymethylfurfural (HMF) to valuable 2,5-diformylfuran (DFF) and 2,5-dihydroxymethylfuran (DHMF) is highly desirable but remains a great challenge owing to its tendency to over-oxidation and over-reduction. In this work, HMF is directly converted into DFF and DHMF without external oxidant or reductant through a Meerwein-Ponndorf-Verley-Oppenauer (MPVO) reaction. In such a MPVO process, HMF is used as both oxidant and reductant and DFF and DHMF are simultaneously produced with a 1:1 molar ratio in the presence of a Lewis acid catalyst. Under high initial HMF concentration, a HMF conversion of up to 44.7 % can be reached within 1 h. Moreover, this atom-efficient transformation route for HMF also provides a promising protocol for the crude separation of DHMF products from DFF products, owing to the lower solubility of DHMF compared to DFF in acetonitrile.

Silanization-Based Zeolite Crystallization: Participation Degree and Pathway.

A clear and deep understanding of zeolite crystallization with the addition of organosilane is desirable for the reasonable design and preparation of hierarchical zeolites. Herein, the effects of different organosilanes on zeolite crystallization were systematically studied. It was found that organosilane plays the role of an inhibitor in the silanization-based zeolite preparation, and this inhibition effect was determined by its participation degree. An organosilane with a high participation degree can result in the prolongation of nucleation and growth periods of zeolite as well as the variation of product properties. More importantly, a dynamic participation pathway of organosilane is proposed, that is, the growth of zeolite is accompanied by the continuous removal of organosilane, leading to an increase of product crystallinity as well as the decrease of mesoporosity. This study gives a new insight into the role that organosilane plays in zeolite crystallization, which will help to direct the rational selection of organosilane and design of crystallization condition for the optimal synthesis of hierarchical zeolites.

Activity modulation of core and shell in nanozeolite@enzyme bi-functional catalyst for dynamic kinetic resolution.

A core-shell nanozeolite@enzyme bi-functional catalyst is prepared by using nanozeolite ß as acidic core and immobilized Candida antarctica lipase B (CALB) as enzyme shell for the purpose of dynamic kinetic resolution (DKR), and polydiallyldimethylammonium chloride (PDDA) is used as interlayer to compart core and shell. The activities of core and shell in bi-functional catalyst are modulated to achieve the matching between racemization and kinetic resolution (KR) rates in DKR, i.e., a slow racemization rate on core while a fast KR rate on shell. Nanozeolite ß with intermediate SiO2/Al2O3 ratio provides proper acid amount for racemization step. A relatively thick layer of PDDA not only improves the activity of CALB by its coverage for surface acidic sites but also limits the accessibility and diffusion of substrate towards the acidic core. The CALB shell with larger immobilized amount and higher enzyme activity offers enhanced driving force of DKR process, leading to higher conversion, selectivity and yield. The preparation and activity modulation of core-shell catalyst provide an ideal method to improve the catalytic performance of bi-functional catalyst.

Microwave-assisted synthesis of Gd(iii)-loaded nanozeolite SOD as MRI contrast agent with remarkable stability in vivo.

Gd3+-loaded nanozeolite sodalite (SOD) is fast prepared through sequential hydrothermal synthesis, detemplation, and Gd3+ ions exchange under microwave irradiation. This microwave-assisted synthesis procedure provides nanozeolite Gd3+-SOD with a uniform particle size of 30 ± 2 nm and well framework structure. The result of its water proton relaxation rate indicates that its positive relaxivity per Gd3+ ion or per nanozeolite particle is relatively high, due to the efficient immobilization and enrichment of Gd3+ ions in the micropores as well as the large surface-to-volume ratio of nanozeolite. Furthermore, the relaxivity per Gd3+ ion displays clear position dependence, i.e., the exchanged Gd3+ ions near the external surface of nanozeolite pay major contribution to the total relaxivity. Moreover, the irreversible ion exchange process indicates that leaching of Gd3+ ion from nanozeolite Gd3+-SOD can be suppressed. The cell viability test shows low toxicity of nanozeolite Gd3+-SOD in vitro. The biodistribution and clearance data demonstrate the fast elimination of nanozeolite Gd3+-SOD by the reticuloendothelial system and steady accumulation in the liver and spleen for a long time, which indicates the negligible leaching of Gd3+ ion in vivo considering the highly stable framework structure of zeolite. In addition, the in vivo MRI demonstrates a brighter contrast enhancement in T1-weighted image compared to the pre-contrast image in the liver. This remarkable stable nanozeolite Gd3+-SOD with a positive relaxivity not only is a potential contrast agent for magnetic resonance imaging but also provides new insight into the utilization of nanozeolite with a unique framework structure.

Protein adsorption onto nanozeolite: effect of micropore openings.

A clear and deep understanding of protein adsorption on porous surfaces is desirable for the reasonable design and applications of porous materials. In this study, the effect of surface micropores on protein adsorption was systematically investigated by comparing adsorption behavior of cytochrome c (Cyto-c) and Candida antarctica Lipase B (CALB) on porous and non-porous nanozeolites silicalite-1 and Beta. It was found that micropore openings on the surface of nanozeolites played a key role in determining adsorption affinity, conformations, and activities of proteins. Both Cyto-c and CALB showed higher affinity to porous nanozeolites than to non-porous ones, resulting in greater conformational change of proteins on porous surfaces which in turn affected their bio-catalytic performance. The activity of Cyto-c improved while that of CALB decreased on porous nanozeolites. Recognition of certain amino acid residues or size-matching secondary structures by micropore openings on the surface of nanozeolites was proposed to be the reason. Moreover, the pore opening effect of porous nanozeolites on protein behavior could be altered by changing protein coverage on them. This study gives a novel insight into the interaction between proteins and microporous materials, which will help to guide the rational fabrication and bio-applications of porous materials in the future.