Treatment in Swelling Solutions Modifying Cellulose Fiber Reactivity – Part 1: Accessibility and Sorption

Of prime importance in reactions involving insoluble cellulosic fibers is the sorption of reagents, which is governed by their degrees of accessibility in substrates. Swelling treatments of cellulosics in alkali solutions alter substrate accessibility leading to changes in their reactivity. In this paper, the first of a two-part series, we collate and examine the results from various studies involving different techniques to characterize modifications in cellulosic fibers after swelling treatments in alkali solutions. Results from measurements of structure and accessibility in fibers with techniques such as water retention, inverse size exclusion chromatography (ISEC), iodine sorption, fiber diameters, and fiber-splitting propensities indicate that the influence of swelling treatments on fiber structure/accessibility is differs with alkali type. The results show that a non-uniform rather than uniform distribution of reagents within structures is a more accurate representation of reactions involving swollen cellulosic fibers. Hence, the observed changes in cellulose-fiber reactivity are governed by the degrees of fiber swelling, and reagent sorption and accessibility during swelling treatments.     

Swelling and Dissolution of Cellulose Part 1: Free Floating Cotton and Wood Fibres in N-Methylmorpholine-N-oxide–Water Mixtures

Summary: Five modes describing the behaviour of cellulose fibres dipped in a chemical have been identified:

• Mode 1: Fast dissolution by disintegration into fragments
• Mode 2: Large swelling by ballooning, and dissolution
• Mode 3: Large swelling by ballooning, and no dissolution
• Mode 4: Homogeneous swelling, and no dissolution
• Mode 5: No swelling and no dissolution

In the case of the behaviour of wood and cotton cellulose fibres in N-methylmorpholine-N-oxide (NMMO) and water mixtures, four domains of water content have been identified. Below 17% of water up to monohydrate (13%), the fibres are disintegrated into rod-like fragments and dissolve (mode 1). In NMMO – water mixtures containing 19–24% water, the cellulose fibres exhibit a heterogeneous swelling by forming balloons (composed of dissolved cellulose holds inside a membrane) separated with non-swollen sections. The whole fibre will completely dissolve (mode 2) in four successive steps (growth of the balloons, burst of the balloons, dissolution of the non-swollen sections and finally dissolution of the membrane). With still greater water contents (25–30%), only the ballooning phenomenon is observed, with a partial dissolution inside the balloon (mode 3). Above 35% of water, the fibres swell homogeneously and are not dissolving (mode 4).     

Contributions to Forming and Analytical Investigations of Solutions of Cellulose and Cellulose Derivatives – A Research and Development Topic of the TITK eV

Modification, forming and analytical characterisation of cellulose and cellulose solutions represents one of the most important research topics of the Thuringian Institute for Textiles and Plastics Research (TITK). The presentation provides information on the current capabilities of the institute and on the analytical methods developed in these fields.     

Interactions of Ionic Liquids with Polysaccharides – 2: Cellulose

Some general comments about ionic liquids (ILs) and carbohydrates are given. The main scope of the review is to discuss the present state of the art of chemical modification of cellulose applying IL as reaction media considering own research results. ILs, namely 1-butyl-3-methylimidazolium chloride (BMIMCl), 1-ethyl- 3-methylimidazolium chloride (EMIMCl), 1-butyl-2,3-dimethylimidazolium chloride (BDMIMCl), 1-allyl-2,3-dimethylimidazolium bromide (ADMIMBr) and 1-ethyl-3- methylimidazolium acetate (EMIMAc) are solvents for cellulose (even for high molecular bacterial synthesized cellulose) and can easily be applied as reaction media for cellulose modification. We investigated the homogeneous acylation, carbanilation and silylation of the biopolymer cellulose. Under mild conditions and within short reaction time at low temperature (65 °C to 80 °C) and low excess of reagent, various cellulose esters and carbanilates, dendronized cellulose and trimethylsilyl cellulose were obtained. The DS of the cellulose derivatives can be controlled by varying the reaction time, reaction temperature and the IL used as reaction medium.     

Cellulose solutions in N-methylmorpholine-N-oxide (NMMO) – degradation processes and stabilizers

Efficient stabilization of cellulose solutions in NMMO(1) against side reactions and their harmful effects meansprevention of both homolytic and heterolytic side reactions, which is mainlyaccomplished by trapping radicals, formaldehyde, andN-(methylene)iminium ions (5). Whileradical trapping is commonly reflected by the antioxidativeefficiency, the effectivity against heterolyticdegradationin the Lyocell dope can be expressed by the newly introduced termformaldehyde trapping capacity (FTC). Propyl gallate (PG,4), the most widely applied Lyocell stabilizer nowadays, actsas a phenolic antioxidant, and is finally oxidized to a deeply colored, highlyconjugated chromophore (11) via ellagicacid (10). It was demonstrated that 4 is alsoa quencher of formaldehyde and N-(methylene)iminium ions,both in organic solutions of NMMO and in Lyocell dope. The processes of radicaltrapping and scavenging of HCHO/5 are competitive in the caseof propyl gallate. A novel oxa-chromanol derivative, PBD (14),was designed as stabilizer for Lyocell solutions. In analogy to propyl gallate,PBD acts as a scavenger of all three dangerous species, namely HCHO,5 and radicals. Upon oxidation by radical species, PBDreleasesacetaldehyde which acts as a very efficient HCHO trap. Thus, in contrast topropyl gallate, radical trapping and HCHO trapping are not competitive. Boththeantioxidative efficiency and the capacity to trap HCHO and 5are higher for PBD as compared to propyl gallate. In preliminary stabilizertesting, mixtures of PBD and PG proved to be especially effective.     

Topography and Field Effects in Secondary Ion Mass Spectrometry – Part I: Conducting Samples

Quantitative chemical characterization of surfaces with topography by secondary ion mass spectrometry (SIMS) remains a significant challenge due to the lack of systematic and validated measurement methods. In this study, we combine an experimental approach using a simple model system with computer simulation using SIMION, to understand and quantify the key factors that give rise to unwanted topographic artefacts in SIMS images of conducting samples with microscale topography. Experimental data are acquired for gold wires (diameters 33 to 125 μm) mounted onto silicon wafers. Significant loss of ion intensities and shadowing arise from the distortion of the extraction field, and the chemical analysis over the whole of the sample surface is difficult. For large primary ion incidence angles of ≥55° to the surface normal, a fraction of the primary ions are scattered from the target and impact the substrate, emitting secondary ions that may be mistaken as originating from the wire. For conducting samples, topographic field effects may be reduced by the use of a smaller extraction voltage and an extraction delay. The effects of an extraction delay on ion intensities, mass resolution and time-of-flight are studied, and its application is demonstrated on an anisotropically etched silicon sample. The use of a simple sample holder with a V-shaped groove to reduce topographic field effects for wires is also presented. Using these results, we provide clear guidance to analysts for the diagnosis and identification of topography effects in SIMS, and present key recommendations to minimize them in practical analysis.     

Reactivity of benzylidene and alkylidenemalonates in radical addition mediated with dialkylzincs – An intriguing story

Benzylidene- and alkylidenemalonates are extremely reactive radical acceptors in dialkylzinc-mediated radical additions. Theoretical investigations showed that the multi-step radical-polar crossover process should be highly exothermic. Not only the addition of the alkyl radical to the complexed substrate is enthalpically favored but what is more, the homolytic substitution at the metal leading to a zinc enolate should also be exothermic, even though it necessitates the cleavage of the C-Zn bond from the complexed α-alkoxycarbonyl radical intermediate. This work was undertaken to highlight the power of chelation in controlling the fate of this type of reaction. Much to our surprise, no unambiguous experimental evidence could be put forward to prove the formation of the expected zinc enolate intermediate. Additionally, benzylidenemalonates and their alkylidene analogues (although to a lesser extent) exhibit an intriguing behavior. The backward reaction (retro-addition) can be triggered at work-up depending upon experimental conditions.     

Re-Emerging Field of Lignocellulosic Fiber – Polymer Composites and Ionizing Radiation Technology in their Formulation

Natural cellulose-based fibers offer low cost, low density composite reinforcement with good strength and stiffness. Because of their annual renewability and biodegradability, natural fibers have materialized as environmentally-friendly alternatives to synthetic fibers in the last two decades. They are replacing synthetic materials in some traditional composites in industrial manufacturing sectors such as automotive, construction, furniture, and other consumer goods. In this work, the use of lignocellulosic fibers in green materials engineering, particularly their application as polymeric composite reinforcement and surface treatment via ionizing radiation are reviewed. Because these cellulose-based materials are intrinsically hydrophilic, they require surface modification to improve their affinity for hydrophobic polymeric matrices, which enhances the strength, durability, and service lifetime of the resulting lignocellulosic fiber-polymer composites. In spite of a long history of using chemical methods in the modification of material surfaces, including the surface of lignocellulosic fibers, recent research leans instead towards application of ionizing radiation. Ionizing radiation methods are considered superior to chemical methods, as they are viewed as clean, energy saving, and environmentally friendly. Recent applications of controlled ionizing radiation doses in the formulation of natural fiber –reinforced polymeric composites resulted in products with enhanced fiber-polymer interfacial bonding without affecting the inner structure of lignocellulosic fibers. These applications are critically reviewed in this contribution.     

Mannose‐BSA Conjugates: Comparison Between Commercially Available Linkers in Reactivity and Bioactivity

Mannosyl ethanolamine and BSA were conjugated together by their amino groups with various homobifunctional cross‐linker reagents: disuccinimidyl carbonate (DSC), disuccinimidyl glutarate (DSG), disuccinimidyl suberate (DSS), ethylene glycolbis(succinimidylsuccinate) (EGS), 1,5‐difluoro‐2,4‐dinitrobenzene (DFDNB), diethyl squarate (DES), and thiophosgene (TP). The resulting mannose-BSA conjugates were subjected to an enzyme‐linked lectin assay (ELLA)to investigate their affinity to concanvalin A (ConA). With these results, the seven linkers were evaluated on the basis of five criteria, i.e., cost, reactivity, sugar loading, homogeneity, and affinity to ConA. Thus, DSS, DFDNB, and DES seemed to have advantages over the other cross-linking reagents.     

Solute�CSolvent Interactions in Aqueous Glycylglycine�CCuCl2 Solutions: Acoustical and Molecular Dynamics Perspective

Acoustical and molecular dynamics studies were carried out to understand the various interactions present in glycylglycine?CCuCl₂ aqueous solutions. Amongst these interactions, hydrogen bonding and solute?Csolvent interactions have been highlighted in this study. The radial distribution function (RDF) was used to investigate solution structure and hydration parameters. Binding of Cu²⁺ with various polar peptide atoms reveals the nature and degree of binding. The formation of complex clusters between glycylglycine and water molecules increases the relaxation time. The first hydration shell considerably influences the structure of the second shell, facilitating the formation of an ordered hydrogen bonded network. Both experimental and theoretical results have proved to be efficient in analyzing the behavior of molecules and to give a clear idea on molecular interactions in solutions.     

Structure and stability of halogenated polymers: Part 2—Chain-chlorinated polystyrene

Chain-chlorinated polystyrene samples have been prepared and characterised, containing from 2·5 to 34·3% chlorine by weight (from 0·1 to 1·3 chlorine atoms per styrene unit). Chlorination has been found to involve mainly substitution of the tertiary hydrogen atoms, followed by methylene substitution at reactant concentrations of more than 1 mole Cl₂ per styrene unit. Reaction with chlorine is quantitative in CCl₄ in the absence of air and the amount of ring-chlorination as a side reaction is very small.Chlorination in the backbone destabilises the polymer, which first loses hydrogen chloride on heating. The double bonds formed provide points of weakness for chain scission, which occurs at lower temperatures than for PS. Under programmed heating, the dehydrochlorination and chain scission reactions overlap to some extent in temperature range, but highly conjugated partially degraded polymer can be made from extensively chain-chlorinated PS. At more than 1 Cl per styrene unit, HCl is almost the sole volatile product, although the conjugated polymer breaks up to chain fragments above 300°C.     

Semi-synthetic Heparins with 2-Deoxy-2-sulfamino-α-l-iduronic Acid Residues: Chemical Reactivity and Biological Activity1

Abstract

Ammonolysis of the epoxide rings of 2,3-anhydro-α-L-guluronic acid residues, generated in alkaline medium from 2-O-sulfated α-L-iduronic acid residues of heparin, quantitatively afforded 2-amino-2-deoxy-α-L-iduronic acid residues. N-sulfation of these residues by TMA·SO₃ complex led to a formal replacement of the original 2-O-sulfate groups of heparin with N-sulfates, without configurational changes. These modified uronic acid residues (no longer amenable to alkaline epoxidation) can be easily N-desulfated. The presence of negative or positive charges at position 2 of the newly generated 2-amino-2-deoxy-α-L-iduronic acid residues influences the in vivo antithrombotic activity and haemorrhagic effects in different ways. A free amino group mainly decreases the haemorrhagic properties of heparin, while a negatively charged N-sulfate group decreases the coagulation parameters.     

The Use of Bone Substitutes in the Treatment of Bone Defects – the Clinical View and History

Summary: Bone has the ability to regenerate and remodel itself. In the clinic circumstances appear when bone defects do not heal spontaneously. These situations frequently result from trauma, congenital abnormities, infection or tumor resection. Hence, filling of the resulting defect by bone transplantation is a common practise with an increasing value in the re-establishment of the musculoskeletal system to promote bone healing. Since decades, efforts have been put to improve the effectiveness of bone substitutes. Conventional approaches with the use of ivory, animal and also human bone were not satisfactory. Negative effects like allergic reactions, rejection reactions, inflammations and other problems occurred. These led to implant failure, non union and amputation, to only mention a few. The introduction of bone banks and the development of standards in bone transplantation brought up the false hope to find a final solution for the treatment of bone loss. Disease transmissions (HIV) by allografts caused critical discussions. Despite all efforts, transplantation of autogenous cancellous bone is still the “gold standard” to induce bone healing. However, autografts are only limited available and are accompanied with high morbidity and mortality during the harvest. The problems associated with autologous and allogenous bone grafts promoted the development of multiple organic and inorganic bone substitutes. Well established substitutes at the present are demineralised bone matrix (DBM), composites and calcium phosphates (hydroxyl apatite and tri-calcium phosphate). These osteoconductive substances have shown to improve new bone formation. Nevertheless, clinical application of these materials is merely successful in a good bony environment but does not induce large progress in critical bone defects.     

N‐Chlorosulfonyloxazolidin‐2‐ones: Synthesis,Structure, and Reactivity Toward Aminoesters

Abstract

Synthesis, structure, and reactivity of chiral N‐chlorosulfonyloxazolidin‐2‐ones are described. Their synthesis were easily carried out starting from the corresponding chiral oxazolidin‐2‐ones and sulfuryl chloride to afford the title compounds 1 in high yields.     

Reactive Extraction of Citric Acid Using Tri-n-octylamine in Nontoxic Natural Diluents: Part 1—Equilibrium Studies from Aqueous Solutions

Use of cheap, nontoxic, and selective solvents could economically provide a solution to the recovery of carboxylic acids produced by the bioroute. In this regard in the present paper, reactive extraction of citric acid was studied. Problems encompassing the recovery of the acid ([H₃A] _aq ^o ?=?0.1?C0.8) was solved by using tertiary amine (tri-n-octylamine, TOA) in natural diluents (rice bran oil, sunflower oil, soybean oil, and sesame oil). TOA was very effective in removal of acid providing distribution coefficient (D) as high as 18.51 (E%?=?95?%), 12.82 (E%?=?93?%), 15.09 (E%?=?94?%), and 16.28 (E%?=?94?%) when used with rice bran oil, sunflower oil, soybean oil, and sesame oil, respectively. Overall extraction constants and association numbers for TOA + rice bran oil, TOA + sunflower oil, TOA + soybean oil, and TOA + sesame oil were evaluated to be 35.48 (mol/l)^?1.46, 29.79 (mol/l)^?1.30, 33.79 (mol/l)^?1.51, and 37.64 (mol/l)^?1.65 and 1.46, 1.30, 1.51, and 1.65, respectively. Specific equilibrium complexation constants (K _E(n/m)) were also predicted using mathematical modeling.     

Solutions of ionic liquids with diverse aliphatic and aromatic solutes – Phase behavior and potentials for applications: A review article

This article principally reviews our research related to liquid–liquid and solid–liquid phase behavior of imidazolium- and phosphonium-based ionic liquids, mainly having bistriflamide ([NTf₂]⁻) or triflate ([OTf]⁻) anions, with several aliphatic and aromatic solutes (target molecules). The latter include: (i) diols and triols: 1,2-propanediol, 1,3-propanediol and glycerol; (ii) polymer poly(ethylene glycol) (PEG): average molecular mass 200, 400 and 2050 – PEG200 (liquid), PEG400 (liquid) and PEG2050 (solid), respectively; (iii) polar aromatic compounds: nicotine, aniline, phenolic acids (vanillic, ferulic and caffeic acid,), thymol and caffeine and (iv) non-polar aromatic compounds (benzene, toluene, p-xylene). In these studies, the effects of the cation and anion, cation alkyl chain and PEG chain lengths on the observed phase behaviors were scrutinized. Thus, one of the major observations is that the anion – bistriflamide/triflate – selection usually had strong, sometimes really remarkable effects on the solvent abilities of the studied ionic liquids. Namely, in the case of the hydrogen-bonding solutes, the ionic liquids with the triflate anion generally exhibited substantially higher solubility than those having the bistriflamide anion. Nevertheless, with the aromatic compounds the situation was the opposite – in most of the cases it was the bistriflamide anion that favoured solubility. Moreover, our other studies confirmed the ability of PEG to dissolve both polar and non-polar aromatic compounds. Therefore, two general possibilities of application of alternative, environmentally acceptable, solvents of tuneable solvent properties appeared. One is to use homogeneous mixtures of two ionic liquids having [NTf₂]⁻ and [OTf]⁻ anions as mixed solvents. The other, however, envisages the application of homogeneous and heterogeneous (PEG + ionic liquid) solutions as tuneable solvents for aromatic solutes.Such mixed solvents have potential applications in separation of the aforesaid target molecules from their aqueous solutions or in extraction from original matrices. From the fundamental point of view the phase equilibrium studies reviewed herein and the diversity of the pure compounds – ionic liquids and target molecules – represent a good base for the discussion of interactions between the molecules that exist in the studied solutions.     

Erratum to: “Aqueous Phenol and Ethylene Glycol Solutions in Electrohydrodynamic Liquid Bridging”

The original version of the article was published in Cent. Eur. J. Chem. 9(3) (2011), pp 391–403. Unfortunately, the original version of this article contains mistakes in the caption of the y-axis of Figs. 5,6 and 10 due to a font conversion problem. The actual units on the y-axis of these figures should be μS cm⁻¹, not mS cm⁻¹.     

Reactivity of α-amino acids at their arenesulfonation in the water-1,4-dioxane and water-2-propanol systems

The kinetics of arenesulfonation of D,L-threonine, D,L-leucine and L-isoleucine with 3-nitrobenzenesulfonyl chloride in the water-1,4-dioxane and water-2-propanol solvents in the temperature range 298-313 K was studied. Calculations of effective values of activation parameters of reactions were carried out. Kinetic parameters of the studied processes were compared with the results of previous studies of the reaction of acyl transfer involving α-amino acids.     

Properties in Reactive Structure Materials: ZrW2 and HfW2 – High Melting Temperatures,Densities, Hardness,and Exothermic Ignition Energies

ZrW₂ and HfW₂ were prepared by melting the constituent elements in an arc-furnace. By cooling through perictectic phase lines above approximately 2000 °C, samples of the nominal 1:2 composition were obtained as products consisting of two phases, of which approximately 95 % adopts the MgCu₂ type structure and 5 % the W structure. In ZrW₂ and in HfW₂, the MgCu₂ type structure enables efficient topological compact spacefilling of the smaller W atoms into the cavities of the three-dimensional net constructed by the larger tetravalent metals Zr and Hf. Correspondingly, very dense and hard alloys are obtained which burn at a crash in air in a strong exothermic ignition reaction. These materials are non-toxic.