Tailored oxidation of hydroxypropyl cellulose under mild conditions for the generation of wet strength agents for paper.

Secondary hydroxyl groups of hydroxypropyl cellulose (HPC) are transformed into reactive carbonyl groups selectively via TEMPO-mediated oxidation in the presence of sodium hypochlorite. By using this oxidation protocol, we introduced carbonyl functions in HPC under mild conditions, with a controlled degree of oxidation (DOx) up to 2.5 and a low degradation of the polysaccharide. The effect of the concentration of sodium hypochlorite on the resulting oxidized alcohol groups has been investigated in detail. Oxidized HPC crosslinks spontaneous at room temperature and mild pH-values with a variety of amines to form water stable hydrogels. If applied on lab-made paper sheet, thermally cross-linking this polymer with amines significantly increased the wet tensile strength. The utilization of such wet strength agents could lead to new approaches in terms of recyclability and biodegradability of wet strength agents interesting for a large number of different paper grades.

Quantification of C-H quenching in near-IR luminescent ytterbium and neodymium cryptates.

Two series of selectively deuterated cryptates with the lanthanoids Yb and Nd have been synthesized, and the luminescence lifetimes for the corresponding near-IR emission bands have been measured. Global fitting of these lifetime data combined with structural analysis allows for the accurate quantification of the contributions of individual C-H oscillators groups in the ligand to the nonradiative deactivation rates of the emissive lanthanoid states.

Spatially Resolved Crosslinking of Hydroxypropyl Cellulose Esters for the Generation of Functional Surface-Attached Organogels.

Chemistry, geometric shape and swelling behavior are the key parameters that determine any successful use of man-made polymeric networks (gels). While understanding of the swelling behavior of both water-swellable hydrogels and organogels that swell in organic solvents can be considered well-advanced with respect to fossil fuel-based polymer networks, the understanding, in particular, of wood-derived polymers in such a network architecture is still lacking. In this work, we focus on organogels derived from hydroxypropyl cellulose (HPC) ester. The latter polymer was functionalized with saturated and unsaturated fatty acids, respectively. Due to their tailored chemical constitution, we demonstrated that such polysaccharide can be crosslinked and simultaneously surface-bound by using a photo-induced radical reaction using a photo-initiator. Based on the choice of fatty acid used in the design of the HPC ester, and by controlling the degree of substitution (DS) obtained during the esterification of the polysaccharide, modular manipulation of the physical properties (e.g., polarity) of the resulting gel is possible. Depending on the initiator employed, different wavelengths of light, from UV to visible, can be utilized for the crosslinking reaction, which facilitates the deployment of a range of light sources and different lithographic methods. Additionally, we showed that altering of the illumination time allows to tailor the netpoint density, and thus, the degree of linear deformation in equilibrium and the swelling kinetics. Finally, we performed a proof-of-principle experiment to demonstrate the application of our material for the generation of spatially resolved polymer patches to enrich organic molecules from a solution within a microfluidic channel.

Reactivity of Isocyanate-Functionalized Lignins: A Key Factor for the Preparation of Lignin-Based Polyurethanes.

Using isocyanate-functionalized Kraft lignin as a reactive macromonomer for the preparation of polyurethane foams by a prepolymer technique is a well-known strategy to incorporate the biomacromolecule into a higher value polymer material. However, as of today the mechanical properties of the resulting materials are still insufficient for a number of possible applications. One reason for this limitation is that the reaction pathway and the morphological arrangement of such foams is of uttermost complexity and depends on a large number of influencing material-intrinsic factors. One important parameter is the reactivity of the functionalized lignin, which has a great impact on the interphase reaction kinetics and thus, on the geometry and mechanical properties of the resulting polyurethane foams. The reactivity is implied, amongst others, by the electron affinity of the isocyanate moiety. Herein, we investigate the reactivity of Kraft lignin modified with different commercially used isocyanates in the reaction with conventional polyols. Therefore, differently reactive prepolymers were synthesized, characterized and polyurethane foams were prepared thereof by using these compounds and the foam formation kinetics, morphological as well as mechanical properties were investigated. Finally, the results were supported by quantum mechanical calculations of the electron affinities of representative model compounds for the lignin-based prepolymers. This work gives rise to a better understanding of the effect of the reactivity and isocyanate structure linked to Kraft lignin on the polyurethane formation and enables rational choice of the isocyanate for pre-functionalization of lignin to prepare materials with better mechanical performance.

Superhydrophobic Hybrid Paper Sheets with Janus-Type Wettability.

We introduce the design of Janus-type paper sheets where one side of the paper exhibits superhydrophobic properties, whereas the other side of the sheet remains hydrophilic and therefore can take up aqueous solutions by capillary wicking. Such papers are being prepared by chemically immobilizing a thin hybrid coating on paper sheets that consists of cross-linked poly(dimethylsiloxane) (PDMS) and inorganic particles of various sizes ranging from nanometers to several tens of micrometers. Both commercially available Whatman No. 1 filter paper and lab-engineered cotton linters-based paper substrates were treated with this approach. The hybrid paper sheets have high chemical durability, mechanical stability, and flexibility because of a covalent attachment of the particles to paper fibers and the inherent elasticity of PDMS chains. In spite of the superhydrophobicity of the coating, the untreated side of the paper substrates preserved its hydrophilicity, resulting in Janus-type wetting and wicking properties, respectively. The functionalized paper samples remained porous and permeable to gases, while possessing a gradual change in chemistry between the two sides exhibiting a dramatic wetting contrast. Such two-sided properties open up new applications for such hybrid paper materials, such as in wound dressings and/or bandages with a liquid directing and confinement ability.

Covalent Attachment of Enzymes to Paper Fibers for Paper-Based Analytical Devices.

Due to its unique material properties, paper offers many practical advantages as a viable platform for sensing devices. In view of paper-based microfluidic biosensing applications, the covalent immobilization of enzymes with preserved functional activity is highly desirable and ultimately challenging. In the present manuscript, we report an efficient approach to achieving the covalent attachment of certain enzymes on paper fibers via a surface-bound network of hydrophilic polymers bearing protein-modifiable sites. This tailor-made macromolecular system consisting of polar, highly swellable copolymers is anchored to the paper exterior upon light-induced crosslinking of engineered benzophenone motifs. On the other hand, this framework contains active esters that can be efficiently modified by the nucleophiles of biomolecules. This strategy allowed the covalent immobilization of glucose oxidase and horseradish peroxidase onto cotton linters without sacrificing their bioactivities and performance upon surface binding. As a proof-of-concept application, a microfluidic chromatic paper-based glucose sensor was developed and achieved successful glucose detection in a simple yet efficient cascade reaction.

Modular Approach to 9-Monosubstituted Fluorene Derivatives Using Mo(V) Reagents.

Oxidative coupling using molybdenum(V) reagents provides fast access to highly functionalized 9-monosubstituted fluorenes. This synthetic approach is highly modular, is high yielding, and tolerates a variety of labile moieties, e.g. amides or iodo groups. The established protocol leads to promising precursors for pharmacologically important analogues of melatonin.

Versatile oxidative approach to carbazoles and related compounds using MoCl5.

The unique oxidizing power of molybdenum pentachloride provides an easy to perform, versatile, and high yielding method to construct carbazoles and the corresponding dibenzo analogues of thiophene, furan, and selenophene. The coupling reaction tolerates a variety of functional groups. The synthesis is highly modular. By this approach a precursor for the naturally occurring carbazole koenigicine was prepared.

Oxidative transformation of aryls using molybdenum pentachloride.

Molybdenum pentachloride combines a strong Lewis acid character with an unusually high oxidation potential creating a powerful reagent for oxidative transformations. Since the oxidative coupling reaction of aryls is induced at an extraordinarily high reaction rate, a variety of labile groups, e.g. iodo, tert-alkyl, etc., are tolerated on the aromatic core. Furthermore, the co-formed molybdenum salts can either be exploited for template effects to obtain uncommon geometries in a preferred manner, or redox-play starts after aqueous workup. Therefore MoCl(5) represents a unique and easily available reagent.

Synthesis of highly functionalized 9,10-phenanthrenequinones by oxidative coupling using MoCl5.

The strong oxidative power of molybdenum pentachloride gives rise to an efficient oxidative C-C bond formation of benzil derivatives to the corresponding 9,10-phenanthrenequinones. A highly complementary method to previous approaches was developed. The required derivatives are accessible in a modular fashion and in excellent yields. By this approach the orchid-derived natural product cypripediquinone A was synthesized for the first time.