Amines are key intermediates in the chemical industry due to their nucleophilic characteristic which confers a high reactivity to them. Thus, they are key monomers for the synthesis of polyamides, polyureas, polyepoxydes, which are all of growing interest in automotive, aerospace, building, or health applications. Despite a growing interest for biobased monomers and polymers, and particularly polyamides, it should be noticed that very few natural amines are available. Actually, there is only chitosan and poly(lysine). In this review we present both fundamental and applied research on the synthesis of biobased primary and secondary amines with current available biobased resources. Their use is described as a building block for material chemistry. Hence, we first recall some background on the synthesis of amines, including the reactivity of amines. Second we focus on the synthesis of biobased amines from all sorts of biomass, from carbohydrate, terpenes, or oleochemical sources. Third, because they need opt...

Biobased Amines: From Synthesis to Polymers; Present and Future.

Nanoparticles (NPs) are novel drug delivery systems that have been attracting more and more attention in recent years, and have been used for the treatment of cancer, infection, inflammation and other diseases. Among the numerous classes of materials employed for constructing NPs, organic polymers are outstanding due to the flexibility of design and synthesis and the ease of modification and functionalization. In particular, NP based amphiphilic polymers make a great contribution to the delivery of poorly-water soluble drugs. For example, natural, biocompatible and biodegradable products like polysaccharides are widely used as building blocks for the preparation of such drug delivery vehicles. This review will detail carbohydrate based amphiphilic polymeric systems for cancer therapy. Specifically, it focuses on the nature of the polymer employed for the preparation of targeted nanocarriers, the synthetic methods, as well as strategies for the application and evaluation of biological activity. Applications of the amphiphilic polymer systems include drug delivery, gene delivery, photosensitizer delivery, diagnostic imaging and specific ligand-assisted cellular uptake. As a result, a thorough understanding of the relationship between chemical structure and biological properties facilitate the optimal design and rational clinical application of the resulting carbohydrate based nano delivery systems for cancer therapy.

Carbohydrate-based amphiphilic nano delivery systems for cancer therapy

Polysaccharides are abundant in nature, renewable, nontoxic, and intrinsically biodegradable. They possess a high level of functional groups including hydroxyl, amino, and carboxylic acid groups. These functional groups can be utilized for further modification of polysaccharides with small molecules, polymers, and crosslinkers; the modified polysaccharides have been used as effective building blocks in fabricating novel biomaterials for various biomedical applications such as drug delivery carriers, cell-encapsulating biomaterials, and tissue engineering scaffolds. This review describes recent strategies to modify polysaccharides for the development of polysaccharide-based biomaterials; typically self-assembled micelles, crosslinked microgels/nanogels, three-dimensional hydrogels, and fibrous meshes. In addition, the outlook is briefly discussed on the important aspects for the current and future development of polysaccharide-based biomaterials, particularly tumor-targeting intracellular drug delivery nanocarriers.

Recent Strategies to Develop Polysaccharide-Based Nanomaterials for Biomedical Applications

An environmentally benign emulsion polymerisation technique was exploited to prepare a bio based polymer from a naturally occurring monoterpene, β-myrcene. The structure of the polymer was ascertained by spectroscopic measurements. Density functional theory was employed to determine the ground state optimised structure of β-myrcene. The persulfate initiated polymyrcene possesses 3,4 and 1,2 vinyl defects along with 1,4 microstructures, whereas the redox analogue contains solely 1,4 addition products. The synthesised polymer displayed a substantially high molecular weight (upto 92 860 Da for persulfate polymyrcene) and subzero (−73 °C) glass transition temperature along with shear thinning behaviour within the experimental conditions, thereby rendering itself as a promising entrant in the domain of bio-based elastomers.

Synthesis, characterization and properties of a bio-based elastomer: polymyrcene

The conversion of a biorenewable plant oil (anethole) to a new fluoropolymer with both low dielectric constant and low water uptake is reported here. First, cationic polymerization of plant oil by using CF3SO3H as an initiator gave a polymer, which was then functionalized by introducing the thermocrosslinkable -OCF═CF2 groups via a three-step procedure. The obtained fluoropolymer can be easily thermally converted to an infusible and insoluble cross-linked network exhibiting low water uptake (<0.24%, in water of 96 °C for 4 days) and low dielectric constant (<2.64 at a range of frequencies varying from 1.0 to at 30 MHz at room temperature). TGA and DMA data showed that the cross-linked network had 5 wt % loss temperature of 400 °C (in N2) and a Tg of 160 °C, respectively. Nanoindentation tests indicated that the cross-linked film had an average hardness of 0.239 GPa and a Young’s modulus of 6.11 GPa. These results mean that the new polymer derived from biorenewable anethole is comparable to the petroleum-b...

Conversion of a Biorenewable Plant Oil (Anethole) to a New Fluoropolymer with Both Low Dielectric Constant and Low Water Uptake

https://hal-univ-pau.archives-ouvertes.fr/hal-01097130/document

Terpene and dextran renewable resources for the synthesis of amphiphilic biopolymers.

The synthesis of citronellal, an added-value chemical for perfumery, was performed through selective and green hydrogenation of citral into citronellal in water. Aqueous suspensions of spherical ammonium-capped palladium nanoparticles with sizes around 3 nm selectively reduced the conjugated carbon–carbon double bond. An excellent selectivity up to 97% in citronellal was achieved at complete conversion in water. The presence of potassium hydroxide proved crucial to control the selectivity and avoid other hydrogenation coproducts. These optimized conditions were further applied to a 135 g substrate loading, affording a relevant turnover number (TON) of 10,000. 

/pdf/highly-selective-and-multigram-hydrogenation-of-citral-into-18cpwgtt.pdf

Gilles Sagorin

Papers

Terpene and dextran renewable resources for the synthesis of amphiphilic biopolymers.

Highly Selective and Multigram Hydrogenation of Citral into Citronellal by Palladium Nanoparticles in Water