Search Results (28)

This study explores the synthesis of photocurable non-isocyanate polyhydroxyethylurethanes (BPHUs) derived from renewable sources, designed for biomedical applications and the development towards advanced light curing processes. The following two pathways were developed: an aliphatic route using 1,4-butanediol-derived cyclic carbonates and an aromatic route with resorcinol-based carbonates. Ring-opening polymerization with dodecanediamine produced BPHU intermediates, which were methacrylated to form photoreactive derivatives (aliphatic MAs and aromatic MAs). Comprehensive characterization, including NMR, GPC, and FTIR, confirmed the successful synthesis. The UV curing of these methacrylated compounds yielded hydrogels with swelling properties. Aliphatic BPHUs achieved a gel content of 91.3% and a swelling of 1057%, demonstrating the flexibility and UV stability suitable for adaptable biomedical applications. Conversely, aromatic BPHUs displayed a gel content of 78.1% and a swelling of 3304%, indicating higher rigidity, which is advantageous for load-bearing uses. Cytotoxicity assessments adhering to the DIN EN ISO 10993-5 standard demonstrated non-cytotoxicity, with an >80% cell viability for both variants. This research underscores the potential of green chemistry in crafting biocompatible, versatile BPHUs, paving the way for eco-friendly materials in implantable medical devices. Full article

Glycerol is a biogenic waste that is generated in both the biodiesel and oleo-chemical industries. The value addition of surplus glycerol is of utmost importance for making these industries economically profitable. In line with this, glycerol is converted into glycerol carbonate, a potential candidate for the industrial production of polymers and biobased non-isocyanate polyurethanes. In addition, glycerol can also be converted into solketal, which is the protected form of glycerol with a primary hydroxyl functional group. In this contribution, we developed a microwave-assisted solvent and catalyst-free method for converting solketal into solketal carbonate. Under conventional heating conditions, the reaction of solketal with dimethyl carbonate resulted in 70% solketal carbonate in 48 h. However, under microwave heating, 90% solketal carbonate was obtained in just 30 min. From the perspective of sustainability and green chemistry, biomass-derived heterogeneous catalysts are gaining importance. Therefore, in this project, several green catalysts, such as molecular sieves (MS, 4Å), Hβ-Zeolite, Montmorillonite K-10 clay, activated carbon from groundnut shell (Arachis hypogaea), biochar prepared from the pyrolysis of sawdust, and silica gel, were successfully used for the carbonyl transfer reaction. The obtained solketal carbonate was thoroughly characterized by ¹H NMR, ¹³C NMR, IR, and MS. The method presented here is facile, clean, and environmentally benign, as it eliminates the use of complicated procedures, toxic solvents, and toxic catalysts. Full article

Exploiting novel crosslinking chemistry, this study pioneers the use of waterborne polyurethane (WPU) to chemically crosslink porcine-derived gelatin, producing enhanced gelatin hydrogel films through a solvent-casting method. Our innovative approach harnesses the reactive isocyanate groups of WPU, coupling them effectively with gelatin’s hydroxyl and primary amino groups to form robust urea and urethane linkages within the hydrogel matrix. This method not only preserves the intrinsic elasticity of polyurethane but also significantly augments the films’ tensile strength and strain. Comprehensive characterizations of these hydrogel films and pre-formed hydrogel reaction mixtures were conducted using viscosity measurements, Fourier Transform Infrared Spectroscopy (FTIR), Thermogravimetric Analysis (TGA), and the universal testing machine (UTM) for tensile-recovery assessments, alongside evaluations of their biocompatibility. The results demonstrated a reduction in pore size with an increase in WPU concentration from 2 to 6% in the developed hydrogels with a decrease in the equilibrium swelling ratio from 15% to 9%, respectively. Further, hydrogels with 6% WPU exhibited the highest tensile stress in both a dry and wet state. The gelatin hydrogel formed with 6% WPU blend also demonstrated the growth and proliferation of CCD-986K (fibroblast) and CCD-1102 (keratinocyte) cells for up to 5 days of co-culturing. The results indicate a notable enhancement in the mechanical properties and biocompatibility of gelatin hydrogels upon the introduction of WPU, positioning these films as superior candidates for biomedical applications such as tissue engineering and wound dressing. Full article

Trinuclear and tetranuclear ruthenium carbonyls of the types Ru₃(CO)_n(NO)₂, Ru₃(N)(CO)_n(NO), Ru₃(N)₂(CO)_n, Ru₃(N)(CO)_n(NCO), Ru₃(CO)_n(NCO)(NO), Ru₄(N)(CO)_n(NO), Ru₄(N)(CO)_n(NCO), and Ru₄(N)₂(CO)_n related to species observed experimentally in the chemistry of Ru₃(CO)₁₀(µ-NO)₂ have been investigated using density functional theory. In all cases, the experimentally observed structures have been found to be low-energy structures. The low-energy trinuclear structures typically have a central strongly bent Ru–Ru–Ru chain with terminal CO groups and bridging nitrosyl, isocyanate, and/or nitride ligands across the end of the chain. The low-energy tetranuclear structures typically have a central Ru₄N unit with terminal CO groups and a non-bonded pair of ruthenium atoms bridged by a nitrosyl or isocyanate group. Full article

Developing recyclable and self-healing non-isocyanate polyurethane (NIPU) from renewable resources to replace traditional petroleum-based polyurethane (PU) is crucial for advancing green chemistry and sustainable development. Herein, a series of innovative cross-linked Poly(hydroxyurethane-urea)s (PHUUs) were prepared using renewable carbon dioxide (CO₂) and vanillin, which displayed excellent thermal stability properties and solvent resistance. These PHUUs were constructed through the introduction of reversible hydrogen and imine bonds into cross-linked polymer networks, resulting in the cross-linked PHUUs exhibiting thermoplastic-like reprocessability, self healing, and closed-loop recyclability. Notably, the results indicated that the VL-TTD*-50 with remarkable hot-pressed remolding efficiency (nearly 98.0%) and self-healing efficiency (exceeding 95.0%) of tensile strength at 60 °C. Furthermore, they can be degraded in the 1M HCl and THF (v:v = 2:8) solution at room temperature, followed by regeneration without altering their original chemical structure and mechanical properties. This study presents a novel strategy for preparing cross-linked PHUUs with self-healing and closed-loop recyclability from renewable resources as sustainable alternatives for traditional petroleum-based PUs. Full article

Non-isocyanate polyurethane synthesis by non-Sn catalysis is an essential challenge toward green polyurethane synthesis. Bismuth compounds are attractive candidates due to their low cost, low toxicity, and availability to urethane chemistry. This work applied various Bi catalysts to the self-polycondensation of a bishydroxyurethane monomer and found BiCl₃ to be an excellent catalyst through optimization. The catalytic activity and price of BiCl₃ are comparable to those of Bu₂SnO, while its toxicity is significantly low. BiCl₃ is, therefore, a promising alternative to Sn-based catalysts in non-isocyanate polyurethane synthesis. Full article

Thiols can react with readily available organic substrates under benign conditions, making them suitable for use in chemical, biological, physical, and materials and engineering research areas. In particular, the highly efficient thiol-based click reaction includes the reaction of radicals with electron-rich enes, Michael addition with electron-poor enes, carbonyl addition with isocyanate S_N2 ring opening with epoxies, and S_N2 nucleophilic substitution with halogens. This mini review provides insights into emerging venues for their industrial applications, especially for the applications of thiol-ene, thiol–isocyanate, and thiol–epoxy reactions, highlighting a brief chemistry of thiols as well as various approaches to polythiol synthesis. Full article

Volatile organic compounds (VOCs) from wood and wood composites are important contributors to odor profiles of indoor environments and can significantly influence human health and well-being. GC-MS/FID and gas chromatography (GC) with olfactometric detection (GC-O) are employed for the identification and characterization of odorants. Four different sample preparation methods are evaluated on wood strands and isocyanate adhesive–based oriented strand boards (OSBs) made from Pinus sylvestris L.: among these, dynamic headspace extraction thermal desorption ((dynamic) HS-TD), head space solid phase microextraction (HS-SPME), head space solid phase microextraction Arrow (HS-SPME Arrow), and liquid injection of a CH₂Cl₂ solvent extract. The olfactometric investigation revealed over 30 odor-active substances of cyclic and acyclic monoterpene, monoterpenoid ketone, monoterpenoid aldehyde, monoterpenoid alcohol, monoterpenoid ester, aliphatic aldehyde, alcohol, and acid and phenolic chemistry. Compared to liquid injection, (dynamic) HS-TD was found to result in a similar number of odorants (20 vs. 24), whereas HS SPME Arrow shows good performance with minimal instrumental effort, notably for monoterpene and aldehyde compounds. Native wood vs. OSB showed high concentrations of saturated and unsaturated aldehydes for the wood board sample. These findings demonstrate the capability of headspace methods for odorant detection and their suitability for standardization towards a database for wood and wood composites. Full article

Bacterially derived polyhydroxyalkanoates (PHAs) are attractive alternatives to commodity petroleum-derived plastics. The most common forms of the short chain length (scl-) PHAs, including poly(3-hydroxybutyrate) (P3HB) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), are currently limited in application because they are relatively stiff and brittle. The synthesis of PHA-b-PHA block copolymers could enhance the physical properties of PHAs. Therefore, this work explores the synthesis of PHBV-b-PHBV using relatively high molecular weight hydroxy-functionalised PHBV starting materials, coupled using facile diisocyanate chemistry, delivering industrially relevant high-molecular-weight block copolymeric products. A two-step synthesis approach was compared with a one-step approach, both of which resulted in successful block copolymer production. However, the two-step synthesis was shown to be less effective in building molecular weight. Both synthetic approaches were affected by additional isocyanate reactions resulting in the formation of by-products such as allophanate and likely biuret groups, which delivered partial cross-linking and higher molecular weights in the resulting multi-block products, identified for the first time as likely and significant by-products in such reactions, affecting the product performance. Full article

Polyurethane is a common polymeric coating, providing abrasion resistance, chemical durability, and flexibility to surfaces in the biomedical, marine, and food processing industries with great promise for future materials due to its tunable chemistry. There exists a large body of research focused on modifying polyurethane with additional functionalities, such as antimicrobial, non-fouling, anticorrosive action, or high heat resistance. However, there remains a need for the characterization and surface analysis of fluoro-modified polyurethanes synthesized with commercially available fluorinated polyol. In this work, we have synthesized traditional solvent-borne polyurethane, conventionally found in food processing facilities, boat hulls, and floor coatings, with polyurethane containing 1%, 2%, and 3% perfluoropolyether (PFPE). Polyurethane formation was confirmed by attenuated total reflectance Fourier-transform infrared (ATR-FTIR) spectroscopy, with the urethane band forming at 1730 cm⁻¹ and the absence of free isocyanate stretching from 2275–2250 cm⁻¹. X-ray photoelectron spectroscopy (XPS) was used to confirm perfluoropolyether polymerization with an increase in the atomic percentage of fluorine. Wettability and hydrophobicity were determined using a dynamic water contact angle with significant differences in advancing the water contact angle with the inclusion of perfluoropolyether blocks (PU–co–1PFPE 131.5° ± 8.0, PU–co–2PFPE 130.9° ± 5.8, and PU–co–3PFPE 128.8° ± 5.2) compared to the control polyurethane (93.6° ± 3.6). The surface orientation of fluorine supported the reduced critical surface tensions of polyurethane modified with PFPE (12.54 mN m⁻¹ for PU–co–3PFPE compared to 17.19 mN m⁻¹ for unmodified polyurethane). This work has demonstrated the tunable chemical qualities of polyurethane by presenting its ability to incorporate fluoropolymer surface characteristics, including low critical surface tension and high hydrophobicity. Full article

In this work, a durable superhydrophobic fabric was fabricated by using a facile UV-induced surface covalent modification strategy. 2-isocyanatoethylmethacrylate (IEM) containing isocyanate groups can react with the pre-treated hydroxylated fabric, producing IEM molecules covalently grafted onto the fabric’s surface, and the double bonds of IEM and dodecafluoroheptyl methacrylate (DFMA) underwent a photo-initiated coupling reaction under UV light radiation, resulting in the DFMA molecules further grafting onto the fabric’s surface. The Fourier transform infrared, X-ray photoelectron spectroscopy and scanning electron microscopy results revealed that both IEM and DFMA were covalently grafted onto the fabric’s surface. The formed rough structure and grafted low-surface-energy substance contributed to the excellent superhydrophobicity (water contact angle of ~162°) of the resultant modified fabric. Notably, such a superhydrophobic fabric can be used for efficient oil–water separation, for example a high separation efficiency of over 98%. More importantly, the modified fabric exhibited excellent durable superhydrophobicity in harsh conditions such as immersion in organic solvents for 72 h, an acidic or alkali solution (pH = 1–12) for 48 h, undergoing laundry washing for 3 h, exposure to extreme temperatures (from −196° to 120°), as well as damage such as 100 cycles of tape-peeling and a 100-cycle abrasion test; the water contact angle only slightly decreased from ~162° to 155°. This was attributed to the IEM and DFMA molecules grated onto the fabric through stable covalent interactions, which could be accomplished using the facile strategy, where the alcoholysis of isocyanate and the grafting of DFMA via click coupling chemistry were integrated into one-step. Therefore, this work provides a facile one-step surface modification strategy for preparing durable superhydrophobic fabric, which is promising for efficient oil–water separation. Full article

Pine seed shells and yerba mate are common wastes leftover from the food and beverage industry. This study presents the development of rigid polyurethane foams (RPUFs) filled with pine seed shells and yerba mate at 5, 10 and 15 wt%. The fillers were characterized for chemical properties using bench chemistry analyses, and the RPUFs were investigated in terms of chemical, morphological, mechanical, thermal and colorimetric characteristics. The main results indicated that yerba mate showed good compatibility with the polyurethane system, probably because its available hydroxyl groups reacted with isocyanate groups to form urethane bonds, producing increases in mechanical and thermal properties. However, pine seed shell did not appear to be compatible. Anisotropy increased slightly, as there was an increase in the percentage of reinforcement. The mechanical properties of the yerba mate reinforced foams proved stable, while there was a loss of overall up to ~50% for all mechanical properties in those reinforced with pine seed shell. Thermal properties were improved up to ~40% for the yerba mate reinforced foams, while those reinforced with pine nuts were stable. It was possible to observe a decrease in the glass transition temperature (T_g) of ~−5 °C for the yerba mate reinforced foams and ~−14 °C for the pine seed shell reinforced ones. Full article

2,5-Disubstituted 1,3,4-oxadiazoles are privileged versatile scaffolds in medicinal chemistry that have exhibited diverse biological activities. Acetyl- (AChE) and butyrylcholinesterase (BChE) inhibitors are used, e.g., to treat dementias and myasthenia gravis. 5-Aryl-1,3,4-oxadiazoles decorated with dodecyl linked via nitrogen, sulfur or directly to this heterocycle have been designed as potential inhibitors of AChE and BChE. They were prepared from commercially available or in-house prepared hydrazides by reaction with dodecyl isocyanate to form hydrazine-1-carboxamides 2 (yields 67–98%) followed by cyclization using p-toluenesulfonyl chloride and triethylamine in 41–100% yields. Thiadiazole isostere was also synthesized. The derivatives were screened for inhibition of AChE and BChE using Ellman’s spectrophotometric method. The compounds showed a moderate dual inhibition with IC₅₀ values of 12.8–99.2 for AChE and from 53.1 µM for BChE. All the heterocycles were more efficient inhibitors of AChE. The most potent inhibitor, N-dodecyl-5-(pyridin-4-yl)-1,3,4-thiadiazol-2-amine 3t, was subjected to advanced reversibility and type of inhibition evaluation. Structure–activity relationships were identified. Many oxadiazoles showed lower IC₅₀ values against AChE than established drug rivastigmine. According to molecular docking, the compounds interact non-covalently with AChE and BChE and block entry into enzyme gorge and catalytic site, respectively. Full article

Polyanionic cellulose carbamates were synthesized by rapid and efficient homogeneous aminolysis of cellulose carbonate half-esters in an ionic liquid/DMF medium. Cellulose bis-2,3-O-(3,5-dimethylphenyl carbamate), as a model compound, reacted with different chloroformates to cellulose carbonates. These intermediates were subjected to aminolysis, for which both the reactivity of different chloroformates towards C6-OH and the reactivity/suitability of the respective carbonate half-ester in the aminolysis were comprehensively studied. Phenyl chloroformate and 4-chlorophenyl chloroformate readily reacted with C6-OH of the model cellulose derivative, while 4-nitrophenyl chloroformate did not. The intermediate 4-chlorophenyl carbonate derivative with the highest DS (1.05) was then used to evaluate different aminolysis pathways, applying three different amines (propargyl amine, β-alanine, and taurine) as reactants. The latter two zwitterionic compounds are only sparingly soluble in pure DMF as the typical reaction medium for aminolysis; therefore, several alternative procedures were suggested, carefully evaluated, and critically compared. Solubility problems with β-alanine and taurine were overcome by the binary solvent system DMF/[EMIM]OAc (1:1, v/v), which was shown to be a promising medium for rapid and efficient homogeneous aminolysis and for the preparation of the corresponding cellulose carbamate derivatives or other compounds that are not accessible by conventional isocyanate chemistry. The zwitterionic cellulose carbamate derivatives presented in this work could be promising chiral cation exchangers for HPLC enantiomer separations. Full article

Carbon dioxide is an important raw material in many industrial technologies, but it is also one of the greenhouse gases that has to be effectively removed from the environment. This contribution provides a brief overview of carbon dioxide-based polymers developed in the laboratories of the Faculty of Chemistry at Warsaw University of Technology. We present some simple and versatile synthetic approaches that can be used to prepare a library of oligocarbonate diols, polycarbonates, poly(ester-carbonates), poly(ether-carbonates) and various types of polyurethanes, including the newly emerging family of environmentally friendly non-isocyanate polyurethanes. The main synthesis strategy involves the reaction of CO₂ with oxiranes to form five-membered cyclic carbonates, which can be utilized as a source of carbonate bonds in polymeric materials obtained by the ester exchange reactions and/or step-growth polyaddition. We also show that cyclic carbonates are valuable starting materials in the synthesis of hyperbranched polymers and polymer networks. The properties of several CO₂-based polymers are presented and their potential application as biomaterials, smart materials, and absorbers with a high CO₂ capture capacity is discussed. Full article