0000000000670110
AUTHOR
Tero Tuuttila
The Effect of Mechanocatalytic Pretreatment on the Structure and Depolymerization of Willow
In this study, the effect of a mechanocatalytic pretreatment on the structure of willow and sugar release from pretreated willow was explored. In the mechanocatalytic approach, the pretreatment consists of solvent-free impregnation with sulfuric acid and a mechanical treatment with ball milling. Willow sawdust and pretreated samples were analyzed with field emission scanning electron microscope and X-ray diffraction. The products in the sugar solution were determined as the total reducing sugars with the 3,5-dinitrosalicylic acid method and monosaccharides with capillary electrophoresis. According to the results, milling increased the sugar production, depending on the sulfuric acid load. T…
Synthesis and thermal behavior of Janus dendrimers, part 2
Abstract The thermal properties of twelve Janus-type dendrimers up to the second generation were evaluated by termogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Compounds consist of the dendritic bisMPA based polyester moieties, and either 3,4-bis-dodecyloxybenzoic acid, 3,5-bis-dodecyloxybenzoic acid or 3,4,5-tris-dodecyloxybenzoic acid moieties, attached to opposite sides of the pentaerythritol core. The thermal stability of the compounds was evaluated by TGA, displaying onset decomposition temperatures ( T d ) at around 250 °C. DSC measurements upon heating and cooling confirmed that OH terminated Janus dendrimers featuring large polarity difference in opposite …
Chiral donor–π-acceptor azobenzene dyes
Abstract Four chiral donor–π-acceptor azobenzene dye conjugates were synthesized and characterized. Chiral moieties, namely (S)-(+)-2-(6-methoxy-2-naphthyl)propionic acid (naproxen) and (S)-2-aminopropionic acid ( l -alanine), were attached to either the donor end or the acceptor site of the azo compound using ester or amide bonds, respectively. The structures of the molecules were verified using 1H NMR, 13C NMR and ESI TOF mass spectrometry; spectral properties were evaluated with UV–vis and CD spectrometry whilst thermal stability was determined by TGA. The compounds displayed a broad absorption maximum in the visible region between 433 and 483 nm. All compounds showed relatively high the…
Thermal and X-ray powder diffraction studies of aliphatic polyester dendrimers
The syntheses and thermal and X-ray powder diffraction analyses of three sets of aliphatic polyester dendrimers based on 2,2-bis(hydroxymethyl)propionic acid as a repeating unit and 2,2-dimethyl-1,3-propanediol, 1,5-pentanediol, and 1,1,1-tris(hydroxymethyl)ethane as core molecules are reported. These dendritic polyesters were prepared in high yields with the divergent method. The thermal properties of these biodendrimers were evaluated with thermogravimetric analysis and differential scanning calorimetry. The thermal decomposition of the compounds occurred around 250 °C for the hydroxyl-ended dendrimers and around 150 °C for the acetonide-protected dendrimers. In addition, the crystallinit…
Acid-catalyzed mechanocatalytic pretreatment to improve sugar release from birch sawdust : Structural and chemical aspects
This study examined acid-catalyzed mechanocatalytic pretreatment of birch sawdust without a separate impregnation step. Catalyst amount and pretreatment time were the key variables. Pretreated material was mixed with water for hydrolysis (100 °C, 60 min). The efficient release of total reducing sugars from birch sawdust is significant to the path towards biofuels and biochemicals. Based on the results, the structure and surface of birch sawdust changed as a function of mechanocatalytic pretreatment. Milling time caused significant transformations in birch structure and also increased the yields of reducing sugars. The highest yield of total reducing sugar from pretreated sawdust was 23.0% a…
Synthesis and characterization of polyene chromophores with hydroxyl functionalization
Abstract Eight hydroxyl functionalized donor–acceptor polyene chromophores 3–10 were synthesized and characterized. Knoevenagel condensation reaction of aromatic polyenals with 2-cyanoacetamide derivatives was utilized to synthesize chromophores with all-E configuration. Chromophores of this kind can be attached covalently to polymers or functionalized with dendrons in order to tune the properties. The structures of the molecules were verified by 1H NMR, 13C NMR, ESI-TOF mass spectrometry and UV–vis measurements. Reduced bond-length alternation of the molecules in DMSO-d6 solution were observed by calculating the average difference of the vicinal coupling constants between adjacent CH CH an…
Acid-catalyzed mechanocatalytic pretreatment to improve sugar release from birch sawdust: Structural and chemical aspects
Abstract This study examined acid-catalyzed mechanocatalytic pretreatment of birch sawdust without a separate impregnation step. Catalyst amount and pretreatment time were the key variables. Pretreated material was mixed with water for hydrolysis (100 °C, 60 min). The efficient release of total reducing sugars from birch sawdust is significant to the path towards biofuels and biochemicals. Based on the results, the structure and surface of birch sawdust changed as a function of mechanocatalytic pretreatment. Milling time caused significant transformations in birch structure and also increased the yields of reducing sugars. The highest yield of total reducing sugar from pretreated sawdust wa…
Unveiling Electronic Transitions in Three Novel Chiral Azo-Compounds Using Linear and Nonlinear Circular Dichroism: A Theoretical−Experimental Study
Herein, we report on the experimental and theoretically study of the linear absorption, electronic circular dichroism (ECD) spectra, as well as the two-photon absorption circular-linear dichroism measurements of three different chiral azo derivatives in dimethylsulfoxide solution. Using potential energy surfaces and frontier orbital analysis, we established the most stable conformation for each molecule and elucidated their different electronic transitions. Our theoretical calculations allowed us to unambiguously identify the spectral position of such transitions and correlate them with the spectral profiles observed in the two-photon absorption spectra. To further elucidate the characteris…
Rapid one-step solvent-free acid-catalyzed mechanical depolymerization of pine sawdust to high-yield water-soluble sugars
Abstract One-step absolute solvent-free acid-catalyzed mechanical depolymerization of pine sawdust (PSD) and commercially available α-cellulose to water-soluble sugars was carried out using ball milling. For comparison purposes, the commonly reported “solvent-free” mechanocatalytic depolymerization of lignocellulose method, which normally involves three steps (acid impregnation in solvent, vacuum drying, and mechanical depolymerization of lignocellulose), was performed. The 3,5-dinitrosalicylic acid (DNS) method was used to measure the total reducing sugar (TRS) of the obtained sugar solution, and major monosaccharides in the solution were analyzed by capillary electrophoresis (CE). More th…
Synthesis and thermal behavior of Janus dendrimers, part 1
Abstract Eight Janus-type dendrimers up to the second generation were synthesized, and their thermal properties were evaluated. Compounds consist of the dendritic bisMPA based polyester moieties, and either 3,4-dihexyloxybenzoic acid or 3,4-dihexadecyloxybenzoic acid moieties, attached to opposite sides of the pentaerythritol core. The structures of the molecules were verified with 1 H NMR, 13 C NMR, ESI TOF mass spectrometry and elemental analysis. The thermal stability was evaluated by thermogravimetric analysis, displaying onset decomposition temperatures ( T d ) ranging from 241 to 308 °C. Phase transitions were studied by differential scanning calorimetry. Based on the performed studie…
Synthesis and characterization of chiral azobenzene dye functionalized Janus dendrimers
Abstract Eight bischromophoric bisMPA based polyester Janus dendrimers emanating from a pentaerythritol core were synthesized and their properties evaluated. 4-((4-(Ethyl(2-(2-(6-methoxynaphthalen-2-yl)propanoyloxy)ethyl)amino)-phenyl)diazenyl)-benzoic acid and 4-((4-(ethyl(2-(2-(6-methoxynaphthalen-2-yl)propanoyloxy)-ethyl)-amino)phenyl)diazenyl)-3-nitrobenzoic acid were attached to the dendritic polyester skeleton to make chiral dendrimers up to the second generation. The structures and the purity of the molecules were verified with 1H NMR, 13C NMR, ESI TOF mass spectrometry, and elemental analysis. Spectral properties were evaluated with UV–vis and CD spectrometer. The compounds displaye…