@article{pourmoazzen_sadeghifar_yang_lucia_2020, title={Cholesterol-modified lignin: A new avenue for green nanoparticles, meltable materials, and drug delivery}, volume={186}, ISSN={["1873-4367"]}, DOI={10.1016/j.colsurfb.2019.110685}, abstractNote={Two fractions of kraft lignin of low and high molecular weight were reacted with cholesteryl chloroformate (Chol.Cl) to produce a modified lignin that demonstrated very high hydrophobicity. Surprisingly, both fractions displayed discernible melting points as opposed to the starting lignin. The suspension in water also gave rise to nanoparticles that displayed sizes in the range of 200−500 nm that were shown to satisfactorily load and release folic acid, a representative hydrophobic molecule, within the context of drug delivery.}, journal={COLLOIDS AND SURFACES B-BIOINTERFACES}, author={Pourmoazzen, Zhaleh and Sadeghifar, Hasan and Yang, Guihua and Lucia, Lucian}, year={2020}, month={Feb} } @article{sadeghifar_ragauskas_2020, title={Perspective on Technical Lignin Fractionation}, volume={8}, ISSN={["2168-0485"]}, DOI={10.1021/acssuschemeng.0c01348}, abstractNote={Technical lignin extracted from pulping and biorefining processes provides a class of complex and polydisperse phenolic polymers. Preparation of lignin with lower structural complexity and polydisp...}, number={22}, journal={ACS SUSTAINABLE CHEMISTRY & ENGINEERING}, author={Sadeghifar, Hasan and Ragauskas, Arthur}, year={2020}, month={Jun}, pages={8086–8101} } @article{pourmoazzen_sadeghifar_chen_yang_zhang_lucia_2020, title={The morphology, self-assembly, and host-guest properties of cellulose nanocrystals surface grafted with cholesterol}, volume={233}, ISSN={["1879-1344"]}, DOI={10.1016/j.carbpol.2020.115840}, abstractNote={Cellulose nanocrystals (CNC) were prepared using acid hydrolysis of cellulose fiber. The CNC modified topo-chemically by grafting of bulky cholesterol moieties which changed subsequent morphology, thermal behavior, lyotropic crystalline properties, and host-guest release behavior. Bond formation between the cellulose nanocrystals surfaces and cholesterol was confirmed by FT-IR and solid-state NMR. The product indicated strong hydrophobic characteristics with an ordered chiral nematic self-assembly. This novel biomaterials were exploited through uptake of folic acid as part of a preliminary host-guest system. The guest molecule released as a function of physiologically relevant pHs was examined.}, journal={CARBOHYDRATE POLYMERS}, author={Pourmoazzen, Zhaleh and Sadeghifar, Hasan and Chen, Jiachuan and Yang, Guihua and Zhang, Kai and Lucia, Lucian}, year={2020}, month={Apr} } @article{sadeghifar_venditti_pawlak_jur_2019, title={Bi-component carbohydrate and lignin nanoparticle production from bio-refinery lignin: A rapid and green method}, volume={14}, ISSN={1930-2126 1930-2126}, url={http://dx.doi.org/10.15376/biores.14.3.6179-6185}, DOI={10.15376/biores.14.3.6179-6185}, abstractNote={A rapid and green preparation of lignin nanoparticles was demonstrated starting from bio-refinery lignin containing grafted carbohydrates. The particles were prepared by recovering a fraction of the lignin, which contained 24% carbohydrate (by weight) as the insoluble fraction in 0.5 M NaOH. The carbohydrate content of this fraction was verified with a wet chemistry analytical technique, nuclear magnetic resonance, and X-ray diffraction. This fraction was then dissolved in a NaOH/urea/water system and added dropwise to water under a high shear, which rapidly formed precipitated particles in a size range of approximately 100 nm. This carbohydrate-containing fraction of the lignin was soluble in a green solvent system that was not suited for lignin alone. The generated particles were stable in different organic solvents and water. Overall, the dissolution of the bio-refinery lignin in the NaOH/urea/water system, followed by precipitation in water can be regarded as a green and rapid method to produce stable nanoparticles. The generated nanoparticles, containing both carbohydrates and lignin, are expected to have unique applications because of their bi-component nature. Furthermore, this is the first publication to show how materials with high levels of lignin can be solubilized in solvents that are conventionally used for cellulose.}, number={3}, journal={BioResources}, publisher={BioResources}, author={Sadeghifar, Hasan and Venditti, Richard A. and Pawlak, Joel J. and Jur, Jesse}, year={2019}, month={Jun}, pages={6179–6185} } @article{sadeghifar_venditti_pawlak_jur_2019, title={Cellulose Transparent and Flexible Films Prepared from DMAc/LiCl Solutions}, volume={14}, ISSN={["1930-2126"]}, DOI={10.15376/biores.14.4.9021-9032}, abstractNote={Cellulose transparent and flexible film was prepared by dissolving micro-crystalline cellulose powder in Dimethylacetamide/Lithium Chloride (DMAc/LiCl) followed by regeneration in acetone and subsequent washing with water. The solution was cast on a glass plate. The interactions of water molecules and the swollen cellulose in the gel were examined by differential scanning calorimetry, DSC. An increased melting point of water in the gel indicated the presence of stronger bonding between water and cellulose than in the non-modified cellulose. The prepared dried films had 63 g/m2 weight and 0.06 mm thickness with 1.14 g/cm3 density.The prepared dry film exhibited high transparency, around 95% with visible light. The transparency and mechanical properties of the films were stable at high temperature (120°C) and exposure to UV irradiation. Thermal analysis of the prepared sample indicated film stability up to 275 °C. The tensile strength of the cellulose film was around 120 MPa with about 10% strain to break. The mechanical properties of the films were stable in alkali and acidic solutions.}, number={4}, journal={BIORESOURCES}, author={Sadeghifar, Hasan and Venditti, Richard and Pawlak, Joel J. and Jur, Jesse}, year={2019}, month={Nov}, pages={9021–9032} } @article{seyednejhad_khalilzadeh_zareyee_sadeghifar_venditti_2019, title={Cellulose nanocrystal supported palladium as a novel recyclable catalyst for Ullmann coupling reactions}, volume={26}, ISSN={0969-0239 1572-882X}, url={http://dx.doi.org/10.1007/s10570-019-02436-7}, DOI={10.1007/s10570-019-02436-7}, number={8}, journal={Cellulose}, publisher={Springer Science and Business Media LLC}, author={Seyednejhad, Sajedeh and Khalilzadeh, Mohammad A. and Zareyee, Daryoush and Sadeghifar, Hasan and Venditti, Richard}, year={2019}, month={Apr}, pages={5015–5031} } @article{khalilzadeh_sadeghifar_venditti_2019, title={Natural Clinoptilolite/KOH: An Efficient Heterogeneous Catalyst for Carboxymethylation of Hemicellulose}, volume={58}, ISSN={0888-5885 1520-5045}, url={http://dx.doi.org/10.1021/acs.iecr.9b02239}, DOI={10.1021/acs.iecr.9b02239}, abstractNote={Potassium hydroxide supported on natural zeolite clinoptilolite (CP) is found to be an efficient catalyst for the carboxymethylation of hemicellulose. Adsorption and dissociation of KOH on the surface of CP were investigated by pH measurement and theoretical modeling analysis using density functional theory. Indeed, the adsorption of KOH on the surface of the CP porous structure provides a cheap solid catalyst with increased basicity. Different ratios of KOH:CP were examined, and the 1:2 ratio gave the best results with almost two times higher efficiency than standard KOH solution, even with shorter reaction time and lower temperature. The carboxymethylated sample with KOH:CP (1:2) indicated less degradation than KOH as catalyst investigated by viscosity measurements. Thermal analysis of the original and modified hemicellulose indicated that the degree of substitutions of the sample calculated through thermal analysis was close to the results from the titration method.}, number={27}, journal={Industrial & Engineering Chemistry Research}, publisher={American Chemical Society (ACS)}, author={Khalilzadeh, Mohammad A. and Sadeghifar, Hasan and Venditti, Richard}, year={2019}, month={Jun}, pages={11680–11688} } @article{adebawo_sadeghifar_tilotta_jameel_liu_lucia_2019, title={Spectroscopic Interrogation of the Acetylation Selectivity of Hardwood Biopolymers}, volume={71}, ISSN={["1521-379X"]}, DOI={10.1002/star.201900086}, abstractNote={Abstract}, number={11-12}, journal={STARCH-STARKE}, author={Adebawo, Funke and Sadeghifar, Hassan and Tilotta, David and Jameel, Hasan and Liu, Yu and Lucia, Lucian}, year={2019}, month={Nov} } @article{amirsoleimani_khalilzadeh_sadeghifar_sadeghifar_2018, title={Surface modification of nanosatrch using nano silver: a potential antibacterial for food package coating}, volume={55}, ISSN={["0975-8402"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-85041908376&partnerID=MN8TOARS}, DOI={10.1007/s13197-017-2996-7}, abstractNote={Starch nanocrystal was prepared using weak sulfuric acid hydrolysis at 40 °C. Transmission electron micrographs of dilute suspensions of starch nanocrystals showed round particles with a diameter ranging from 20 to 40 nm. SEM of freeze dried samples showed separated particles between 40 and 100 nm and confirmed production of starch nano particles. XRD patterns obtained for the prepared nanostarch and raw starch sample showed no special pattern of crystallinity for starch sample. Extracted nanostarch showed pattern of crystallinity with the peaks at Bragg angles (2θ) at about 15° and 23°, and a doublet at 17° and 18°. The crystalline structure of prepared sample was A-type. FTIR spectra confirmed the particles oxidation. Nano silver particle was precipitated on the starch nano particle. UV spectra confirmed the presence of silver particle on the starch particles. Inhibitions tests of nanostarch bearing nano silver on three types of bacteria was investigated. The inhibition test results were 25 µg/mL for S. aureus, and S. typhi, and 12.5 µg/mL for E. coli.}, number={3}, journal={JOURNAL OF FOOD SCIENCE AND TECHNOLOGY-MYSORE}, author={Amirsoleimani, Mina and Khalilzadeh, Mohammad A. and Sadeghifar, Fatemeh and Sadeghifar, Hasan}, year={2018}, month={Mar}, pages={899–904} } @misc{cheraghi_taher_bijad_sadeghifar_2017, title={A Review: Stripping Voltammetric Methods as a High Sensitive Strategy for Trace Analysis of Ions, Pharmaceutical and Food Samples}, volume={13}, ISSN={["1875-6727"]}, DOI={10.2174/1573411012666160601130929}, abstractNote={Electrochemical techniques are powerful tools for trace analysis of important food, clinical and environmental compounds in real samples. In between electrochemical methods, stripping voltammetry technique is a very selective and highly sensitive method for the determination of nanomolar level of electroactive species in solution. Detection limits for electroactive compounds at sub-ppb concentrations have been reported using stripping voltammetric methods. Therefore, in this review, we focus on application of stripping voltammetric sensor for trace level analysis of metal ion, drug and environmental compounds. This review describes basic stripping voltammetric sensors and ability of them in the real sample analysis. Stripping voltammetric sensors can be used in industry for the analysis of food samples and they are a good alternative for HPLC method. Fast response and good limit of detection are the main reason that encourages us to write a review. Keywords: Stripping voltammetric, trace level analysis, sensor, electroactive compound analysis.}, number={1}, journal={CURRENT ANALYTICAL CHEMISTRY}, author={Cheraghi, Somaye and Taher, Mohammad A. and Bijad, Majede and Sadeghifar, Hasan}, year={2017}, pages={5–12} } @article{sadeghifar_venditti_jur_gorga_pawlak_2017, title={Cellulose-Lignin Biodegradable and Flexible UV Protection Film}, volume={5}, ISSN={2168-0485 2168-0485}, url={http://dx.doi.org/10.1021/acssuschemeng.6b02003}, DOI={10.1021/acssuschemeng.6b02003}, abstractNote={There is significant interest in biodegradable and transparent UV protection films from renewable resources for many different applications. Herein, the preparation and characterization of semitransparent flexible cellulose films containing low amounts of covalently bonded lignin with UV-blocking properties are described. Azide modified cellulose dissolved in dimethylacetamide/lithium chloride (DMAc/LiCl) was reacted with propargylated lignin to produce 0.5%, 1%, and 2% by weight lignin containing materials. Cellulose-lignin films were prepared by regeneration in acetone. These covalently bonded cellulose-lignin films were homogeneous, unlike the simple blends of cellulose and lignin. Prepared films showed high UV protection ability. Cellulose film containing 2% lignin showed 100% protection of UV-B (280–320 nm) and more than 90% of UV-A (320–400 nm). The UV protection of prepared films was persistent when exposed to thermal treatment at 120 °C and UV irradiation. Thermogravimetric analysis of the films s...}, number={1}, journal={ACS Sustainable Chemistry & Engineering}, publisher={American Chemical Society (ACS)}, author={Sadeghifar, Hasan and Venditti, Richard and Jur, Jesse and Gorga, Russell E. and Pawlak, Joel J.}, year={2017}, month={Nov}, pages={625–631} } @article{tayeb_sadeghifar_hubbe_rojas_2017, title={Lipoxygenase-mediated peroxidation of model plant extractives}, volume={104}, ISSN={["1872-633X"]}, DOI={10.1016/j.indcrop.2017.04.041}, abstractNote={Three unsaturated fatty acids, namely 9-cis,12-cis-linoleic acid, 1,2,3-tri-cis, cis-9,12-octadecadienoyl (glycerol trilinolein) and 1,2,3-tri-cis-9-octadecenoyl (triolein) were selected as models of components of plant extractives to monitor the hydroperoxygenation induced by soybean lipoxygenase (LOX), which was applied as an oxidative catalyst at room temperature. The fatty acids were monitored in colloidal dispersions in relation to their molecular changes using 1H/13C nuclear magnetic resonance (NMR), Fourier transform infrared (FTIR) and UV spectroscopies. The detection of the hydroperoxy group was limited due to its unstable nature. However, the reduction of protons associated with the diene groups and the substitution of hydroperoxy groups at the allylic positon in conjugated lipids were detected by the induced chemical shift of HOO-bearing 13C and 1H resonances and the oxygen absorption owing to changes in the molecule. Moreover, compared to the two other substrates, no oxygen substitution was observed in triolein, in accordance with its lower level of saturation and the absence of bis-allylic carbon. Our results are of relevance to plant fiber processing, since fatty acids are major constituents of hydrophobic deposits that cause a range of manufacturing challenges.}, journal={INDUSTRIAL CROPS AND PRODUCTS}, author={Tayeb, Ali H. and Sadeghifar, Hasan and Hubbe, Martin A. and Rojas, Orlando J.}, year={2017}, month={Oct}, pages={253–262} } @article{keyvanfard_hatami_gupta_agarwal_sadeghifar_khalilzadeh_2017, title={Liquid phase analysis of methyldopa in the presence of tyrosine using electrocatalytic effect of a catechol derivative at a surface of NiO nanoparticle modified carbon paste electrode}, volume={230}, ISSN={["1873-3166"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-85009892166&partnerID=MN8TOARS}, DOI={10.1016/j.molliq.2017.01.038}, abstractNote={Abstract An electrocatalytic based sensor fabricated for square wave voltammetric determination of methyldopa in the presence of tyrosine. For this goal, carbon paste electrode modified with NiO nanoparticle (NiO/NPs) and 2-(3,4-dihydroxyphenethyl)isoindoline-1,3-dione (DHPID) (CPE/DHPID/NiO/NPs) suggested as a highly selective sensor. The CPE/DHPID/NiO/NPs showed an excellent character for electrocatalytic oxidization of methyldopa in aqueous solution. For the mixture containing methyldopa and tyrosine, the oxidation peaks potential well separated from each other with differential potential ~ 500 mV. Methyldopa peak current increased linearly with its concentration at the ranges of 0.08–500 μM. The CPE/DHPID/NiO/NPs was successfully used for the analysis of methyldopa in drug samples.}, journal={JOURNAL OF MOLECULAR LIQUIDS}, author={Keyvanfard, Mohsen and Hatami, Mehdi and Gupta, Vinod Kumar and Agarwal, Shilpi and Sadeghifar, Hasan and Khalilzadeh, Mohammad A.}, year={2017}, month={Mar}, pages={290–294} } @article{sadeghifar_argyropoulos_2016, title={Macroscopic Behavior of Kraft Lignin Fractions: Melt Stability Considerations for Lignin-Polyethylene Blends}, volume={4}, ISSN={["2168-0485"]}, DOI={10.1021/acssuschemeng.6b00636}, abstractNote={Questions that pertain to the behavior of softwood kraft lignin fractions as opposed to the whole lignin still prevail. In an effort to further understand such effects at a macroscopic level, we have examined the issue of melt stability of polyethylene (PE) in blends with fractionated and unfractionated softwood kraft lignin. While methylation of the phenolic OH groups significantly stabilizes any lignin/PE melt, more in depth data demonstrate that when separate, acetone soluble (ASKL) and acetone insoluble (AIKL) kraft lignin fractions behave completely differently than the original unfractionated material. The low molecular weight methylated ASKL offers unexpected plasticizing action to PE melts, possibly as a consequence of its low molecular weight and spherical configuration. The higher molecular weight AIKL offers relatively stable PE melts, possibly manifesting its rigid nature and higher glass transition temperature likely occurring due to π stacking operating among its aromatic rings. Mixing these...}, number={10}, journal={ACS SUSTAINABLE CHEMISTRY & ENGINEERING}, author={Sadeghifar, Hasan and Argyropoulos, Dimitris S.}, year={2016}, month={Oct}, pages={5160–5166} } @article{karimi-maleh_hatami_moradi_khalilzadeh_amiri_sadeghifar_2016, title={Synergic effect of Pt-Co nanoparticles and a dopamine derivative in a nanostructured electrochemical sensor for simultaneous determination of N-acetylcysteine, paracetamol and folic acid}, volume={183}, ISSN={["1436-5073"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-84986255571&partnerID=MN8TOARS}, DOI={10.1007/s00604-016-1946-9}, number={11}, journal={MICROCHIMICA ACTA}, author={Karimi-Maleh, Hassan and Hatami, Mehdi and Moradi, Reza and Khalilzadeh, Mohammad A. and Amiri, Sedighe and Sadeghifar, Hasan}, year={2016}, month={Nov}, pages={2957–2964} } @article{sadeghifar_sen_patil_argyropoulos_2016, title={Toward Carbon Fibers from Single Component Kraft Lignin Systems: Optimization of Chain Extension Chemistry}, volume={4}, ISSN={["2168-0485"]}, DOI={10.1021/acssuschemeng.6b00848}, abstractNote={Single component softwood kraft lignins have been sought after as precursors to carbon fibers. This noble goal can be achieved by adding carbon onto lignin via propargylation. The reactivity of propargylated lignins may then be modulated via methylation, thus eliminating the onset of gelation via phenoxyl radical initiated random polymerization. This article demonstrates that properly installed propargyl groups of an acetone soluble kraft lignin (ASKL) fraction can be thermally polymerized to high molecular weights in a controlled manner. In order to create single component chain extended softwood kraft lignin systems for carbon fiber applications, one needs to regulate the amount and the positioning of the propargyl groups on the lignin. This became possible, and it is now demonstrated that the propargylation of lignin needs to occur first, followed by methylation and not the other way around. Such a sequence offers substantial benefits for the onset of a Claisen rearrangement to occur between the propar...}, number={10}, journal={ACS SUSTAINABLE CHEMISTRY & ENGINEERING}, author={Sadeghifar, Hasan and Sen, Sanghamitra and Patil, Shradha V. and Argyropoulos, Dimitris S.}, year={2016}, month={Oct}, pages={5230–5237} } @article{delgadillo_corona_toriz_contreras_sadeghifar_baobing_yang_lucia_delgado_2015, title={Coacervated liposoluble fructan-based host-guest microspheres as unique drug delivery materials}, volume={5}, ISSN={["2046-2069"]}, DOI={10.1039/c5ra10164f}, abstractNote={A new approach to drug release with microspheres from acetylated liposoluble fructans is demonstrated. Modification of solubility by acetylation supported their preparation by precipitation–coacervation that was able to encapsulate ∼33% of ibuprofen.}, number={83}, journal={RSC ADVANCES}, author={Delgadillo, Erika and Corona, Rosa I. and Toriz, Guillermo and Contreras, Hector J. and Sadeghifar, Hasan and Baobing, Wang and Yang, Guihua and Lucia, Lucian A. and Delgado, Ezequiel}, year={2015}, pages={67759–67766} } @article{sadeghifar_argyropoulos_2015, title={Correlations of the Antioxidant Properties of Softwood Kraft Lignin Fractions with the Thermal Stability of Its Blends with Polyethylene}, volume={3}, ISSN={["2168-0485"]}, DOI={10.1021/sc500756n}, abstractNote={Since technical lignins are increasingly considered as additives to polyolefins, an effort is made here to understand the fundamental antioxidant properties of softwood kraft lignin and its fractions on the thermal stability of its blends with polyethylene. Lower molecular weight acetone soluble kraft lignin (ASKL) fractions showed better antioxidant properties than unfractionated and acetone insoluble kraft lignin (AIKL). By selectively methylating the phenolic hydroxyl groups of the lignin and its fractions, it was shown that the lignin had no antioxidant ability. The phenolic OH groups in lignin, therefore, play a vital role toward imparting antioxidant characteristics in it. To further understand the role of lignin during the thermal processing of polyethylene, we measured the oxidation induction temperature (OITtemp) of its blends with softwood kraft lignin and its fractions. Once again, the role of the phenolic OH was found to be extremely important toward the thermal oxidative characteristics of kr...}, number={2}, journal={ACS SUSTAINABLE CHEMISTRY & ENGINEERING}, author={Sadeghifar, Hasan and Argyropoulos, Dimitris S.}, year={2015}, month={Feb}, pages={349–356} } @article{carpenter_scholle_sadeghifar_francis_boltersdorf_weare_argyropoulos_maggard_ghiladi_2015, title={Synthesis, Characterization, and Antimicrobial Efficacy of Photomicrobicidal Cellulose Paper}, volume={16}, ISSN={["1526-4602"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-84938937944&partnerID=MN8TOARS}, DOI={10.1021/acs.biomac.5b00758}, abstractNote={Toward our goal of scalable, antimicrobial materials based on photodynamic inactivation, paper sheets comprised of photosensitizer-conjugated cellulose fibers were prepared using porphyrin and BODIPY photosensitizers, and characterized by spectroscopic (infrared, UV-vis diffuse reflectance, inductively coupled plasma optical emission) and physical (gel permeation chromatography, elemental, and thermal gravimetric analyses) methods. Antibacterial efficacy was evaluated against Staphylococcus aureus (ATCC-2913), vancomycin-resistant Enterococcus faecium (ATCC-2320), Acinetobacter baumannii (ATCC-19606), Pseudomonas aeruginosa (ATCC-9027), and Klebsiella pneumoniae (ATCC-2146). Our best results were achieved with a cationic porphyrin-paper conjugate, Por((+))-paper, with inactivation upon illumination (30 min, 65 ± 5 mW/cm(2), 400-700 nm) of all bacterial strains studied by 99.99+% (4 log units), regardless of taxonomic classification. Por((+))-paper also inactivated dengue-1 virus (>99.995%), influenza A (∼ 99.5%), and human adenovirus-5 (∼ 99%). These results demonstrate the potential of cellulose materials to serve as scalable scaffolds for anti-infective or self-sterilizing materials against both bacteria and viruses when employing a photodynamic inactivation mode of action.}, number={8}, journal={BIOMACROMOLECULES}, author={Carpenter, Bradley L. and Scholle, Frank and Sadeghifar, Hasan and Francis, Aaron J. and Boltersdorf, Jonathan and Weare, Walter W. and Argyropoulos, Dimitris S. and Maggard, Paul A. and Ghiladi, Reza A.}, year={2015}, month={Aug}, pages={2482–2492} } @article{sadeghifar_dickerson_argyropoulos_2014, title={Quantitative P-31 NMR analysis of solid wood offers an insight into the acetylation of its components}, volume={113}, ISSN={["1879-1344"]}, DOI={10.1016/j.carbpol.2014.07.046}, abstractNote={As a solid substrate, wood and its components are almost invariably examined via spectroscopic or indirect methods of analysis. Unlike earlier approaches, in this effort we dissolve pulverized wood in ionic liquid and then directly derive its functional group contents by quantitative (31)P NMR. As such, this novel analytical methodology is thoroughly examined and an insight into the detailed way acetylation proceeds on solid wood and its components is provided as a function of wood density and within its various anatomical features. As anticipated, the efficiency of acetylation was found to be greater within low density wood than in high density wood. The lignin, the cellulose and the hemicelluloses of the low density wood was found to be acetylated nearly twice as fast with remarkable differences in their quantitative degree of acetylation amongst them. This direct analytical data validates the applied methodology and confirms, for the first time, that the order of acetylation in solid wood is lignin>hemicellulose>cellulose and no reactivity differences exist between early wood and late wood.}, journal={CARBOHYDRATE POLYMERS}, author={Sadeghifar, Hasan and Dickerson, James P. and Argyropoulos, Dimitris S.}, year={2014}, month={Nov}, pages={552–560} } @article{argyropoulos_sadeghifar_cui_sen_2014, title={Synthesis and Characterization of Poly(arylene ether sulfone) Kraft Lignin Heat Stable Copolymers}, volume={2}, ISSN={["2168-0485"]}, DOI={10.1021/sc4002998}, abstractNote={In this effort we aim at documenting our understanding of using the phenolic hydroxyl groups of technical softwood kraft lignin in replacing the multifunctional phenolic component required for the synthesis of poly(arylene ether) sulfones. To do this we use a two-pronged approach that uses fractionated softwood kraft lignin whose phenolic hydroxyl groups have been systematically protected in order to avoid gelation when copolymerized with 4, 4′-diflourodiphenyl sulfone (DFDPS). This has been done by careful 31P NMR profiling of the various hydroxyl groups present in the lignin as a function of the degree of phenolic hydroxyl group protection. For all copolymers, weight average molecular weights (Mw), polydispersity indices (PDI), glass transition temperatures (Tg), and thermal stability profiles (TGA) were obtained, providing an integrated picture of the scientific and technological ramifications of this work. Overall, this effort provides the foundations for creating lignin copolymers of controlled and m...}, number={2}, journal={ACS SUSTAINABLE CHEMISTRY & ENGINEERING}, author={Argyropoulos, Dimitris S. and Sadeghifar, Hasan and Cui, Chengzhong and Sen, Sanghamitra}, year={2014}, month={Feb}, pages={264–271} } @article{ayoub_venditti_pawlak_sadeghifar_salam_2013, title={Development of an acetylation reaction of switchgrass hemicellulose in ionic liquid without catalyst}, volume={44}, ISSN={0926-6690}, url={http://dx.doi.org/10.1016/j.indcrop.2012.10.036}, DOI={10.1016/j.indcrop.2012.10.036}, abstractNote={Hemicellulose material is an abundant and relatively under-utilized hetero-polysaccharides material present in lignocellulosic materials. In this research, an alkaline treatment was applied to switchgrass in order to extract hemicelluloses to subsequently produce an acetylated product. An extraction at 75 °C recovered 27% of the biomass as a predominantly hemicellulose material with a number average degree of polymerization of ∼500 determined by gel permeation chromatography. These hemicelluloses were acetylated with acetic anhydride in 1-allyl-3-methylimidazolium chloride ([Amim]+Cl−) ionic liquid in a complete homogeneous procedure without catalyst for the first time. It was determined that the yield and degree of substitution increased with reaction temperature from 30 to 80 °C and reaction time from 1 to 20 h. The product was characterized by FTIR spectroscopy, NMR, gel permeation chromatography for molecular weight and water contact angle analysis. FTIR spectroscopic analysis showed that the characteristic absorption intensities of acetylated hemicellulose increased and the hydroxyl group decreased with the increase in the degree of substitution. Increased degree of substitution increased the water contact angle and thermal stability in nitrogen. It was possible to cast films of the acetylated hemicellulose although the films were brittle. The results obtained indicate a promising combination between the effective extraction of hemicellulose from grasses and an environmentally friendly process using acetic anhydride in an ionic liquid without a catalyst to generate hemicellulose acetate with high degree of polymerization for use in various industrial applications.}, journal={Industrial Crops and Products}, publisher={Elsevier BV}, author={Ayoub, Ali and Venditti, Richard A. and Pawlak, Joel J. and Sadeghifar, Hasan and Salam, Abdus}, year={2013}, month={Jan}, pages={306–314} } @article{sen_sadeghifar_argyropoulost_2013, title={Kraft Lignin Chain Extension Chemistry via Propargylation, Oxidative Coupling, and Claisen Rearrangement}, volume={14}, ISSN={["1526-4602"]}, DOI={10.1021/bm4010172}, abstractNote={Despite its aromatic and polymeric nature, the heterogeneous, stochastic, and reactive characteristics of softwood kraft lignin seriously limit its potential for thermoplastic applications. Our continuing efforts toward creating thermoplastic lignin polymers are now focused at exploring propargylation derivatization chemistry and its potential as a versatile novel route for the eventual utilization of technical lignins with a significant amount of molecular control. To do this, we initially report the systematic propargylation of softwood kraft lignin. The synthesized derivatives were extensively characterized with thermal methods (DSC, TGA), (1)H, (13)C, and quantitative (31)P NMR and IR spectroscopies. Further on, we explore the versatile nature of the lignin pendant propargyl groups by demonstrating two distinct chain extension chemistries; the solution-based, copper-mediated, oxidative coupling and the thermally induced, solid-state, Claissen rearrangement polymerization chemistries. Overall, we show that it is possible to modulate the reactivity of softwood kraft lignin via a combination of methylation and chain extension providing a rational means for the creation of higher molecular weight polymers with the potential for thermoplastic materials and carbon fibers with the desired control of structure-property relations.}, number={10}, journal={BIOMACROMOLECULES}, author={Sen, Sanghamitra and Sadeghifar, Hasan and Argyropoulost, Dimitris S.}, year={2013}, month={Oct}, pages={3399–3408} } @article{carpenter_feese_sadeghifar_argyropoulos_ghiladi_2012, title={Porphyrin-Cellulose Nanocrystals: A Photobactericidal Material that Exhibits Broad Spectrum Antimicrobial Activity†}, volume={88}, ISSN={0031-8655}, url={http://dx.doi.org/10.1111/j.1751-1097.2012.01117.x}, DOI={10.1111/j.1751-1097.2012.01117.x}, abstractNote={Abstract}, number={3}, journal={Photochemistry and Photobiology}, publisher={Wiley}, author={Carpenter, Bradley L. and Feese, Elke and Sadeghifar, Hasan and Argyropoulos, Dimitris S. and Ghiladi, Reza A.}, year={2012}, month={Mar}, pages={527–536} } @article{sadeghifar_cui_argyropoulos_2012, title={Toward Thermoplastic Lignin Polymers. Part 1. Selective Masking of Phenolic Hydroxyl Groups in Kraft Lignins via Methylation and Oxypropylation Chemistries}, volume={51}, ISSN={["0888-5885"]}, DOI={10.1021/ie301848j}, abstractNote={This work offers a comprehensive understanding of the conditions required for the selective masking of the phenolic hydroxyl groups in technical kraft lignins, which is pivotal in determining their subsequent chemical and thermal reactivity. To this effect, we have examined the chemistry and developed the conditions for the facile, mild, and selective masking of the phenolic hydroxyl groups in softwood and hardwood kraft lignins. We have compared two series of methylated softwood kraft lignins synthesized using different methylation chemistries. Our data show that (when used as specified) dimethyl sulfate in aqueous NaOH selectively converts the phenolic hydroxyl groups of kraft lignin to its methylated derivatives without apparent side reactions. In contrast, methyl iodide (in the presence of excess K2CO3 in N,N-dimethylformamide) was found to be rather ineffective and unselective. Various milder methylation conditions were also examined for both softwood and hardwood kraft lignins using dimethyl sulfate...}, number={51}, journal={INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH}, author={Sadeghifar, Hasan and Cui, Chengzhong and Argyropoulos, Dimitris S.}, year={2012}, month={Dec}, pages={16713–16720} } @article{feese_sadeghifar_gracz_argyropoulos_ghiladi_2011, title={Photobactericidal Porphyrin-Cellulose Nanocrystals: Synthesis, Characterization, and Antimicrobial Properties}, volume={12}, ISSN={1525-7797 1526-4602}, url={http://dx.doi.org/10.1021/bm200718s}, DOI={10.1021/bm200718s}, abstractNote={Adherence and survival of pathogenic bacteria on surfaces leading to concomitant transmission to new hosts significantly contributes to the proliferation of pathogens, which in turn considerably increases the threat to human health, particularly by antibiotic-resistant bacteria. Consequently, more research into effective surface disinfection and alternative materials (fabrics, plastics, or coatings) with antimicrobial and other bioactive characteristics is desirable. This report describes the synthesis and characterization of cellulose nanocrystals that were surface-modified with a cationic porphyrin. The porphyrin was appended onto the cellulose surface via the Cu(I)-catalyzed Huisgen-Meldal-Sharpless 1,3-dipolar cycloaddition having occurred between azide groups on the cellulosic surface and porphyrinic alkynes. The resulting, generally insoluble, crystalline material, CNC-Por (5), was characterized by infrared and diffusion (1)H NMR spectroscopies, gel permeation chromatography, and thermogravimetric analysis. Although only suspended, and not dissolved, in an aqueous system, CNC-Por (5) showed excellent efficacy toward the photodynamic inactivation of Mycobacterium smegmatis and Staphylococcus aureus , albeit only slight activity against Escherichia coli . The synthesis, properties, and activity of CNC-Por (5) described herein serve as a benchmark toward our overall objectives of developing novel, potent, bioactive, photobactericidal materials that are effective against a range of bacteria, with potential utilization in the health care and food preparation industries.}, number={10}, journal={Biomacromolecules}, publisher={American Chemical Society (ACS)}, author={Feese, Elke and Sadeghifar, Hasan and Gracz, Hanna S. and Argyropoulos, Dimitris S. and Ghiladi, Reza A.}, year={2011}, month={Oct}, pages={3528–3539} } @article{sadeghifar_filpponen_clarke_brougham_argyropoulos_2011, title={Production of cellulose nanocrystals using hydrobromic acid and click reactions on their surface}, volume={46}, ISSN={["1573-4803"]}, DOI={10.1007/s10853-011-5696-0}, number={22}, journal={JOURNAL OF MATERIALS SCIENCE}, author={Sadeghifar, Hasan and Filpponen, Ilari and Clarke, Sarah P. and Brougham, Dermot F. and Argyropoulos, Dimitris S.}, year={2011}, month={Nov}, pages={7344–7355} }