Life Cycle Assessment of Innovative Carbon Dioxide Selective Membranes from Low Carbon Emission Sources: A Comparative Study.

Carbon capture has been an important topic of the twenty-first century because of the elevating carbon dioxide (CO2) levels in the atmosphere. CO2 in the atmosphere is above 420 parts per million (ppm) as of 2022, 70 ppm higher than 50 years ago. Carbon capture research and development has mostly been centered around higher concentration flue gas streams. For example, flue gas streams from steel and cement industries have been largely ignored due to lower associated CO2 concentrations and higher capture and processing costs. Capture technologies such as solvent-based, adsorption-based, cryogenic distillation, and pressure-swing adsorption are under research, but many suffer from higher costs and life cycle impacts. Membrane-based capture processes are considered cost-effective and environmentally friendly alternatives. Over the past three decades, our research group at Idaho National Laboratory has led the development of several polyphosphazene polymer chemistries and has demonstrated their selectivity for CO2 over nitrogen (N2). Poly[bis((2-methoxyethoxy)ethoxy)phosphazene] (MEEP) has shown the highest selectivity. A comprehensive life cycle assessment (LCA) was performed to determine the life cycle feasibility of the MEEP polymer material compared to other CO2-selective membranes and separation processes. The MEEP-based membrane processes emit at least 42% less equivalent CO2 than Pebax-based membrane processes. Similarly, MEEP-based membrane processes produce 34-72% less CO2 than conventional separation processes. In all studied categories, MEEP-based membranes report lower emissions than Pebax-based membranes and conventional separation processes.

Utilization of Slaughterhouse Waste in Value-Added Applications: Recent Advances in the Development of Wood Adhesives.

Globally, slaughterhouses generate large volumes of animal byproducts. While these byproducts are an important resource of industrial protein that could potentially be utilized in various value-added applications, they are currently either underutilized in high-value applications or being used for production of relatively low-value products such as animal feed and pet food. Furthermore, some of the byproducts of animal slaughtering cannot enter food and feed chains and thus their disposal possesses a serious environmental concern. An innovative utilization of the proteinaceous waste generated by slaughterhouses comprises of waste processing to extract proteins, which are then incorporated into industrial processes to produce value-added bio-based products. In this report, we review the current processes for extraction of protein from proteinaceous waste of slaughterhouses, and utilization of the recovered protein in the development of protein-based wood adhesives.

Development of hydrolysed protein-based plywood adhesive from slaughterhouse waste: effect of chemical modification of hydrolysed protein on moisture resistance of formulated adhesives.

Specified risk materials (SRM) constitute the proteinaceous waste of slaughterhouses and are currently being disposed off either by incineration or by land filling. Over the last few years, our efforts have focused on developing technology platforms for deployment of this renewable resource for various value-added industrial applications. This report describes a technology for utilization of SRM for the development of an environmentally friendly plywood adhesive with an improved water resistance property. The feedstock (SRM) was first thermally hydrolysed according to a standard protocol, and the hydrolysed protein fragments (peptides) were recovered from the hydrolysate. The recovered peptides were chemically modified through esterification reaction using ethanol, and then chemically crosslinked with polyamideamine-epichlorohydrin (PAE) resin to develop a wood adhesive system. Plywood specimens were then developed using the peptides-PAE resin-based adhesive. The effects of crosslinking time, solid content of the adhesive formulation, ratio of peptides and crosslinking agent in the formulation, and curing conditions of specimen preparation on lap shear strength of resulting plywood specimens were systematically evaluated. Despite the hydrophilic nature of hydrolysed protein fragments, the peptides-PAE resin formulations exhibited remarkable water resistance property after curing. Capping of polar carboxyl groups of peptides by converting them to esters further improved the water resistance property of this adhesive system. Under the optimum conditions of adhesive preparation and curing, the ethyl ester derivative of peptides and PAE resin-based formulations resulted in plywood specimens having comparable dry as well as soaked shear strengths to those of commercial phenol formaldehyde resin.

Enhancing the Adhesive Strength of a Plywood Adhesive Developed from Hydrolyzed Specified Risk Materials.

The current production of wood composites relies mostly on formaldehyde-based adhesives such as urea formaldehyde (UF) and phenol formaldehyde (PF) resins. As these resins are produced from non-renewable resources, and there are some ongoing issues with possible health hazard due to formaldehyde emission from such products, the purpose of this research was to develop a formaldehyde-free plywood adhesive utilizing waste protein as a renewable feedstock. The feedstock for this work was specified risk material (SRM), which is currently being disposed of either by incineration or by landfilling. In this report, we describe a technology for utilization of SRM for the development of an environmentally friendly plywood adhesive. SRM was thermally hydrolyzed using a Canadian government-approved protocol, and the peptides were recovered from the hydrolyzate. The recovered peptides were chemically crosslinked with polyamidoamine-epichlorohydrin (PAE) resin to develop an adhesive system for bonding of plywood specimens. The effects of crosslinking time, peptides/crosslinking agent ratio, and temperature of hot pressing of plywood specimens on the strength of formulated adhesives were investigated. Formulations containing as much as 78% (wt/wt) peptides met the ASTM (American Society for Testing and Materials) specifications of minimum dry and soaked shear strength requirement for UF resin type adhesives. Under the optimum conditions tested, the peptides⁻PAE resin-based formulations resulted in plywood specimens having comparable dry as well as soaked shear strength to that of commercial PF resin.

Targeted intracellular delivery of resveratrol to glioblastoma cells using apolipoprotein E-containing reconstituted HDL as a nanovehicle.

The objective of this study is to transport and deliver resveratrol to intracellular sites using apolipoprotein E3 (apoE3). Reconstituted high-density lipoprotein (rHDL) bearing resveratrol (rHDL/res) was prepared using phospholipids and the low-density lipoprotein receptor (LDLr)-binding domain of apoE3. Biophysical characterization revealed that resveratrol was partitioned into the phospholipid bilayer of discoidal rHDL/res particles (~19 nm diameter). Co-immunoprecipitation studies indicated that the LDLr-binding ability of apoE3 was retained. Cellular uptake of resveratrol to intracellular sites was evaluated in glioblastoma A-172 cells by direct fluorescence using chemically synthesized NBD-labeled resveratrol (res/NBD) embedded in rHDL/res. Competition and inhibition studies indicate that the uptake is by receptor mediated endocytosis via the LDLr, with co-localization of apoE3 and res/NBD in late endosomes/lysosomes. We propose that rHDL provides an ideal hydrophobic milieu to sequester resveratrol and that rHDL containing apoE3 serves as an effective "nanovehicle" to transport and deliver resveratrol to targeted intracellular sites.

Calixarene-Mediated Liquid Membrane Transport of Choline Conjugates 2: Transport of Drug-Choline Conjugates and Neurotransmitters.

Lower rim carboxylic acid calix[n]arenes and upper rim phosphonic acid functionalized calix[4]arenes effect selective transport of distinct molecular payloads through a liquid membrane. The secret to this success lies in the attachment of a receptor-complementary handle. We find that the trimethylammonium ethylene group present in choline is a general handle for the transport of drug and drug-like species. Furthermore, neurotransmitters possessing ionizable amine termini are also transported. Some limitations to this strategy have been uncovered as payloads become increasingly lipophilic. These developments reveal new approaches to synthetic receptor-mediated selective small molecule transport in vesicular and cellular systems.

Pb, Sr and Ba calix[6]arene hexacarboxylic acid octahedral complexation: a dramatic effect of dealkylation.

Calix[6]arene hexacarboxylic acid binds instantly and with low symmetry to Pb, Sr and Ba. Later a highly symmetric up-down alternating conformation emerges. The solution structures are identical to their p-tert-butylcalix[6]arene hexacarboxylic acid counterparts. With either receptor an octahedral cage is formed around the metal. The transformation from low to high symmetry however proceeds at significantly faster rates for the de-t-butylated host.

p-tert-Butylcalix[6]arene hexacarboxylic acid as host for Pb(II), Sr(II) and Ba(II).

p-tert-Butylcalixarene hexacarboxylic acid initially binds with low symmetry, to later adopt a highly symmetric up-down alternating conformation in the presence of Pb, Sr or Ba. The conformational dynamics for the three ions are distinct, from 15 hours, to 20 days, to 38 days, respectively.

Adsorptive removal of cesium using bio fuel extraction microalgal waste.

An adsorption gel was prepared from microalgal waste after extracting biodiesel oil by a simple chemical treatment of crosslinking using concentrated sulfuric acid. The adsorbent exhibited notably high selectivity and adsorption capacity towards Cs(+) over Na(+) from aqueous solutions, within the pH range of slightly acidic to neutral. The adsorption followed Langmuir isotherm and the maximum adsorption capacity of the gel for Cs(+) calculated from Langmuir model was found to be 1.36 mol kg(-1). Trace concentration of Cs(+) ions present in aqueous streams was successfully separated from Na(+) ions using a column packed with the adsorbent at pH 6.5. The adsorption capacity of the gel towards Cs(+) in column operation was 0.13 mol kg(-1). Although the adsorbed Cs(+) ions were easily eluted using 1M hydrochloric acid solution, simple incineration is proposed as an alternative for the treatment of adsorbent loaded with radioactive Cs(+) ions due to the combustible characteristics of this adsorbent.

p-tert-Butylcalix[6]arene hexacarboxylic acid conformational switching and octahedral coordination with Pb(II) and Sr(II).

p-tert-Butylcalix[6]arene hexaacetic acid is in a symmetric cone conformation in CHCl3, but it becomes conformationally flexible in CHCl3/CH3CN (1 : 1). In this mixture the host has a strong binding affinity towards Pb(II) and instantly forms a complex of low symmetry--shortly thereafter structural reorganization occurs resulting in a high symmetry complex of Pb(II) in an octahedral cage of carboxylates. Sr(II) and Ba(II) display similar behavior over a longer period of time.

Calixarene-Mediated Liquid-Membrane Transport of Choline Conjugates.

A series of supramolecular calixarenes efficiently transport distinct molecular species through a liquid membrane when attached to a receptor-complementary choline handle. Calix-[6]arene hexacarboxylic acid was highly effective at transporting different target molecules against a pH gradient. Both carboxylic- and phosphonic-acid-functionalized calix[4]arenes effect transport without requiring a pH or ion gradient. NMR binding studies, two-phase solvent extraction, and three-phase transport experiments reveal the necessary and subtle parameters to effect the transport of molecules attached to a choline "handle". On the other hand, rescorin[4]arene cavitands, which have similar guest recognition profiles, did not transport guest molecules. These developments reveal new approaches towards attempting synthetic-receptor-mediated selective small-molecule transport in vesicular and cellular systems.

N-aminoguanidine modified persimmon tannin: a new sustainable material for selective adsorption, preconcentration and recovery of precious metals from acidic chloride solution.

A new adsorption gel has been developed by immobilizing N-aminoguanidine (AG), a chelating ligand, on persimmon tannin extract through consecutive reactions. Adsorption behavior of the gel was investigated for the adsorptive separation and recovery of precious metal ions from varying concentration of HCl medium. The adsorption isotherms of precious metal ions on the gel were described by the typical monolayer type of Langmuir model and the maximum adsorption capacities were evaluated as 8.90 mol kg(-1) for Au(III), 2.01 mol kg(-1) for Pd(II) and 1.01 mol kg(-1) for Pt(IV). Real time applicability of the gel was examined for the recovery of precious metals from actual leach liquor of e-waste leached with chlorine containing hydrochloric acid. The gel was found to be highly efficient and selective for the uptake of targeted metal ions in the presence of excess base metal ions and also exhibited superior selectivity over commercially available anion exchange resins.

Multiple proton ionizable calixarene derivatives with different ring sizes and complexation ability as efficient ionophores for complexation and solvent extraction of trivalent indium.

The solvent extraction behavior of multiple proton ionizable p-tert-butylcalix[4]arene and [6]arene carboxylic acid derivatives towards indium has been investigated along with an acyclic monomeric analogue from weakly acidic media into chloroform. The extraction mechanism is ion exchange and carboxylic acid groups are adequate ligating sites for extraction. The cyclic structure of calixarene ligands to accommodate the potential guest species and the cooperativity effect of multifunctional groups significantly affect the complexation behavior and calixarene derivatives are found to be excellent extractants over the monomeric analogue. The composition of the extracted complex depends on the solution pH and attempts to determine the composition of the extracted complex for the extraction of indium have been stymied by complications arising from the formation of polynuclear species of indium and bridged polymeric species of calixarene carboxylic acid derivatives. One mole of calix[4]arene derivative extracts 2.5 moles of indium whereas the calix[6]arene derivative tends to extract 4.0 moles of indium. The loaded indium is back extracted with 1 mol dm(-3) hydrochloric acid solution. Though quantitative back extraction of indium was achieved from the fully loaded calix[6]arene derivative, it was only achieved up to 85% in the case of the calix[4]arene derivative.

Methylene crosslinked calix[6]arene hexacaarboxylic acid resin: a highly efficient solid phase extractant for decontamination of lead bearing effluents.

Calixarene-based cation exchange resin has been developed by methylene crosslinking of calix[6]arene hexacarboxylic acid derivative and the resin has been exploited for solid phase extraction of some toxic heavy metal ions. The selectivity order of the resin towards some metal ions follows the order Pb(II) > Cu(II)> Zn(II), Ni(II), Co(II). The maximum lead ion binding capacity of the resin was found to be 1.30 mmol g(-1) resin. The loaded lead was quantitatively eluted with dilute acid solution regenerating the resin. Mutual separation of Pb(II), Cu(II) and Zn(II) was achieved by using the column packed with the resin.

Technoeconomic analysis of five microalgae-to-biofuels processes of varying complexity.

The economics surrounding five algae-to-fuels process scenarios were examined. The different processes modeled were as follows: an open pond producing either triacylglycerides (TAG) or free fatty acid methyl ester (FAME), a solar-lit photobioreactor producing either FAME or free fatty acids (FFA), and a light emitting diode irradiated (LED-lighted) photobioreactor producing TAG. These processes were chosen to represent both classical and esoteric approaches presented in the open literature. Viable (or suggested) processing techniques to liberate and purify (and convert) the microalgal triacylglycerides were then modeled to accompany each growth option. The investment and cost per kg of fuel or fuel precursor for each process was determined. The open pond produced TAG at ∼$7.50/kg, while the process using the LED-lit photobioreactor produced TAG at ∼$33/kg. The scenario containing the solar-lit photobioreactor produced FAME at ∼$25/kg, while the open pond produced FAME at ∼$4/kg. The scenario containing the solar-lit photobioreactor produced FFA at ∼$29/kg. The open pond scenarios appear to be closest to the $1/kg pricepoint at this time, and thus are the most viable economic options. Future technological advancements that reduce the cost of bioreactor vessels, LED lighting, and solvent recovery, may reduce the oil production costs of these scenarios to a more attractive level.

Cation complexation with p-tert-butylcalix[5]arene pentacarboxylic acid derivative: an allosteric regulation of the first metal ion for stepwise extraction of the second ion.

A calix[5]arene based solvent extraction reagent 3, appending carboxylic acid groups at the lower rim, has been developed and its complexation behavior towards some transition metal ions has been studied. The host 3 can selectively and quantitatively extract Pb(II) ions above pH 1.8 while other divalent ions such as Cu(II), Zn(II), Co(II), Ni(II) are extracted quantitatively only above pH 3.0. The outstanding Pb(II) selectivity of 3 comes from the size fit complementarity effect of the Pb(II) ion in the calix[5]arene cavity. One molecule of 3 extracts two Pb(II) ions in a stepwise manner. The first Pb(II) ion is extracted into the deep cavity of the calix[5]arene defined by phenoxy oxygen atoms. The first complexed Pb(II) ion acts as a template to bring the host into a cone conformation and induces a positive allosteric effect for the extraction of the second Pb(II) ion at an oxygen rich coordinating site composed of carboxyl groups. Both the Pb(II) ions are extracted through an ion exchange mechanism and the electroneutral complex in the organic phase is formed by the release of an equivalent number of hydrogen ions into aqueous solution. The loaded Pb(II) is easily back-extracted from Pb(II)-complexed 3 using dilute acid solution.