Isopropylamine Research Articles

Relative toxicity of the components of the original formulation of Roundup® to five North American anurans

The responses of five North American frog species that were exposed in an aqueous system to the original formulation of Roundup® were compared. Carefully designed and un-confounded laboratory toxicity tests are crucial for accurate assessment of potential risks from the original formulation of Roundup® to North American amphibians in aquatic environments. The formulated mixture of this herbicide as well as its components, isopropylamine (IPA) salt of glyphosate and the surfactant MON 0818 (containing polyethoxylated tallowamine (POEA)) were separately tested in 96h acute toxicity tests with Gosner stage 25 larval anurans. Rana pipiens, R. clamitans, R. catesbeiana, Bufo fowleri, and Hyla chrysoscelis were reared from egg masses and exposed to a series of 11 concentrations of the original formulation of Roundup ® herbicide, nine concentrations of MON 0818 and three concentrations of IPA salt of glyphosate in static (non-renewal) aqueous laboratory tests. LC50 values are expressed as glyphosate acid equivalents (ae) or as mg/L for MON 0818 concentrations for comparison between the formulation and components. R. pipiens was the most sensitive of five species with 96h-LC50 values for formulation tests, for the five species, ranging from 1.80 to 4.22mg ae/L, and MON 0818 exposures with 96h-LC50 values ranging from 0.68 to 1.32mg/L. No significant mortality was observed during exposures of 96h for any of the five species exposed to glyphosate IPA salt at concentrations up to 100 times the predicted environmental concentration (PEC). These results agree with previous studies which have noted that the surfactant MON 0818 containing POEA contributes the majority of the toxicity to the herbicide formulations for fish, aquatic invertebrates, and amphibians. These study results suggest that anurans are among the most sensitive species, and emphasize the importance of testing the herbicide formulation in addition to its separate components to accurately characterize the toxicity and potential risk of the formulation.

Combined use of isopropylamine and trifluoroacetic acid in methanol-containing mobile phases for chiral supercritical fluid chromatography

In chiral supercritical fluid chromatography (SFC), mobile-phase additives are often used to improve enantioseparations and peak shapes. An acidic or basic additive is chosen, depending on the nature of the compound. This work highlights the simultaneous use of the acidic additive trifluoroacetic acid (TFA) and the basic additive isopropylamine (IPA) in supercritical fluid chromatography for enantioseparations. To evaluate the combination of TFA and IPA, 59 chiral pharmaceutical compounds were analyzed on four polysaccharide-based chiral stationary phases (CSPs): Lux® Cellulose-1, Lux® Cellulose-2, Lux® Cellulose-4 and Lux® Amylose-2. The results show that an important increase in enantioselectivity of the chromatographic system can occur when combining trifluoroacetic acid and isopropylamine in the mobile phase (MP), compared to the individual use of these additives. However, the combination of isopropylamine and trifluoroacetic acid in a supercritical methanol-containing mobile phase can also lead to problems as a result of the formation of salt complexes between the two additives. Combining the additives trifluoroacetic acid and isopropylamine and taking the appropriate measures to avoid salt formation, i.e. reducing the additives’ concentrations, can lead to simpler chiral SFC screening conditions that display even broader enantioselectivity.

Green nano-emulsion intervention for water-soluble glyphosate isopropylamine (IPA) formulations in controlling Eleusine indica ( E. indica)

This article describes the development of environmentally friendly nano-emulsion system for water-soluble herbicide application. Pseudoternary phase diagrams were established in the emulsion system of fatty acid methyl esters (FAMEs)/alkylpolyglucosides (APG) and/or 3-(3-hydroxypropyl)-heptamethyltrisiloxane (organosilicone)/water encompassed with 41% (w/w) glyphosate isopropylamine (IPA) as herbicide active. Pre-formulations were selected from isotropic (L) region in the phase diagrams and their emulsion system characteristics were determined. The microemulsion systems were chosen and then dispersed into water using low-energy stirring method (200 rpm for 5 min). Oil-in-water (O/W) nano-emulsions were formed with particle sizes of diameter less than 200 nm. The nano-emulsion systems showed significantly lower surface tension than a commercial formulation (Roundup®). In the biological application study, treatments of nano-emulsion formulations and Roundup® were applied on narrow-leaved weed Eleusine indica. Multiple doses of glyphosate IPA of the treatments were applied for the construction of dose–response curves for determination of effective dose (ED 50). The nano-emulsion formulation showed lower ED 50 was 0.40 kg a.e./ha in controlling the weed than Roundup® was 0.48 kg a.e./ha. This finding suggested that the possibility of using nano-emulsion system to increase penetration and uptake of glyphosate IPA.

Preparation of Silica Nanoparticles from Organic Laboratory Waste of Silica Gel HF254 and Their Use as a Highly Efficient Catalyst for the One‐Pot Synthesis of 2,3‐Dihydro‐1H‐isoindolone Derivatives

AbstractReaction of an isocyanide with an iminium ion intermediate, formed by reaction between 6‐formyl‐2,3‐dimethoxybenzoic acid and secondary amines (dibenzyl‐ or benzyl(isopropyl)amine) in the presence of silica nanoparticles (silica NPs, ca. 70 nm) proceeds smoothly at room temperature to afford 2,3‐dihydro‐1H‐isoindolone derivatives in high yields.

A toolbox approach for the rapid evaluation of multi-step enzymatic syntheses comprising a ‘mix and match’ E. coli expression system with microscale experimentation

This work describes an experimental ‘toolbox’ for the rapid evaluation and optimisation of multi-step enzymatic syntheses comprising a ‘mix and match’ E. coli-based expression system and automated microwell scale experimentation. The approach is illustrated with a de novo designed pathway for the synthesis of optically pure amino alcohols using the enzymes transketolase (TK) and transaminase (TAm) to catalyze asymmetric carbon-carbon bond formation and selective chiral amine group addition respectively. The E. coli expression system, based on two compatible plasmids, enables pairs of enzymes from previously engineered and cloned TK and TAm libraries to be evaluated for the sequential conversion of different initial substrates. This is complemented by the microwell experimentation which enables efficient investigation of different biocatalyst forms, use of different amine donors and substrate feeding strategies. Using this experimental ‘toolbox’, one-pot syntheses of the diastereoisomers (2S,3S)-2-aminopentane-1,3-diol (APD) and (2S,3R)-2-amino-1,3,4-butanetriol (ABT) were designed and performed, which gave final product yields of 90% mol/mol for APD and 87% mol/mol for ABT (relative to the initial TK substrates) within 25 hours. For the synthesis of APD, the E coli TK mutant D469E was paired with the TAm from Chromobacterium violaceum 2025 while for ABT synthesis the wild-type E. coli TK exhibited the highest specific activity and ee( enantiomeric excess) of >95%. For both reactions, whole-cell forms of the TK-TAm biocatalyst performed better than cell lysates while isopropylamine (IPA) was a preferable amine donor than methylbenzylamine (MBA) since side reactions with the initial TK substrates were avoided. The available libraries of TK and TAm enzymes and scalable nature of the microwell data suggest this ‘toolbox’ provides an efficient approach to early stage bioconversion process design in the chemical and pharmaceutical sectors.

The reactions of 4-chloro-2-butanol and 3-chloro-1-butanol with aqueous sodium hydroxide, and 1-chloro-2-propanol, and 2-chloro-1-propanol with isopropyl amine

The total reaction of 4-chloro-2-butanol 1 with NaOH(aq) is dominated (74%) by intramolecular substitution (SNi), besides which bimolecular substitution (SN2, 12%) and 1,4-elimination (i.e. fragmentation, contrary to earlier arguments) exhibit a significant contribution (11%). The total reaction of 3-chloro-1-butanol 2 instead is dominated by 1,4- (72%) and 1,2-elimination (25%), the substitution reactions being just observable (SNi 2% and SN2 1%). In 1 both the +I-effect and the conformational factors in the intermediate γ−chloroalkoxy anion favour the SNi-reaction, whereas in 2 the situation is opposite and the location of Cl on a secondary carbon also makes the SNi-reaction less favourable. The relative proportions of 1,4- and 1,2-eliminations for 2 can be explained by thermodynamic basis since the consequent products are more stable than the corresponding products from 1. 1-chloro-2-propanol 3 and 2-chloro-1-propanol 4 both react with isopropyl amine giving the same product, namely 1-isopropylamino-2-propanol, which indicates that the reaction proceeds through the propylene oxide intermediate. Compound 1 also reacted with isopropyl amine predominantly via S Ni-reaction, giving first 2-methyloxetane which then further gave 4isopropylamino-2-butanol, whereas 2 gave 3-isopropylamino-1-butanol through a direct SN2reaction.

Packed column supercritical fluid chromatography of isomeric polypeptide pairs

The characterization and determination of peptides is of great importance in the pharmaceutical industry as is the ability to rapidly perform targeted determinations of bioactive peptides in complex matrices. The purpose of the presented work is to assess the feasibility of packed column supercritical fluid chromatography (SFC) for the separation of two-pairs of water soluble peptides of identical mass, composition and charge that differ only in amino acid sequence. Upon evaluating a variety of conditions, trifluoroacetic acid (HTFA) in conjunction with methanol as the modifier proved to be, in general, the most successful mobile phase additive for elution of the two isomeric peptide pairs from all nitrogenous stationary phases. In contrast, water and ammonium acetate gave distorted peak shapes and therefore proved to be less satisfactory as neutral additives. The basic additive, iso-propylamine (IPAm), coupled with HA-Pyridine yielded the highest resolution factor for the complete study. Aminopropyl and HA-Pyridine columns with 5 μm particle size and 60 Å pore size were found to be best for resolution of each peptide pair. Bare silica and phenyl-hexyl stationary phases did not afford any separation. The primary roles of the carbon dioxide and methanol modifier are believed to provide (a) stationary phase solvation and (b) peptide solubility and transport; while, HTFA is postulated to fully protonate each peptide and form ion pairs between its conjugate base and cationic peptide analyte. The separation process, therefore, is best viewed as ion pair supercritical fluid chromatography (IP-SFC). For the case where IPAm gave good resolution on the HA-Pyridine column, the peptides are probably in the neutral state.

A novel route for synthesis of temperature responsive nanoparticles

AbstractWe report the preparation of responsive silica nanoparticles by reaction of epoxy modified silica with stimuli responsive poly (acrylic acid‐N‐isopropylacrylamide) (poly (AA‐co‐NIPAAm)). A series of copolymers of poly (AA‐co‐NIPAAm) were synthesized by a novel route, employing solid state condensation of polyacrylic acid and isopropyl amine in different feed ratios (44 mol %–100 mol % AA). The structure of the copolymers was characterized by FT‐IR, 1H‐NMR. The lower critical solution temperature (LCST) was found to vary with the copolymer composition. The pH dependence of the LCST was also observed, and the copolymers exhibited a higher LCST at neutral pH than at acidic pH (4–5). Selected copolymers were used to prepare responsive core‐shell particles. Silica nanoparticles modified using glycidoxy propyl trimethoxy propyl silane were reacted with the responsive copolymer to form responsive core‐shell particles. The influence of reaction conditions on the modification of silica particles and reaction with responsive copolymers was investigated. The hydrodynamic behavior of the synthesized thermo responsive nanoparticles was also studied. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

The toxicity of Roundup ® 360 SL formulation and its main constituents: Glyphosate and isopropylamine towards non-target water photoautotrophs

The toxicity of commercial formulation of Roundup ® 360 SL, widely used, nonselective herbicide and its main constituents, glyphosate (PMG), equimolar (1:1) isopropylamine salt of glyphosate (GIPA) and isopropylamine (IPA) was examined towards eight aquatic microphotoautotrophs; seven cyanobacterial strains representing either saline or freshwater communities, and common eukaryotic algae Chlorella vulgaris Beijerinck. Autotrophs were cultured 21 days in their appropriate standard media supplemented with various amounts of Roundup ®, glyphosate, GIPA and IPA. The determination of the growth of examined photoautotrophs was performed by time-course measurements of total chlorophyll content in experimental cultures. The growth rates related to corresponding concentrations of chemicals, the EC 50 values and generation doubling time were determined in order to present the toxicity Roundup ® 360 SL formulation and its main constituents. Market available formulation of Roundup ® was found to possess toxicity significantly higher than this, attributed to its main constituents; however both these compounds, isopropylamine and glyphosate, also inhibited the growth of examined strains in a dose-dependent manner. Notably, the interpretation of toxicity of the examined substances was found to be significantly dependent on the method of EC 50 calculation. The choice of molar or weight concentration of substances tested separately and in specific formulation was found to be essential in this matter. Due to these findings the EC 50 values were calculated based either on molar or on weight concentrations. Considering Roundup ® 360 SL formulation, these values ranged from 10 −3 up to 10 −1 mM and they were one order of magnitude lower than those found for isopropylamine. Quite surprisingly the minimum EC 50 values found for glyphosate did not reach micromolar concentrations, whereas most of the EC 50 values revealed to IPA did not exceed this range. Notably, in all the cases except for Synechocystis aquatilis Sauvageau, isopropylamine alone was indicated as more toxic than glyphosate.

Synthesis of ZSM-5 zeolite hollow spheres with a core/shell structure

Hollow and core/shell ZSM-5 spheres were simply synthesized through in situ transformation of mesoporous silica spheres (MSS) into MFI-type zeolite with the assistant of isopropylamine (IPA) as a structure-directing agent (SDA). IPA, with a mild structure-directing ability for the construction of MFI structure, triggered a stepwise crystallization of MSS after Al addition. First, the sphere surface was crystallized to a shell of ZSM-5 crystals. The silica and alumina species in the core condensed and crystallized to ZSM-5 thereafter, forming zeolite crystal aggregates inside the spheres. The obtained ZSM-5 spheres were highly crystalline materials and maintained the shape of pristine MSS, but exhibited a hollow and core/shell structure. The techniques of XRD, FT-IR, SEM, N2 adsorption-desorption, 29Si and 27Al MAS NMR were employed to trace the crystallization process, which allowed us to propose a “templating and surface to core” crystallization mechanism. This strategy may serve as an alternative way for synthesizing hollow zeolite spheres.

Transaminations with isopropyl amine: equilibrium displacement with yeast alcohol dehydrogenase coupled to in situ cofactor regeneration

Enantiopure chiral amines synthesis using omega-transaminases is hindered by an unfavourable equilibrium, but when using isopropylamine as the amine donor the equilibrium can be completely displaced by using a specific dehydrogenase in situ for removal of formed acetone.

Physicochemical Characteristics of SAPO-34 Molecular Sieves Synthesized with Mixed Templates as MTO Catalysts

In the present work, a variety of SAPO-34 catalysts have been prepared using various templates such as a single or mixtures of tetraethylammonium hydroxide (TEAOH), morpholine, diethylamine (DEA), triethylamine (TEA), dipropylamine (DPA), isopropylamine (IPA) and Diethanolamine (DEtA). It is shown that crystal morphology and physicochemical properties were affected by the kinds of templates and mixture contents. Especially, inexpensive SAPO-34 catalyst with good crystal properties and catalytic performance was obtained by using mixed template of DEA and TEAOH. Through N2 isotherm, XRD, SEM, NH3 TPD and 29Si-NMR techniques, the effect of mixed template on the crystal morphology, acidity and Si distribution were investigated. Catalytic activity and life stability of SAPO-34 in MTO reaction was improved by using mixed template because of the distinction of the crystal size, acidity and Si distribution.

Design and Control of the Monoisopropylamine Process

The monoisopropylamine (MIPA) process provides an interesting example of plantwide economic design optimization and plantwide control. The process consists of a tubular reactor and three distillation columns. There are both gas and liquid recycles. Fresh feed streams of isopropyl alcohol and ammonia are introduced into the process. The desired products are MIPA and water. An undesirable byproduct of di-isopropylamine (DIPA) is also produced and is recycled to extinction since its formation reaction is reversible. An excess of ammonia in the reactor inhibits the DIPA reaction, so ammonia is also recycled. The purpose of this paper is to present the details of the process for use by other workers as a test case for use in plantwide design and control studies. A heuristic economic optimum design and a control structure are developed. The process illustrates the classical design trade-off between reactor costs versus separation costs. In addition, the process has two recycles, which are both distillate products from different distillation columns, and this leads to another trade-off. Using more ammonia recycle produces less DIPA recycle. So the optimum design must balance the separation costs of the two recycles. Two of the distillation columns can be effectively controlled using a single temperature and a reflux-to-feed ratio control structure. The third column requires a dual control structure ratio (one temperature and one composition).

Synthesis and characterisation of aliphatic amides in application to surface protection

Aliphatic amides were synthesised in the laboratory using analytical grade fatty acids and isopropyl amine. These amides were then characterised for corrosion inhibition and surface protection properties. The amides were found to inhibit corrosion of carbon steel in 3 wt-% sodium chloride solution. Surface analysis using X-ray photoelectron spectroscopy revealed that the mechanism of inhibition is chemisorption type of adsorption.

Comparative effects of the formulation of glyphosate-surfactant herbicides on hemodynamics in swine

Introduction. Most of the glyphosate-surfactant herbicides (GlySH) are formulated commercial products containing isopropylamine (IPA) salt of glyphosate (IPAG), variable amount of a surfactant, and water. Although glyphosate is only slightly toxic to rats, ingestion of GlySH may lead to severe effects, including death, in humans. We conducted a study to evaluate the cardiovascular effects of the components of GlySH. Methods. We used five groups of male piglets, each receiving infusion of normal saline (control), glyphosate in NaOH base, IPA, IPAG, and polyoxyethyleneamine (POEA), respectively. We chose concentrations that are similar to those in the commonly used GlySH (41% of IPAG and 15% surfactant). Results. We found that IPAG reduced the mean arterial blood pressure (MABP) and left-ventricular stroke work index (LVSWI) during the infusion, but both recovered gradually. It also decreased the cardiac index but increased the pulmonary capillary wedge pressure, central venous pressure (CVP), and mean pulmonary arterial pressure (MPAP). POEA infusion reduced the cardiac index and LVSWI, but not the MABP. It also increased the pulmonary capillary wedge pressure, CVP, MPAP, and pulmonary vascular resistance index. IPA increased the MABP, which was higher than those in the control, IPAG, and POEA groups. Glyphosate in NaOH base infusion did not affect the hemodynamics but slightly reduced the blood pH and base excess (BE) values. POEA and IPAG also resulted in metabolic acidosis, with lactate formation and decreased BE values. Conclusion. We conclude that both POEA and IPAG infusion affected hemodynamics and resulted in death in piglets, whereas glyphosate (NaOH base) had no similar effects.

Efficacy and Economics of Summer Fallow Conventional and Reduced-Tillage Programs for Sugarcane

During the summer fallow period of the sugarcane production cycle, glyphosate in conjunction with frequent tillage is used to destroy sugarcane regrowth and reduce perennial weed infestations. For tillage to be reduced or eliminated in fallowed fields, weed control must be maintained and sugarcane must be completely destroyed so as not to interfere with the subsequent planting operation. Field studies were conducted to evaluate glyphosate rates and formulations for control of sugarcane, bermudagrass, and johnsongrass. Glyphosate (isopropylamine salt) applied in April at 1.68, 2.24, and 2.80 kg ai/ha controlled 15-cm sugarcane at least 95% 42 d after treatment (DAT). Control of 25- and 40-cm sugarcane was maximized at 1.68 kg/ha (91 and 86% control, respectively). In another study, 25-cm sugarcane was controlled equally with isopropyl amine and potassium salt glyphosate formulations. Bermudagrass control 40 d after glyphosate was applied at 1.12 kg/ha was 86% and increased to 98% when the same rate was applied sequentially. In fallowed sugarcane fields, conventional-tillage, reduced-tillage, and no-tillage programs were implemented from mid-April through mid-August to evaluate weed control and economics. When a glyphosate application was substituted for a tillage operation, bermudagrass and johnsongrass control was increased compared with the conventional tillage alone program, but differences in sugarcane and sugar yield among the various programs the following year were not observed. Based on 2006 costs, elimination of a single tillage operation reduced cost $18.49/ha and addition of glyphosate (2.8 kg/ha plus application cost) increased cost $43.47/ha. Total cost for the conventional tillage–alone fallow program was $110.94/ha; where herbicide was used in the reduced-tillage and no-tillage programs, total cost was $19.47 to $77.38/ha more.

Reactive Surface Coatings Based on Polysilsesquioxanes: Defined Adjustment of Surface Wettability

We have investigated a generally applicable protocol for a substrate-independent reactive polymer coating that offers interesting possibilities for further molecular tailoring via simple wet chemical derivatization reactions. Poly(methylsilsesquioxane)-poly(pentafluorophenyl acrylate) hybrid polymers have been synthesized by RAFT polymerization, and stable reactive surface coatings have been prepared by spin-coating on the following substrates: Si, glass, gold, PMMA, PDMS, and steel. These coatings have been used for a defined adjustment of surface wettability by surface-analogous reaction with various amines (e.g., glutamic acid to obtain hydrophilic surfaces (Theta(a) = 18 degrees) or perfluorinated amines to obtain hydrophobic surfaces (Theta(a) = 138 degrees)). Besides the successful covalent attachment of small molecules and polymers, amino-functionalized nanoparticles could also be deposited on the surface, resulting in nanostructured coatings, thereby expanding the accessible contact angle of hydrophobic surfaces further to Theta(a) = 152 degrees. The surface-analogous conversion of the reactive coating with isopropyl amine produced in situ temperature-responsive coatings. Using the presented simple, generally applicable protocol for substrate-independent reactive polymer coatings, the contact angle of water could be switched reversibly by almost 60 degrees.

Amidation of acrylic acid grafted polyethylene film with isopropylamine and temperature‐responsive character of the resulting amidated film

AbstractAn acrylic acid (AA) grafted polyethylene (PE) film with a homogeneous distribution of grafted chains was prepared by the photografting of AA onto a low‐density PE film with a thickness of 30 μm. The AA‐grafted PE film was subjected to amidation with isopropylamine (IPA) at 25°C in water as a solvent. Up to 80 mol % of the carboxyl groups of the AA‐grafted chains could be successfully converted to N‐isopropylacrylamide (NIPAAm) residues through the control of the amidation conditions, such as the reaction time, amount of the condensation reagent, and concentration of IPA. The resulting amidated PE film exhibited a temperature‐responsive character: the film swelled and shrank in water below and above a temperature range of about 40–60°C, respectively. The extent of the character of the amidated PE film was greater than that of NIPAAm‐ and NIPAAm/AA‐grafted PE films prepared by the photografting of NIPAAm monomer and NIPAAm/AA binary monomers, respectively. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

Deprotonation of hydrogen bonded Schiff bases by three strong nitrogen bases

Three Schiff bases obtained from substituted salicylaldehydes and 2-hydroxy-1-naphthaldehyde and aliphatic amines were investigated in terms of possible withdrawal of tautomeric proton from intramolecular hydrogen bridge. Three strong nitrogen bases: 1,8-bis(dimethylamino)naphtalene (DMAN), 1,1,3,3-tetramethylguanidine (TMG) and 1,8-bis(tetramethylguanidino)naphthalene (TMGN) were used as deprotonating agents in acetonitrile solution at room temperature. In the specified conditions it was found that only in the case of 5-nitrosalicylaldehyde and isopropyl amine derivative this process could be performed using TMG and TMGN as a base. The other derivatives, where bridged proton is shifted to oxygen or nitrogen atom, do not undergo such reaction. The deprotonation process was monitored by nitrogen and proton NMR measurements.

Discrepancy between TPD- and FTIR-based measurements of Brønsted and Lewis acidity for sulfated zirconia

Temperature-programmed desorptions (TPD) of isopropylamine (IPA), NH3, and pyridine were compared with diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) of pyridine to determine the effect of H2O on the Brønsted and Lewis acidities of two sulfated zirconia (SZ) catalysts. Although the traditional interpretation of pyridine infrared spectra showed an apparent increase in Brønsted acidity upon treating SZ with H2O, TPD spectra showed that H2O displaced IPA from approximately one-fifth of the Lewis sites with no corresponding increase in Bronsted acidity. Water treatment prior to TPD displaced similar amounts of both NH3 and pyridine. The primary effect of H2O is displacement of weakly adsorbed basic probe molecules from Lewis sites, rather than the conversion of Lewis sites to Brønsted sites. Finally, different types of analyses (e.g. infrared or TPD) of catalyst acidity yield dramatically different conclusions regarding Brønsted and Lewis acidity.