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1.
Copolymers with prolonged growth regulating activity for agriculture were prepared by the copolymerization of acrylamide with vinyl esters of 2,4-dichlorophenoxy acetic acid and 2,4-dichlorophenoxy butyric acid. Some kinetic relations were established. Reactivity ratios for the systems acrylamide-vinyl ester of phenoxyacetic acid (r1 = 4,08 ± 0,08 and r2 = 0,943 ± 0,16) and acrylamide-vinyl ester of 2,4-dichlorophenoxy butyric acid (r1 = 1.50 ± 0,09 and r2 = 1,02 ± 0,18) were determined. Conditions of preparing water soluble copolymers with good yield and sufficient high content of physiologically active units were established.  相似文献   

2.
Molecular and Crystal Structure of Dioxano-bis(2,4-dichlorophenoxyacetato)-copper (II) Cu2(2,4-D)4 · 5 Dioxan The cupric salt of 2,4-D crystallizes from dioxane solution in the space group P 1 with 2 formula units C16H10O6Cl4Cu and 5 dioxane molecules in the unit cell. The lattice constants are a = 12.557 Å, b = 14.391 Å, c = 9.537 Å, α = 112.56°, β = 99.62° and γ = 92.77°. By X-ray structure analysis the coordination around the Cu atoms was especially investigated.  相似文献   

3.
The kinetics of the dependence of pH, oxalate, and hydrogen peroxide concentrations on the degradation performance of the herbicide 2,4‐dichlorophenoxyethanoic acid (2,4‐D) was studied in a novel ferrous oxalate/H2O2/UV system. The formation and destruction of the primary intermediate, 2,4‐dichlorophenol (2,4‐DCP), was also monitored in the study. A rate enhancement of about 2.9 times was found when 1.2 mM of oxalate was added to the conventional Fe2+/H2O2/UV process. However, excess oxalate suppressed the reaction due to the scavenging and light attenuation effects. The 2,4‐D transformation at a lower initial pH was faster than that at a higher pH, and the different reaction mechanisms were investigated. In addition to the decay rates, the yield of the intermediate 2,4‐DCP was also affected by the initial solution pH. The increment of hydrogen peroxide concentration did not increase the initial decay rates of 2,4‐D, yet it improved the overall removal of 2,4‐D and elevated the formation of the corresponding intermediate (2,4‐DCP). Copyright © 2004 Society of Chemical Industry  相似文献   

4.
The thermal hazard of 2,4‐dinitroanisole (2,4‐DNAN) was evaluated by microcalorimetry methods. The specific heat capacity, melting enthalpy, and the solidification heat of 2,4‐DNAN were determined with a Micro‐DSCIII calorimeter. The thermal decomposition behavior of 2,4‐DNAN at four different heating rates was studied by using a C‐500 type calvet microcalorimeter. The kinetic and thermodynamic parameters were obtained from the analysis of the heat flow data. The critical temperature of thermal explosion (Tb) and the initial decomposition temperature (Tp0) were determined to distinctly evaluate the thermal hazard of 2,4‐DNAN.  相似文献   

5.
About the Autoxidation of the Linoleic Acid Methyl Ester in Water II. Isolation and Identification of 4-Hydroperoxy-nonen-2, 3-al-1 and 8-Hydroperoxycaprylic Acid Methyl Ester From the water soluble complex reaction products, formed in the ‘water reaction’ of 9,12-linoleic acid methyl ester, two new, till now unknown, lipidhydroperoxides are chromatographically isolated and analysed with chemical and physical methods. The results show that they are hydroperoxycaprylic acid methyl ester and hydroperoxy-2,3-trans-nonenal-(1). For the ultimate analysis data, both the hydroperoxides were first reduced with SnCl2 to the corresponding hydroxy compounds. The reduction product of the first hydroperoxide was found to be 4,4′-nitroazobenzoic acid ester and that of second as 2,4-dinitrophenylhydrazon.  相似文献   

6.
The reaction of (bipy)Ni(cod) ( 1 ) (bipy = 2,2′‐bipyridyl, cod = cycloocta‐1,5‐diene) with dioxygen and acetone at −20°C affords (bipy)Ni(C9H16O3) ( 2 ) (C9H16O32— = 2,4,6,6‐tetramethyl‐tetrahydropyran‐2,4‐diolate), which has been characterized by NMR, MS and an X‐ray crystal structure determination. Acidolysis of compound 2 with two equivalents of acetyl acetone (Hacac) yields (bipy)Ni(acac)2 and C9H18O3 ( 3 ) (2,4,6,6‐tetramethyl‐tetrahydropyran‐2,4‐diol), a cyclic trimer of acetone.  相似文献   

7.
BACKGROUND: Dinitrotoluenes (DNTs) are environmentally persistent, making the remediation of contaminated streams and groundwater difficult. Zero‐valent iron (Fe0) can be used as an electron source for the reduction of recalcitrant DNTs in waste‐water and thus enhance their biodegradability. However, little is known about the qualitative effects of major anions and cations present in waste‐water on the reduction of DNTs by Fe0. RESULTS: The presence of Na2SO4 and NaCl at levels between 0.25 and 2 mmol L?1 was observed to enhance the reactivity of Fe0 towards 2,4‐DNT. The positive effect of K2SO4 is stronger than that of Na2SO4 at the same level (1 mmol L?1). Varying (NH4)2SO4 from 0.1 to 1.0 mmol L?1 improved the efficiency of 2,4‐DNT degradation by Fe0. The effects of varying NaNO3 and NaNO2 from 0 mmol L?1 to 4.7 mmol L?1 and 0 mmol L?1 to 5.8 mmol L?1, respectively, were also investigated. Both NaNO3 and NaNO2 at low concentration improved the efficiency of 2,4‐DNT degradation by Fe0, however, at high concentration, inhibiting effects appeared. CONCLUSION: SO42?, Cl?, Na+, K+ and NH4+ notably enhanced 2,4‐DNT reduction by Fe0 at the tested concentrations. The positive effect of K+, Cl? was relatively stronger than that of Na+ and sulfate (SO42?). However, the effect of NH4+ was relatively weaker at concentrations greater than 1.0 mmol L?1. The presence of low concentrations of NO3? and NO2? promoted 2,4‐DNT reduction by Fe0 and inhibited the reaction. The results suggest that 2,4‐DNT reduction by Fe0 can be controlled by the ions composition of the waste‐water. Copyright © 2010 Society of Chemical Industry  相似文献   

8.
The process for catalytic synthesis of toluene‐2,4‐diisocyanate (TDI) from dimethyl carbonate (DMC) consists of two steps. Starting from the catalytic reaction between toluene‐2,4‐diamine (TDA) and DMC, dimethyl toluene‐2,4‐dicarbamate (TDC) is formed, and then decomposed to TDI. For the first step, the yield of TDC is 53.5% at a temperature of 250 °C, over Zn(OAc)2/α–Al2O3 catalyst. For the second step, the yield of TDI is 92.6% at temperatures of 250–270 °C and under pressure of 2.7 kPa, over uranyl zinc acetate catalyst, when di‐n‐octyl sebacate(DOS) is used as heat‐carrier, and a mixture of tetrahydrofuran (THF) and nitrobenzene is used as solvent. © 2001 Society of Chemical Industry  相似文献   

9.
BACKGROUND: Little attention has been paid to the use of large‐sized scrap cast iron for reduction of refractory organic pollutants at neutral pH and in the presence of dissolved oxygen (DO). RESULTS: Scrap cast iron and copper‐modified cast iron with fresh surfaces have a high reactivity towards the reduction of 2,4‐dinitrotoluene (2,4‐DNT). The extent of conversion reached around 80% and 97% respectively, though it gradually decreased with repeated reactions to relatively stable values of 63% and 72%, and recovered once the reacted filings were cleaned by dilute acid. After 50 days reaction, no dissolved copper appeared in the copper‐modified cast iron process. The mass loss of copper due to physical detachment reached 1.1% of the total coated copper within the initial 20 reaction days, and only 0.3% appeared in the next 30 days. 2,4‐DNT oxidizes scrap cast iron to generate mainly FeFe2O4 with DO, however, it oxidizes scrap copper‐modified cast iron to generate mainly γ‐FeO(OH) and α‐FeO(OH). CONCLUSION: Both samples of cast iron were successfully applied in the treatment of neutral wastewater containing 2,4‐DNT with high reactivity and good repeatable efficiency. Electrode reaction rate was enhanced by the deposited copper, which has strong chemical and physical stability. Copyright © 2011 Society of Chemical Industry  相似文献   

10.
Reactions of N‐(2,4‐dinitrophenyl)‐4‐arylpyridinium chlorides (aryl (Ar) = phenyl and 4‐biphenyl) with piperazine or homopiperazine caused opening of the pyridinium ring and yielded polymers that consisted of 5‐piperazinium‐3‐arylpenta‐2,4‐dienylideneammonium chloride (? N(CH2CH2)2N+ (Cl?)?CH? CH?C(Ar)? CH?CH? ) or 5‐homopiperazinium‐3‐arylpenta‐2,4‐dienylideneammonium chloride (? N(CH2CH2CH2)(CH2CH2)N+ (Cl?)?CH? CH?C(Ar)? CH?CH? ) units. 1H NMR spectral analysis suggested that the π‐electrons of the penta‐2,4‐dienylideneammonium group of the polymers were delocalized. UV‐visible spectral measurements revealed that the π‐conjugation system expanded along the polymer chains because of the orbital interaction between electrons of the two nitrogen atoms of the piperazinium and homopiperazinium rings. However, the π‐conjugation length depended on the distance between the two nitrogen atoms; that is, the polymers containing the piperazinium ring had a longer π‐conjugation length than those containing the homopiperazinium ring. Conversion of the piperazinium and homopiperazinium rings from the boat to the chair form led to a decrease in the π‐conjugation length. The surface of pellets that were molded from the polymers exhibited metallic luster, and these polymers underwent electrochemical oxidation in solution. Copyright © 2010 Society of Chemical Industry  相似文献   

11.
Quantitative Separation of 2,4-Dinitrophenylhydrazones of the Carbonyl-compounds Resulting from Butter Fat with the Help of Thin-layer Chromatography The volatile flavour-components from moldy and fresh butter as well as those from butter heated for different lengths of time were separated by molecular distillation and the carbonyles obtained were converted to 2,4-dinitrophenylhydrazones, which were then fractionated by thin-layer chromatography and the individual components of each fraction separated by partition chromatography. 11 fractions of the 2,4-dinitrophenylhydrazones were obtained from the carbonyles of the moldy butter, comprising of petanone-2, heptanone-2 and nonanone-2. Heated butter gave 9 fractions containing, amongst others, odd numbered methyl ketones from C3 to C15 and from fresh butter many fractions were obtained in which diacetyl and acetoin were present. The identification of the aforesaid hydrazones was based on the Rf.-values as well as spectrophotometric measurements.  相似文献   

12.
Mg–Zn–Al layered double hydroxides (LDHs) with varying amounts of zinc were prepared by the coprecipitation method. Solids were analyzed by XRD and N2 physisorption, confirming the formation of pure LDH phase; and the production of mixed oxides with high specific surface areas (182–276 m2 g−1) after calcination. Band gap energy was also determined, presenting the expected decreasing tendency on increasing zinc amounts. These mixed oxides were tested both for the adsorption of 2,4 dichlorophenoxiacetic acid (2,4-d) and for the photocatalytic degradation of 2,4-d and phenol. Nearly total (97%) degradation of initial 1.45 mmol L−1 of 2,4-d, with 1 g calcined LDH per liter, was accomplished in 9 h, while phenol half-life was as short as 3.5 h, with the catalyst with lowest zinc amount (5 wt.%). Langmuir adsorption isotherms are presented. Solids were also characterized by XRD and FTIR analysis after photocatalytic and adsorption activity, to determine the presence of 2,4-d. The versatility of LDH decomposition products in the elimination of different contaminants by different mechanisms puts them forward as a viable alternative for environmental remediation.  相似文献   

13.
To remove the nitro aromatic compounds (NACs) and SO32? from distillate of 2,4,6‐trinitrotoluene (TNT) red water, the carboxylated and aminated polystyrene (PSt) microspheres were used as adsorbents. GC‐MS and HPLC analysis were used to determine the types and concentrations of NACs before and after adsorption. The carboxylated PSt, which was prepared by modifying PSt with phthlandione (PA), could remove the neutral NACs including 2,6‐dinitrotoluene (2,6‐DNT), 2,4‐dinitrotoluene (2,4‐DNT), 1,3,5‐trinitrobenzene (1,3,5‐TNB), and 2,4,6‐trinitrotoluene (2,4,6‐TNT), with the acid 2,4‐dinitrophenol (2,4‐DNP) and SO32? remained in the distillate. The aminated PSt that was synthesized by activating PSt with chloroacetyl chloride follow by reaction with 1,2‐ethanediamine (EDA) could remove all the NACs and SO32?. The results suggested that EDA‐PSt adsorbed the NACs though multimode interactions, i.e., hydrogen bond and electrostatic attraction. After adsorption using EDA‐PSt, chemical oxygen demand (COD) was reduced from 86.1 to 11.2 mg L?1, and a colorless, transparent, and nontoxic solution with neutral pH value was obtained. Five grams of EDA‐PSt could purify 1600 cm3 of distillate of TNT red water, and the adsorbents could be recycled by elution with methanol to desorb the neutral NACs followed by elution with 0.1 mol L?1 NaOH to wash off 2,4‐DNP and SO32?. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

14.
Non‐cationic and amphipathic indoloazepinone‐constrained (Aia) oligomers have been synthesized as new vectors for intracellular delivery. The conformational preferences of the [l ‐Aia‐Xxx]n oligomers were investigated by circular dichroism (CD) and NMR spectroscopy. Whereas Boc‐[l ‐Aia‐Gly]2,4‐OBn oligomers 12 and 13 and Boc‐[l ‐Aia‐β3h‐l ‐Ala]2,4‐OBn oligomers 16 and 17 were totally or partially disordered, Boc‐[l ‐Aia‐l ‐Ala]2‐OBn ( 14 ) induced a typical turn stabilized by C5‐ and C7‐membered H‐bond pseudo‐cycles and aromatic interactions. Boc‐[l ‐Aia‐l ‐Ala]4‐OBn ( 15 ) exhibited a unique structure with remarkable T‐shaped π‐stacking interactions involving the indole rings of the four l ‐Aia residues forming a dense hydrophobic cluster. All of the proposed FITC‐6‐Ahx‐[l ‐Aia‐Xxx]4‐NH2 oligomers 19 – 23 , with the exception of FITC‐6‐Ahx‐[l ‐Aia‐Gly]4‐NH2 ( 18 ), were internalized by MDA‐MB‐231 cells with higher efficiency than the positive references penetratin and Arg8. In parallel, the compounds of this series were successfully explored in an in vitro blood–brain barrier (BBB) permeation assay. Although no passive diffusion permeability was observed for any of the tested Ac‐[l ‐Aia‐Xxx]4‐NH2 oligomers in the PAMPA model, Ac‐[l ‐Aia‐l ‐Arg]4‐NH2 ( 26 ) showed significant permeation in the in vitro cell‐based human model of the BBB, suggesting an active mechanism of cell penetration.  相似文献   

15.
Layered double hydroxides (LDHs) have high surface area and high anion exchange capacity, so they have been proposed to be an effective scavenger for contaminants. In this study, the adsorption of 2,4-dichlorophenoxyacetate (2,4-D) on Mg/Al–NO3 LDHs with varying layer charge density was investigated with particular attention on the effect of the orientation of the interlayer nitrate. Three Mg/Al LDHs were synthesized with Al3+/(Al3+ + Mg2+) molar ratios of 3.3 (LDH3), 2.6 (LDH4) and 2.1 (LDH5). The results of adsorption experiments showed that LDH5 exhibited an S-type isotherm with a low 2,4-D adsorption capacity due to the low accessibility of 2,4-D to the interlayer space. The accessibility was restricted by the small basal spacing of LDH5 as a result of the parallel orientation of the interlayer nitrate with respect to the hydroxide sheet. Thus, the 2,4-D adsorption occurred mainly on the external surface of the material. On the contrary, LDH3, which has the highest layer charge density among the samples, contains nitrate with an orientation perpendicular to the hydroxide sheet of LDH3. The interlayer nitrate was readily exchanged by 2,4-D. Thus, in addition to the adsorption on the external surface, the replacement of the interlayer nitrate by 2,4-D contributed to a higher adsorbed amount of 2,4-D; the 2,4-D adsorption of LDH3 exhibited an L-type isotherm. For LDH4 that contained interlayer nitrate with both parallel and perpendicular orientations, the adsorption characteristics were between those of LDH3 and LDH5. This work has demonstrated the dependence of 2,4-D adsorption characteristics on the nitrate orientation in LDHs, as a consequence of changing layer charge density.  相似文献   

16.
8‐Benzyl‐substituted tetrahydropyrazino[2,1‐f]purinediones were designed as tricyclic xanthine derivatives containing a basic nitrogen atom in the tetrahydropyrazine ring to improve water solubility. A library of 69 derivatives was prepared and evaluated in radioligand binding studies at adenosine receptor (AR) subtypes and for their ability to inhibit monoamine oxidases (MAO). Potent dual‐target‐directed A1/A2A adenosine receptor antagonists were identified. Several compounds showed triple‐target inhibition; one of the best compounds was 8‐(2,4‐dichloro‐5‐fluorobenzyl)‐1,3‐dimethyl‐6,7,8,9‐tetrahydropyrazino[2,1‐f]purine‐2,4(1H,3H)‐dione ( 72 ) (human AR: Ki A1 217 nM , A2A 233 nM ; IC50 MAO‐B: 508 nM ). Dichlorinated compound 36 [8‐(3,4‐dichlorobenzyl)‐1,3‐dimethyl‐6,7,8,9‐tetrahydropyrazino[2,1‐f]purine‐2,4(1H,3H)‐dione] was found to be the best triple‐target drug in rat (Ki A1 351 nM , A2A 322 nm; IC50 MAO‐B: 260 nM ), and may serve as a useful tool for preclinical proof‐of‐principle studies. Compounds that act at multiple targets relevant for symptomatic as well as disease‐modifying treatment of neurodegenerative diseases are expected to show advantages over single‐target therapeutics.  相似文献   

17.
BACKGROUND: Heterogeneous Fenton catalysts have been used to treat various organic pollutants in an aqueous environment. The present study has investigated the degradation of 2,4‐dinitrophenol (2,4‐DNP), a priority pollutant generated by such industries as pharmaceuticals, pesticides, pigments and dyes. Degradation of 2,4‐DNP (100 mg L?1) was studied using Fe3+ loaded on Al2O3 as a heterogeneous catalyst in the presence of H2O2, and the efficiency compared with the homogeneous Fe3+/H2O2 based Fenton‐like process. The effect of different parameters for both processes, such as catalyst loading, H2O2 concentration, initial solution pH, initial substrate concentration and temperature were investigated and the optimum operating conditions determined. RESULTS: Under optimal operating conditions of the homogeneous system ([Fe3+] 125 mg L?1; [H2O2] 250 mg L?1; pH 3; room temperature), 92.5% degradation was achieved in 35 min for an initial 2,4‐DNP concentration of 100 mg L?1. In the case of immobilized Fe (Fe3+–Al2O3 catalyst), degradation improved to 98.7% under the condition 10 wt% [Fe3+–Al2O3] 1 g L?1 catalyst loading; [H2O2] 250 mg L?1; pH 3; at room temperature for the same duration. CONCLUSIONS: This study demonstrated the stability and reusability of the prepared heterogeneous catalyst. This process is a viable technique for treatment of aqueous solutions containing contaminants. Copyright © 2012 Society of Chemical Industry  相似文献   

18.
Homopolymerization of disubstituted styrenes (2,4‐ and 2,5‐dimethylstyrene) and trisubstituted styrene (2,4,6‐trimethylstyrene) and their copolymerization with styrene were carried out using diphenylzinc–metallocene–methylaluminoxane initiator systems for metallocene (n‐BuCp)2TiCl2 and for half‐metallocene CpTiCl3. The studied comonomers were found to be less reactive than p‐tertbutylstyrene, p‐methylstyrene and styrene. The results indicate that, even though the methyl group has I+ inductive effect, di‐ and tri‐methylstyrenes are reluctant to undergo either homopolymerization or copolymerization. This behavior suggests that the reactivity is regulated not only by the inductive effect of the alkyl group but also by the steric impediment caused by the crowding of the substituents on the benzene ring. Copyright © 2006 Society of Chemical Industry  相似文献   

19.
Substituted 2‐tropolone natural products are found in plants and fungi. Their biosynthesis is thought to occur by ring expansion from a cyclohexadienone precursor, but this reaction has not previously been demonstrated experimentally. Treatment of 6‐hydroxy‐6‐hydroxymethylcyclohexa‐2,4‐dienone with the non‐haem iron(II)‐dependent extradiol catechol dioxygenase MhpB from Escherichia coli results in the formation of the 2‐tropolone ring‐expansion product through a pinacol‐type rearrangement. Three further substituted cyclohexa‐2,4‐dienone analogues were prepared, and treatment of each analogue was found to give the substituted 2‐tropolone ring‐expansion product. This ring expansion could also be effected nonenzymatically by treatment with 1,4,7‐triazacyclononane and FeCl2. This is a novel transformation for non‐haem iron‐dependent enzymes, and this is the first experimental demonstration of the proposed ring‐expansion reaction in tropolone biosynthesis.  相似文献   

20.
The reaction of the Cu(II) bis N,O‐chelate‐complexes of L‐2,4‐diaminobutyric acid, L‐ornithine and L‐lysine {Cu[H2N–CH(COO)(CH2)nNH3]2}2+(Cl)2 (n = 2–4) with terephthaloyl dichloride or isophthaloyl dichloride gives the polymeric complexes {‐OC–C6H4–CO–NH–(CH2)n–CH(nh2)(COO)Cu(OOC)(NH2)CH–CH2)n–NH‐}x 1 – 5 . From these the metal can be removed by precipitation of Cu(II) with H2S. The liberated ω,ω′‐N,N′‐diterephthaloyl (or iso‐phthaloyl)‐diaminoacids 6 – 10 react with [Ru(cymene)Cl2]2, [Ru(C6Me6)Cl2]2, [Cp*RhCl2]2 or [Cp*IrCl2]2 to the ligand bridged bis‐amino acidate complexes [Ln(Cl)M–(OOC)(NH2)CH–(CH2)nNH–CO]2–C6H4 11 – 14 .  相似文献   

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