- Occurrence of agmatine pathway for putrescine synthesis in Selenomonas ruminatium
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Selenomonas ruminantium synthesizes cadaverine and putrescine from L-lysine and L-ornithine as the essential constituents of its peptidoglycan by a constitutive lysine/ornithine decarboxylase (LDC/ODC). S. ruminantium grew normally in the presence of the specific inhibitor for LDC/ODC, DL-α-difluoromethylornithine, when arginine was supplied in the medium. In this study, we discovered the presence of arginine decarboxylase (ADC), the key enzyme in agmatine pathway for putrescine synthesis, in S. ruminantium. We purified and characterized ADC and cloned its gene (adc) from S. ruminantium chromosomal DNA. ADC showed more than 60% identity with those of LDC/ODC/ADCs from Gram-positive bacteria, but no similarity to that from Gram-negative bacteria. In this study, we also cloned the aguA and aguB genes, encoding agmatine deiminase (AguA) and N-carbamoyl-putrescine amidohydrolase (AguB), both of which are involved in conversion from agmatine into putrescine. AguA and AguB were expressed in S. ruminantium. Hence, we concluded that S. ruminantium has both ornithine and agmatine pathways for the synthesis of putrescine.
- Liao, Shaofu,Poonpairoj, Phuntip,Ko, Kyong-Cheol,Takatuska, Yumiko,Yamaguchi, Yoshihiro,Abe, Naoki,Kaneko, Jun,Kamio, Yoshiyuki
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- Novel characteristics of Selenomonas ruminantium lysine decarboxylase capable of decarboxylating both L-lysine and L-ornithine
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Lysine decarboxylase (LDC; EC 4.1.1.18) of Selenomonas ruminantium is a constitutive enzyme and is involved in the synthesis of cadaverine, which is an essential constituent of the peptidoglycan for normal cell growth. We purified the 5. ruminantium LDC by an improved method including hydrophobic chromatography and studied the fine characteristics of the enzyme. Kinetic study of LDC showed that 5. ruminanitum LDC decarboxylated both L-lysine and L-ornithine with similar Km, and the decarboxylase activities towards both substrates were competitively and irreversibly inhibited by DL-α-difluoromethylornithine, which is a specific inhibitor of ornithine decarboxylase (EC 4.1.1.17). We also showed a drastic descent of LDC activity owing to the degradation of LDC at entry into the stationary phase of cell growth.
- Takatsuka, Yumiko,Onoda, Motoko,Sugiyama, Takeyoshi,Muramoto, Koji,Tomita, Toshio,Kamio, Yoshiyuki
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- Turtschamide, a cytotoxic putrescine bisamide from Corydalis turtschaninovii
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A putrescine bisamide with a unique cyclic structure derived from l-tyrosine, turtschamide (1), was isolated from the tubers of Corydalis turtschaninovii. The structure of 1 was established by extensive spectroscopic study, and its absolute configuration was determined by a combination of NOE experiment and application of the Marfey's method. Turtschamide (1) exhibited cytotoxicity against the A549, SK-OV-3, SK-MEL-2, and HCT-15 cells.
- Kim, Ki Hyun,Choi, Sang Un,Lee, Kang Ro
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- Analysis of catalytic determinants of diaminopimelate and ornithine decarboxylases using alternate substrates
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Diaminopimelate decarboxylase (DAPDC) and ornithine decarboxylase (ODC) are pyridoxal 5′-phosphate dependent enzymes that are critical to microbial growth and pathogenicity. The latter is the target of drugs that cure African sleeping sickness, while the former is an attractive target for antibacterials. These two enzymes share the (β/α)8 (i.e., TIM barrel) fold with alanine racemase, another pyridoxal 5′-phosphate dependent enzyme critical to bacterial survival. The active site structural homology between DAPDC and ODC is striking even though DAPDC catalyzes the decarboxylation of a D stereocenter with inversion of configuration and ODC catalyzes the decarboxylation of an L stereocenter with retention of configuration. Here, the structural and mechanistic bases of these interesting properties are explored using reactions of alternate substrates with both enzymes. It is concluded that simple binding determinants do not control the observed stereochemical specificities for decarboxylation, and a concerted decarboxylation/proton transfer at Cα of the D stereocenter of diaminopimelate is a possible mechanism for the observed specificity with DAPDC.
- Fogle, Emily J.,Toney, Michael D.
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- Nickel and nickel-magnesia catalysts active in the hydrogenation of 1,4-butanedinitrile
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Several NiO-MgO systems were synthesized to be studied as nickel catalysts for the hydrogenation of 1,4-butanedinitrile in the gas phase and compared with a bulk NiO of controlled morphology. All samples were characterized by XRD, BET, TPR, TPD, SEM, and H2 chemisorption techniques. The Ni-MgO systems had higher activities than the Ni bulk catalyst. The most active catalyst at all reaction temperatures was type R4CB which had homogeneous particles of about 1000 A, the highest metal surface area, and the highest coverage with weakly bound hydrogen. The presence of basic magnesia suppresses the condensation reactions and consequently favors the elimination of amines, and prevents catalyst deactivation. The selectivity toward the different products not only depends on the catalytic properties but can also be modified by controlling the hydrogen/dinitrile ratio. The highest selectivity to 4-aminobutanenitrile was achieved by catalyst R4CB, with 85% at 100% conversion and working at a space velocity of 13,000 h-1 and 343 K. This selectivity could be increased by lowering the hydrogen/butanedinitrile ratio.
- Serra, Marc,Salagre, Pilar,Cesteros, Yolanda,Medina, Francisco,Sueiras, Jesus E.
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- Preparation and Thermal Square Planar-Octahedral Transformation of Nickel(II) Complexes Containing 1,2-Butanediamine or 3,3-Dimethyl-1,2-butanediamine in Solid Phase
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Nickel(II) complexes of 1,2-butanediamine (1,2-bn) and 3,3-dimethyl-1,2-butanediamine (dmbn), were prepared, and their thermal behavior was investigated in solid phase.The original complexes were all violet, octahedral diaquabis(diamine) complexes (X2; X=Cl, Br, NO3 or ClO4).The 1,2-bn complexes with Cl- or Br- and the dmbn complex with NO3- showed a two-step thermochromism, violet->yellow->violet blue, upon heating.These steps correspond to structural changes to a square planar anhydride, and then to an octahedral dianiono complex.The complexes of both ligands with ClO4- underwent only thermal deaquation, changing into orange square planar anhydride.Other salts, the 1,2-bn complex with NO3- and the dmbn complexes with Cl- or Br-, were converted into octahedral dianiono complexes by thermal deaquation-anation which occurs in one step.The differences among the thermal reactivities of the complexes with different diamines can be understood on the basis of steric hindrance caused by the substituent groups on the diamine.
- Ihara, Yoshinori,Wada, Akiko,Fukuda, Yutaka,Sone, Kozo
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- CHENGES IN POLYAMINES AND RELATED ENZYMES WITH LOSS OF VIABILITY IN RICE SEEDS.
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Putrescine, spermidine and spermine of high vigour, low vigour and non viable (classes 1, 2 and 3 respectively) seeds of Oryza sativa increased with loss of viability.The largest concentration of spermine was found in non-viable embryos.Spermine was absent in the husks of all the three categories of seeds.Arginine decarboxylase was greatest in high vigoured seeds and its activity gradually declined with loss of viability.However, diamine oxidase and polyamine oxidase activities gradually increased with the loss of viability of the seeds while DNA, RNA and protein contents decreased.The total content of polyamines increased on kinetin treatment but declined on ABA treatment.DNA, RNA and protein followed the same trend as polyamines.The polyamine contents increased by ca 3- and 4-fold, respectively, in high vigoured and low vigoured seeds on 1E-4 M kinetin treatment.The activity of ADC followed the same change as that of the polyamines in both cases, but the reverse was observed for the activities of diamine and polyamine oxidases.Key Word Index - Oryza sativa; Gramineae; rice; spermine; spermidine; putrescine; arginine; arginine decarboxylase; polyamine oxidase.
- Mukhopadhyay, A.,Choudhuri, M. M.,Sen, K.,Ghosh, B.
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- Further insight into the inhibitory action of a LIM/double zinc-finger motif of an agmatinase-like protein
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Agmatine is a precursor for polyamine biosynthesis also associated to neurotransmitter, anticonvulsant, antineurotoxic and antidepressant actions in the brain. It results from decarboxylation of l-arginine by arginine decarboxylase and it is hydrolyzed to urea and putrescine by agmatinase. Recently, we have described a new protein which also hydrolyzes agmatine although its sequence greatly differs from all known agmatinases. This agmatinase-like protein (ALP) contains a LIM-like double Zn-finger domain close to its carboxyl terminus, whose removal results in a truncated variant with a 10-fold increased kcat, and a 3-fold decreased Km value for agmatine. Our proposal was that the LIM-domain functions as an autoinhibitory, regulatory entity for ALP. Results in this report provide additional support for the postulated inhibitory effect. The purified isolated LIM domain was shown to be competitively inhibitory to a truncated variant ALP (lacking the LIM-domain), but not to the wild-type species. The C453A variant was shown to be a Zn2 +-free enzyme with kinetic parameters similar to those of the truncated-ALP. A molecular dynamic simulation of a modeled LIM-domain 3D structure showed that, as a consequence of C453A mutation, the coordination of the zinc ion is broken and the structure of the zinc finger is melted. The inhibitory action of the LIM/double Zinc-finger motif was associated to a significant conformational change, as detected by tryptophan fluorescence studies, but was not related to changes in the association of the enzyme with the catalytically essential Mn2 +.
- Cofre, Jaime,Montes, Paola,Vallejos, Alejandro,Benítez, José,García, David,Martínez-Oyanedel, José,Carvajal, Nelson,Uribe, Elena
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- Polyamine modification by acrolein exclusively produces 1,5-diazacyclooctanes: A previously unrecognized mechanism for acrolein-mediated oxidative stress
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Acrolein, a toxic unsaturated aldehyde generated as a result of oxidative stress, readily reacts with a variety of nucleophilic biomolecules. Polyamines, which produced acrolein in the presence of amine oxidase, were then found to react with acrolein to produce 1,5-diazacyclooctane, a previously unrecognized but significant downstream product of oxidative stress. Although diazacyclooctane formation effectively neutralized acrolein toxicity, the diazacyclooctane hydrogel produced through a sequential diazacyclooctane polymerization reaction was highly cytotoxic. This study suggests that diazacyclooctane formation is involved in the mechanism underlying acrolein-mediated oxidative stress.
- Tsutsui, Ayumi,Imamaki, Rie,Kitazume, Shinobu,Hanashima, Shinya,Yamaguchi, Yoshiki,Kaneda, Masato,Oishi, Shinya,Fujii, Nobutaka,Kurbangalieva, Almira,Taniguchi, Naoyuki,Tanaka, Katsunori
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- Hydrogenation of N-Heteroarenes Using Rhodium Precatalysts: Reductive Elimination Leads to Formation of Multimetallic Clusters
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A rhodium-catalyzed method for the hydrogenation of N-heteroarenes is described. A diverse array of unsubstituted N-heteroarenes including pyridine, pyrrole, and pyrazine, traditionally challenging substrates for hydrogenation, were successfully hydrogenated using the organometallic precatalysts, [(η5-C5Me5)Rh(N-C)H] (N-C = 2-phenylpyridinyl (ppy) or benzo[h]quinolinyl (bq)). In addition, the hydrogenation of polyaromatic N-heteroarenes exhibited uncommon chemoselectivity. Studies into catalyst activation revealed that photochemical or thermal activation of [(η5-C5Me5)Rh(bq)H] induced C(sp2)-H reductive elimination and generated the bimetallic complex, [(η5-C5Me5)Rh(μ2,η2-bq)Rh(η5-C5Me5)H]. In the presence of H2, both of the [(η5-C5Me5)Rh(N-C)H] precursors and [(η5-C5Me5)Rh(μ2,η2-bq)Rh(η5-C5Me5)H] converted to a pentametallic rhodium hydride cluster, [(η5-C5Me5)4Rh5H7], the structure of which was established by NMR spectroscopy, X-ray diffraction, and neutron diffraction. Kinetic studies on pyridine hydrogenation were conducted with each of the isolated rhodium complexes to identify catalytically relevant species. The data are most consistent with hydrogenation catalysis prompted by an unobserved multimetallic cluster with formation of [(η5-C5Me5)4Rh5H7] serving as a deactivation pathway.
- Kim, Sangmin,Loose, Florian,Bezdek, Máté J.,Wang, Xiaoping,Chirik, Paul J.
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p. 17900 - 17908
(2019/11/19)
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- Imprinted Apportionment of Functional Groups in Multivariate Metal-Organic Frameworks
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Sophisticated chemical processes widely observed in biological cells require precise apportionment regulation of building units, which inspires researchers to develop tailorable architectures with controllable heterogeneity for replication, recognition and information storage. However, it remains a substantial challenge to endow multivariate materials with internal sequences and controllable apportionments. Herein, we introduce a novel strategy to manipulate the apportionment of functional groups in multivariate metal-organic frameworks (MTV-MOFs) by preincorporating interlocked linkers into framework materials. As a proof of concept, the imprinted apportionment of functional groups within ZIF-8 was achieved by exchanging imine-based linker templates with original linkers initially. The removal of linker fragments by hydrolysis can be achieved via postsynthetic labilization, leading to the formation of architectures with controlled heterogeneity. The distributions of functional groups in the resulting imprinted MOFs can be tuned by judicious control of the interlocked chain length, which was further analyzed by computational methods. This work provides synthetic tools for precise control of pore environment and functionality sequences inside multicomponent materials.
- Feng, Liang,Wang, Kun-Yu,Lv, Xiu-Liang,Powell, Joshua A.,Yan, Tian-Hao,Willman, Jeremy,Zhou, Hong-Cai
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supporting information
p. 14524 - 14529
(2019/10/02)
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- The Total Synthesis of Spermine Alkaloid Kukoamine Bimesylate
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The first total synthesis of kukoamine B bimesylate was completed from 1,4-diaminobutane dihydrochloride in 12 steps with a 11.4% overall yield, and all the steps could be carried out at a kilogram scale. The cyano groups were used as the precursor of amino groups to avoid the competitive reaction delicately. The aza-Michael addition reaction, amidation and hydrogenation of the cyano group sequence was streamlined as a general approach towards the synthesis of polyamine structures.
- Dong, Kai
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supporting information
p. 2669 - 2672
(2018/12/14)
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- Method for preparing polyamine by direct ammoniation of polyhydroxy compound
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A method for preparing polyamine by direct ammoniation of a polyhydroxy compound is disclosed. By using a polyhydroxy compound, ammonia gas or liquefied ammonia as a raw material and using a carrier-loaded liquid-phase reduced transition metal as a catalyst, an ammoniation reaction of the polyhydroxy compound under mild conditions is realized. The catalyst has high selectivity of polyamine. The catalyst can be recovered and recycled.
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Paragraph 0046; 0047
(2016/10/24)
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- mellow amination by homogeneous catalysis of the method for the production of primary amines
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The invention relates to a method for producing primary amines by means of the alcohol amination of alcohols with ammonia, with water being eliminated. The method comprises the steps of: (a) a homogenously-catalysed reaction of a reaction mixture which contains at least one alcohol, ammonia, at least one non-polar solvent, and at least one catalyst containing at least one element selected from groups 8, 9 and 10 of the periodic table in the liquid phase, a product mixture (P) thus being obtained; (b) separating the phases of product mixture (P) which was obtained in step (a), if necessary after a reduction in temperature, a reduction in pressure and/or the addition of at least one polar solvent with a miscibility gap in relation to the non-polar solvent, and thus obtaining at least one polar product phase (A) and at least one non-polar phase (B) containing at least one portion of the catalyst that was introduced, with said non-polar phase (B) being separated off, (c) returning at least one portion of the non-polar phase (B) into the reaction in step (a), and (d) separating the amination product from the polar product phase (A). The non-polar solvent introduced in (a) and the catalyst introduced in step (a) are selected such that the catalyst in the non-polar phase (B) becomes enriched.
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Paragraph 0265; 0266
(2016/10/09)
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- METHOD FOR PRODUCING ALKANOL AMINES BY HOMOGENEOUSLY CATALYZED ALCOHOL AMINATION
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PROBLEM TO BE SOLVED: To provide a method for producing alkanol amines by alcohol amination of diols using ammonia under elimination of water. SOLUTION: The invention relates to a method for producing alkanol amines which comprise a primary amino group (-NH2) and a hydroxyl group (-OH), by alcohol amination of diols comprising two hydroxyl groups (-OH) using ammonia under elimination of water. The reaction is homogeneously catalyzed in the presence of at least one complex catalyst which contains at least one element selected from groups 8, 9 and 10 of the periodic table and at least one donor ligand. SELECTED DRAWING: None COPYRIGHT: (C)2016,JPO&INPIT
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Paragraph 0088; 0097
(2016/10/27)
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- Applications of dynamic combinatorial chemistry for the determination of effective molarity
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A new strategy for determining thermodynamic effective molarities (EM) for macrocylisation reactions using dynamic combinatorial chemistry under dilute conditions is presented. At low concentrations, below the critical value, Dynamic Libraries (DLs) of bifunctional building blocks contain only cyclic species, so it is not possible to quantify the equilibria between linear and cyclic species. However, addition of a monofunctional chain stopper can be used to promote the formation of linear oligomers allowing measurement of EM for all cyclic species present in the DL. The effectiveness of this approach was demonstrated for DLs generated from mixtures of 1,3-diimine calix[4]arenes, linear diaminoalkanes and monoaminoalkanes. For macrocycles deriving from one bifunctional calixarene and one diamine, there is an alternating pattern of EM values with the number of methylene units in the diamine: odd numbers give significantly higher EMs than even numbers. For odd numbers of methylene units, the alkyl chain can adopt an extended all anti conformation, whereas for even numbers of methylene units, gauche conformations are required for cyclisation, and the associated strain reduces EM. The value of EM for the five-carbon linker indicates that this macrocycle is a strainless ring. This journal is
- Ciaccia, Maria,Tosi, Irene,Baldini, Laura,Cacciapaglia, Roberta,Mandolini, Luigi,Di Stefano, Stefano,Hunter, Christopher A.
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p. 144 - 151
(2015/02/19)
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- · Uniform catalyst by using alcohol aminosilicone di-, tri-and a method of manufacturing a polyphenylenepolyamine
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The invention relates to a method for producing primary amines, which contain at least one functional group of the formula (-CH2-NH2) and at least one further primary amino group, by the alcohol amination of reactants, which contain at least one functional group of the formula (-CH2-OH) and at least one further functional group (-X), wherein (-X) is selected from hydroxyl groups and primary amino groups, using ammonia with removal of water, wherein the reaction is carried out in a homogeneously catalyzed manner in the presence of at least one complex catalyst containing at least one element selected from groups 8, 9 and 10 of the periodic table and at least one donor ligand.
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Paragraph 0099; 0114
(2016/10/09)
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- Characterization of unstable products of flavin- and pterin-dependent enzymes by continuous-flow mass spectrometry
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Continuous-flow mass spectrometry (CFMS) was used to monitor the products formed during the initial 0.25-20 s of the reactions catalyzed by the flavoprotein N-acetylpolyamine oxidase (PAO) and the pterin-dependent enzymes phenylalanine hydroxylase (PheH) and tyrosine hydroxylase (TyrH). N,N′-Dibenzyl-1,4-diaminobutane (DBDB) is a substrate for PAO for which amine oxidation is rate-limiting. CFMS of the reaction showed formation of an initial imine due to oxidation of an exo-carbon-nitrogen bond. Nonenzymatic hydrolysis of the imine formed benzaldehyde and N-benzyl-1,4-diaminobutane; the subsequent oxidation by PAO of the latter to an additional imine could also be followed. Measurement of the deuterium kinetic isotope effect on DBDB oxidation by CFMS yielded a value of 7.6 ± 0.3, in good agreement with a value of 6.7 ± 0.6 from steady-state kinetic analyses. In the PheH reaction, the transient formation of the 4a-hydroxypterin product was readily detected; tandem mass spectrometry confirmed attachment of the oxygen to C(4a). With wild-type TyrH, the 4a-hydroxypterin was also the product. In contrast, no product other than a dihydropterin could be detected in the reaction of the mutant protein E332A TyrH.
- Roberts, Kenneth M.,Tormos, José R.,Fitzpatrick, Paul F.
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p. 2672 - 2679
(2014/05/20)
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- Photostimulated reduction of nitriles by SmI2
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Despite their high electron-withdrawing strength, nitriles are not good electron acceptors and therefore are hard to reduce. In this work, using photostimulation in the visible region, we examined the reactivity of aliphatic and aromatic, mono- and dicyano compounds in reaction with SmI2. A proton donor that complexes efficiently with SmI2 must be used. Maximum yield was obtained at ca.0.2 M MeOH. Aromatic nitriles were more reactive than aliphatic nitriles, which exhibited negligible yields. Phenylacetonitrile presents an intermediate reactivity. The mechanism of the reaction involves coordination of the SmI2 to the lone pair of the nitrile nitrogen followed by an inner sphere electron transfer. Surprisingly, m-dicyanobenzene was less reactive than the monocyano derivative benzonitrile. This was traced to the lower ability of the dicyano compound to coordinate to the SmI2 due to, as was shown by quantum mechanical calculations, its lone pair having an energy significantly lower than that of benzonitrile. It is noteworthy that at the SmI2 initial concentration used (0.04M), light penetrates only the 0.4 mm outer layer of the reaction mixture. Therefore the photostimulation effect observed was due to irradiation of only 4% of the total reaction volume, implying that under optimal conditions the effect should be 25 times larger.
- Rao, Chintada Nageswara,Hoz, Shmaryahu
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experimental part
p. 4029 - 4034
(2012/06/29)
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- PROCESS FOR THE PREPARATION OF PRIMARY AMINES BY HOMOGENEOUSLY CATALYZED ALCOHOL AMINATION
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Preparing a primary amine by alcohol amination of alcohol with ammonia and elimination of water includes reacting, in a homogeneously catalyzed reaction, a mixture of alcohol, ammonia, nonpolar solvent, and catalyst, in a liquid phase, to obtain a product mixture. The process then includes phase separating the product mixture into a polar product phase and a nonpolar product phase, and separating off the nonpolar product phase. At least some of the nonpolar phase returns to the homogenously catalyzed reaction. The process further includes separating off amination product from the polar product phase. At least some of the catalyst is in the nonpolar phase, and the catalyst accumulates in the nonpolar phase.
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Page/Page column 14-15; 16
(2012/09/22)
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- PROCESS FOR PREPARING ALKANOLAMINES BY HOMOGENEOUSLY CATALYZED ALCOHOL AMINATION
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Process for preparing alkanolamines which have a primary amino group (—NH2) and a hydroxyl group (—OH) by alcohol amination of diols having two hydroxyl groups (—OH) by means of ammonia with elimination of water, wherein the reaction is carried out homogeneously catalyzed in the presence of at least one complex catalyst comprising at least one element selected from groups 8, 9 and 10 of the Periodic Table and also at least one donor ligand.
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Page/Page column 13-14; 16
(2012/09/22)
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- PROCESS FOR PREPARING DI-, TRI- AND POLYAMINES BY HOMOGENEOUSLY CATALYZED ALCOHOL AMINATION
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Process for preparing primary amines which have at least one functional group of the formula (—CH2—NH2) and at least one further primary amino group by alcohol amination of starting materials having at least one functional group of the formula (—CH2—OH) and at least one further functional group (—X), where (—X) is selected from among hydroxyl groups and primary amino groups, by means of ammonia with elimination of water, wherein the reaction is carried out homogeneously catalyzed in the presence of at least one complex catalyst comprising at least one element selected from groups 8, 9 and 10 of the Periodic Table and also at least one donor ligand.
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Page/Page column 12; 17
(2012/09/22)
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- PROBIOTIC MICROORGANISMS FOR THE REDUCTION OF MANURE ODOR
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Described are microorganism which are able to reduce the generation of feces odor by decreasing the amount of at least one of the compounds methyl mercaptan, a sulphide compound, cadavarine, putrescine, indole or skatole, and wherein said decrease in the amount of said compounds is independent of the growth of the microorganism. Also described are compositions, comprising such microorganisms, e.g. food, feed or pharmaceutical compositions and the use of such microorganisms for suppressing feces odor or the preparation of foodstuff or feedstuff, as well as corresponding methods for the production of food or feed composition and additives for food, feed or drinks.
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- PROCESS FOR PRODUCING DIAMINE AND POLYAMIDE
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By a method for producing a diamine comprising the step of purifying a diamine from an aqueous solution containing a diamine salt, the method comprising a step of adding an alkaline substance to the aqueous solution and then filtering the resulting solution by allowing the solution to pass through a nanofiltration membrane to remove the salt, thereby obtaining an aqueous diamine solution, a diamine suitable as a raw material for a polyamide can be obtained by a simpler operation than by a conventional extraction operation with an organic solvent.
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(2011/01/11)
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- Metabolism of N-alkylated spermine analogues by polyamine and spermine oxidases
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N-alkylated polyamine analogues have potential as anticancer and antiparasitic drugs. However, their metabolism in the host has remained incompletely defined thus potentially limiting their utility. Here, we have studied the degradation of three different spermine analogues N,N′-bis-(3-ethylaminopropyl)butane-1,4-diamine (DESPM), N-(3-benzyl-aminopropyl)-N′-(3-ethylamino-propyl)butane-1,4-diamine (BnEtSPM) and N,N′-bis-(3-benzylaminopropyl)butane-1,4-diamine (DBSPM) and related mono-alkylated derivatives as substrates of recombinant human polyamine oxidase (APAO) and spermine oxidase (SMO). APAO and SMO metabolized DESPM to EtSPD [Km(APAO) = 10 μM, kcat(APAO) = 1.1 s -1 and Km(SMO) = 28 μM, kcat(SMO) = 0.8 s-1, respectively], metabolized BnEtSPM to EtSPD [Km(APAO) = 0.9 μM, kcat(APAO) = 1.1 s-1 and Km(SMO) = 51 μM, kcat(SMO) = 0.4 s-1, respectively], and metabolized DBSPM to BnSPD [Km(APAO) = 5.4 μM, k cat(APAO) = 2.0 s-1and Km(SMO) = 33 μM, kcat(SMO) = 0.3 s-1, respectively]. Interestingly, mono-alkylated spermine derivatives were metabolized by APAO and SMO to SPD [EtSPM Km(APAO) =16 μM, kcat(APAO) = 1.5 s -1; Km(SMO) = 25 μM, kcat(SMO) = 8.2 s -1; BnSPM Km(APAO) = 6.0 μM, kcat(APAO) = 2.8 s-1; Km(SMO) =19 μM, kcat(SMO) = 0.8 s-1, respectively]. Surprisingly, EtSPD [Km(APAO) = 37 μM, kcat(APAO) = 0.1 s-1; Km(SMO) =48 μM, kcat(SMO) = 0.05 s-1] and BnSPD [Km(APAO) = 2.5 μM, kcat(APAO) = 3.5 s-1; Km(SMO) =60 μM, kcat(SMO) = 0.54 s-1] were metabolized to SPD by both the oxidases. Furthermore, we studied the degradation of DESPM, BnEtSPM or DBSPM in the DU145 prostate carcinoma cell line. The same major metabolites EtSPD and/or BnSPD were detected both in the culture medium and intracellularly after 48 h of culture. Moreover, EtSPM and BnSPM were detected from cell samples. Present data shows that inducible SMO parallel with APAO could playanimportant roleinpolyamine based drug action, i.e. degradation of parent drug and its metabolites, having significant impact on efficiency of these drugs, and hence for the development of novel N-alkylated polyamine analogues. Springer-Verlag 2009.
- Haekkinen, Merja R.,Hyvoenen, Mervi T.,Auriola, Seppo,Casero Jr., Robert A.,Vepsaelaeinen, Jouko,Khomutov, Alex R.,Alhonen, Leena,Keinaenen, Tuomo A.
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experimental part
p. 369 - 381
(2010/11/18)
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- Salt suitable for an acid generator and a chemically amplified positive resist composition containing the same
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The present invention provides a salt represented by the formula (I): wherein P1, P2 and P3 each independently represent a C1-C30 alkyl group which may be substituted with at least one selected from a hydroxyl group, a C3-C12 cyclic hydrocarbon group and a C1-C12 alkoxy group, or a C3-C30 cyclic hydrocarbon group which may be substituted with at least one selected from a hydroxyl group and a C1-C12 alkoxy group, provided that all of P1, P2 and P3 are not simultaneously phenyl groups which may be substituted, Q1 and Q2 each independently represent a fluorine atom or a C1-C6 perfluoroalkyl group, and R represents a group represented by the formula: wherein A1 represents —OH or —Y1—OH, n represents an integer of 1 to 9, and Y1 represents a divalent C1-C6 saturated aliphatic hydrocarbon group; a group represented by the formula: wherein ring X1 represents a C3-C30 monocyclic or polycyclic hydrocarbon group in which one —CH2— group is substituted with —CO—, and at least one hydrogen atom in the monocyclic or polycyclic hydrocarbon group may be substituted with a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C4 perfluoroalkyl group, a C1-C6 hydroxyalkyl group, a hydroxyl group or a cyano group; a group represented by the formula: wherein ring X2 represents a C3-C30 monocyclic or polycyclic hydrocarbon group in which a hydrogen atom of one —CH2— group is substituted with a hydroxyl group, and at least one hydrogen atom in the monocyclic or polycyclic hydrocarbon group may be substituted with a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C4 perfluoroalkyl group, a C1-C6 hydroxyalkyl group, a hydroxyl group or a cyano group; a group represented by the formula: wherein ring X3 represents a C3-C30 monocyclic or polycyclic hydrocarbon group in which one —CH2— group is substituted with —COO—, and at least one hydrogen atom in the monocyclic or polycyclic hydrocarbon group may be substituted with a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C4 perfluoroalkyl group, a C1-C6 hydroxyalkyl group, a hydroxyl group or a cyano group, and m represents an integer of 0 to 12; or a group represented by the formula: wherein ring X4 represents a C6-C30 polycyclic hydrocarbon group having tricycle or more, and at least one hydrogen atom in the polycyclic hydrocarbon group may be substituted with a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C4 perfluoroalkyl group, a C1-C6 hydroxyalkyl group or a cyano group, and l represents an integer of 1 to 12. The present invention further provides a chemically amplified resist composition comprising the salt represented by the above-mentioned formula (I).
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- Functionalized Photoreactive Compounds
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The present invention concerns functionalized photoreactive compounds of formula (I), that are particularly useful in materials for the alignment of liquid crystals. Due to the adjunction of an electron withdrawing group to specific molecular systems bearing an unsaturation directly attached to two unsaturated ring systems, exceptionally high photosensitivities, excellent alignment properties as well as good mechanical robustness could be achieved in materials comprising said functionalized photoreactive compounds of the invention.
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- Chemosensor for the optical detection of aliphatic amines and diamines
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Two new chemosensor dyes with either one or two trifluoroacetophenone recognition moieties have been investigated in terms of reversibly interacting with amines and diamines. The Royal Society of Chemistry.
- Reinert, Susanne,Mohr, Gerhard J.
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p. 2272 - 2274
(2008/12/23)
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- Insulin-producing cells derived from stem cells
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The disclosure provides, among other things, insulin-producing cells derived from stem cells, such as human stem cells and neural stem cells. The disclosure discloses a relationship between caudalizing factors and the differentiation of insulin-producing cells.
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- PROCESS FOR ISOLATION OF AN ORGANIC AMINE
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The invention relates to a process for the isolation of an organic amine from a composition comprising the organic amine and an acid, or a salt of the organic amine and the acid, wherein the process comprises steps wherein ammonia or hydrazine is added to the composition thereby forming a multi-phase system comprising an organic amine -rich phase and an acid-rich phase, the organic amine-rich phase and the acid-rich phase obtained in step (i) are separated, and the organic amine is isolated from the organic amine -rich phase.
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Page/Page column 11
(2008/06/13)
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- Process for the catalytic hydrogenation of a nitrile
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Process for the catalytic hydrogenation of a nitrite in the presence of an amine and a catalyst wherein the catalyst is a liquid-rinsed Raney-type catalyst contacted with a hydroxide prior to contacting the catalyst with the amine. The process results in higher selectivity in the formation of diamines from diniriles.
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Page/Page column 5
(2008/06/13)
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- Fluorescent sensors for diamines
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A series of seven diamine sensors was prepared using dimers of a quinolone aldehyde chromophore. Binding to six different diamine guests was explored by a combination of NMR, absorption and fluorescence spectroscopy. It was shown that the dimeric sensors bound the diamine guests by formation of a bis-iminium ion which produced large changes in the fluorescence of the quinolone core. Issues of selectivity between guests are discussed. The Royal Society of Chemistry 2005.
- Secor, Kristen,Plante, Jeffrey,Avetta, Christopher,Glass, Timothy
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p. 4073 - 4077
(2007/10/03)
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- Magnesium-Catalyzed Proficient Reduction of Oximes to Amines Using Ammonium Formate
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Various aldoximes and ketoximes were selectively reduced to the corresponding amines by catalytic transfer hydrogenation employing low cost magnesium powder and ammonium formate at room temperature. Many other functionalities such as halogens, -OH, -OCH3, -COOH and -CH 3 remained unaffected. The hydrogenation is fast, mild, clean, cost effective and high yielding.
- Abiraj,Gowda, D. Channe
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p. 599 - 605
(2007/10/03)
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- One-pot sequence for the decarboxylation of α-amino acids
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Treatment of an α-amino acid with N-bromosuccinimide in water at pH 5 or in an alcoholic-aqueous ammonium chloride mixture, followed by addition of nickel(II) chloride and sodium borohydride, effected an overall decarboxylation via an intermediate nitrile to afford the corresponding amine in good yield.
- Laval, Gilles,Golding, Bernard T.
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p. 542 - 546
(2007/10/03)
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- Zinc/ammonium formate: A new facile system for the rapid and selective reduction of oximes to amines
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Various oximes, both aldoximes and ketoximes, are selectively reduced to corresponding amines employing low cost zinc dust and ammonium formate despite presence of other functional groups such as halogens, -OH, -OCH3, -COOH, -CN, > C = C 3.
- Abiraj,Gowda, D. Channe
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p. 332 - 334
(2007/10/03)
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- Kinetics and thermodynamics of amine and diamine signaling by a trifluoroacetyl azobenzene reporter group
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(Matrix presented) (Trifluoroacetyl)azobenzene dyes were previously employed as amine reporter groups (chemosensors) in a dendrimer-based monomolecular imprinting system. Kinetic and binding studies with a range of amines and diamines show that the highly selective signaling observed for alkane diamines by these imprinted dendrimers arises from a kinetic effect due to intramolecular general base-catalyzed carbinolamine formation with the dye itself. The relationship between diamine structure and carbinolamine stability and rate of formation is described.
- Mertz, Eric,Beil, James B.,Zimmerman, Steven C.
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p. 3127 - 3130
(2007/10/03)
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- Reactions in microemulsion media: Schiff bases with targeting/anchoring module as kinetic sensors to map the polarity pocket of a microemulsion droplet
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The hydrolysis of some tailor-made Schiff bases having flexible spacers between aldimine groups and alkoxy groups at ortho (o) or para (p) position in the benzene ring has been investigated in microemulsion media. The kinetic data of acid-catalyzed hydrolysis in anionic (sodium lauryl sulphate: NaLS) and cationic (cetyltrimethyl ammoniumbromide: CTAB) microemulsion media have been explained considering the localization of the Schiff bases at various probable pockets of the microemulsion droplet. The results are in conformity to the solubilization studies of the reported Schiff bases in microemulsions (Dash et al., Spectrochim Acta 1996, 52A, 349). The change in reactivity due to change in the spacer length and position of the alkoxy group in the Schiff bases has been rationalized on the basis of localization sites of the reaction center at different polarity pockets of the reaction media.
- Mishra,Patel, Namita,Dash,Behera
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p. 458 - 464
(2007/10/03)
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- Polyamides bearing functionalized side chains useful as water soluble hypolipidemic agents
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This invention relates to derivatives of polyanhydroaspartic acid which are non-systemic water soluble polymers and which are intended to be lipid lowering agents. The pharmaceutical compositions/formulations incorporating these compounds are also discussed.
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- Oxidation of acetylpolyamines by maize polyamine oxidase
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The oxidation of acetylpolyamines by celt wall polyamine oxidase from maize shoots was investigated. The purified enzyme catalysed the oxidation of N1-acetylspermine, N1-acetylspermidine, and N8-acetylspermidine at the same optimal pH (6.5), but with lower relative velocities and higher K(m) than those found for spermine and spermidine oxidation. The enzyme cleaved N1-acetylspermine and N8-acetylspermidine, at the same positions as in spermine and spermidine oxidation, with the production of H2O2, 1,3- diaminopropane and the corresponding aminoaldehydes. Polyamine oxidase was quickly inactivated by catalysis, and the aminoaldehyde derived from N1- acetylspermine behaved as a competitive inhibitor of the enzyme (K(m) = 20 μM). These findings suggest that cell wait polyamine oxidase from maize shoots does not effect the interconversion pathway of acetylpolyamines found in vertebrates.
- Federico, Rodolfo,Ercolini, Luca,Laurenzi, Maria,Angelini, Riccardo
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p. 339 - 341
(2007/10/03)
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- Hydrolysis of schiff bases in (CTAB-CHCl3-H2O) reversed micelles: Role of spacers
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The schiff bases of the type (p-C16H33O-C6H4CH = N)2(CH2)m (1, m=0, 2, 3, 4 and 6) and the ortho isomer (2, m=0, 2, 4, 6) have been synthesized and the hydrolysis of these compounds these compounds have been studied in CTAB-CHCl3-H2O reversed micellar system under acidic condition.Significant variation of the reaction rate has been observed due to variation in the number of methylene groups in the spacer and due to the change in the position of the cetyloxy group.Difference in the rate of disappearance of schiff base and appearance of the product is ascribed to a mechanism involving a carbinolamine intermediate.
- Senapati, S.,Dash, P.K.,Mishra, B.K.,Behera, G.B.
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p. 227 - 229
(2007/10/02)
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- HPLC and NMR investigation of the serum amine oxidase catalyzed oxidation of polyamines.
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In the presence of amine oxidases polyamines arrest cell proliferation owing to the generation of hydrogen peroxide and amino aldehydes. In this investigation the bovine serum amine oxidase catalyzed oxidation of polyamines has been studied by HPLC analysis of dansylated reaction products with or without NaBH4 reduction and by NMR spectroscopy of the reaction products and 3-aminopropanal was found to be a major reaction product. These findings were further substantiated by analysis of the reaction products by ion-exchange chromatography and by analysis of the products formed by oxidation of polyamines by the cofactor of Cu amine oxidases, 6-hydroxydopa. 3-Aminopropanal is unstable and can give rise to acrolein by beta-elimination.
- Houen,Bock,Jensen
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- Decolorization of polyalkylene polyamines
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A process for decolorizing polyalkylene polyamines, which comprises contacting one or more polyalkylene polyamines having an average molecular weight of greater than about 200 and less than about 1000 with carbon at a temperature greater than or equal to about 100° C. and less than or equal to about 300° C. under conditions effective to reduce the color rating of the one or more polyalkylene polyamines.
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- CYCLIC HYDROCARBONS WITH AN AMINOALKYL SIDECHAIN
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Provided are cyclic hydrocarbons of Formula I with an aminoalkyl sidechain that are useful for treating phospholipase A2 mediated conditions, diabetes, and obesity.
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- Hydroboration/Amination of N-Trimethylsilyl Protected Olefinic Amines and Diolefins: Synthesis of Isomerically Pure Diamines
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N-Trimethylsilyl protected olefinic amines and terminal diolefins were hydroborated with dimethylborane and the resulting organoboranes were treated with in situ generated chloramine or chloralkylamines to produce isomerically pure diamines or N-substituted diamines in good yields.
- Kabalka, George W.,Wang, Zhe
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p. 2113 - 2118
(2007/10/02)
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- Triazinyl reactive dyestuffs in which triazinyl group is further substituted with a beta-chloroethylsulfonyl- or vinylsulfonylbutyrylamino moiety
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Reactive dyes of the formula STR1 in which D is the radical of an organic dye of the monoazo, polyazo, metal complex azo, anthraquinone, phthalocyanine, formazan, azomethine, dioxazine, phenazine, stilbene, triphenylmethane, xanthene, thioxanthrone, nitroaryl, naphthoquinone, pyrenequinone or perylenetetracarbimide series, R is hydrogen or substituted or unsubstituted C1-4 -alkyl, X is a substituent which is detachable as an anion, B is a radical of the formula STR2 R1 and R2, independently of each other, are hydrogen or substituted or unsubstituted C1-4 -alkyl or phenyl, A is a substituted or unsubstituted aliphatic or aromatic bridge member, Y is a --CO--Z or --SO2 --Z radical, Z is an aliphatic, aromatic or heterocyclic reactive radical, and n is 1 or 2, are suitable for dyeing or printing cellulose-containing and nitrogen-containing materials and in high dyeing yield produce dyeings and prints having good fastness properties.
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- Covalently-modified polyanionic bacterial polysaccharides, stable covalent conjugates of such polysaccharides and immunogenic proteins with bigeneric spacers, and methods of preparing such polysaccharides and conjugates and of confirming covalency
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Covalently modified bacterial polysaccharides and proteins; covalent conjugates of such polysaccharides linked by a bigeneric spacer, which permits proof of covalency and facilitates purification of conjugated materials, with immunogenic bacterial membrane or other proteins, which conjugates are useful components of bacterial vaccines; and methods of preparing such polysaccharides, proteins and conjugates and of confirming the covalency of the linkage between polysaccharides and proteins.
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- Reduction of Heterocycles with Nickel-Aluminum Alloy
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Pyrazines, pyridazines, isoxazoles, oxazole, 4-methylpyrimidine, and indole are reduced by nickel-aluminum alloy in potassium hydroxide solution.The reaction is simple to carry out and does not require special apparatus or hydrogen atmospheres.The products were the fully hydrogenated species although benzene rings were not attacked. 4-Methylpyrimidine gave 1,3-diaminobutane and oxazole gave 2-(methylamino)ethanol.It was found that the reaction frequently exhibited an induction period.
- Lunn, George
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p. 1043 - 1046
(2007/10/02)
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- Triazine derivatives
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The invention relates to polymers of triazine compounds containing piperidine groups which may serve as low volatile and migration-resistant light stabilizers for synthetic polymers. They have the structure STR1 and are obtained from cyanuric halides, diamines and polyalkylpiperidylamino compounds.
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