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1.
Tetraethylammonium tetrahydroborate, Et4NBH4, in suspension in refluxing decane-dodecane mixtures has been pyrolysed at temperatures between 175 and 190 °C. Et3NBH3, which is produced by partial decomposition of Et4NBH4, reacts with Et4NBH4 to give the intermediate Et4NB3H8. Et4NBH4 and Et3NBH3 are also involved in the conversion of Et4NB3H8. to (Et4N)2B9H9, (Et4N)2B10H10, Et4NB11H14 and (Et4N)2B12H12 which are formed in varying proportions during the pyrolysis. A 1:1 Et4NBH4Et3NBH3 mixture gives the same mixture of final products in the same proportions as Et4NBH4 alone, but the reaction time is shorter.Results obtained under various conditions, for instance without solvent at 10−2 torr (50% yield), are explained by the transfer of BH3 groups occurring not only through Et3NBH3, but also by solid—solid reactions involving Et4NBH4. A more complete reaction of Et3NBH3 is obtained, giving quantitative yields, only when Et3N is evacuated from the reaction mixture. Optimum conditions for the formation of each hydroborate are examined.  相似文献   

2.
An influence of soil drought (7 or 14 d) and 7 d recovery on changes of leaf fluorescence excitation spectra at wavelengths of 450, 520, 690, and 740 nm (F450, F520, F690, F740) for drought resistant and sensitive genotypes of triticale and maize was compared. In non-stressed plants the differences between maize and triticale were observed for F450 and F520, but not for F690 and F740. Drought caused the increase in F450, F520, and F690 and this increase was more distinct for drought sensitive genotypes. After re-hydration, chlorophyll fluorescence mostly recovered to values of control plants. Drought caused significant increase in F690/F740 but not in F450/F690 and F450/F520. For triticale, highest increase in F690/F740 was observed in the 4th and 7th leaves of resistant genotype and contrarily in maize for the sensitive one. After recovery, the F450/F520, F450/F690, and F690/F740 ratios mostly returned to values of control plants.  相似文献   

3.
Interaction between the sodium salt of a DNA extracted from salmon sperm (41% GC) with [Pt(NH3)4]Cl2, [Pt(NH2? (CH2)2? NH? (CH2)2? NH2Cl]Cl, cis-Pt(NH2? (CH2)2? NH2)Cl2, cis-Pt(NH3)2Cl2, trans-Pt(NH3)2Cl2, K[Pt(C2H4)Cl3], and K2[PtCl4) indicates at least three types of complexation. A correlation is found between the change of pH and the number of platinum atoms fixed per (AT + GC) unit. The first binding site is located on the G-C pairs (guanine–cytosine), most likely the N-7(G) site, as it was shown in a previous study of the guanosine-platinum salts. The fixation of the second platinum atom by the pair (AT + GC) takes place with liberation of protons. In the case of the complexes cis-Pt(NH2? (CH2)2? NH2)Cl2, cis-Pt(NH3)2Cl2, and trans-Pt(NH3)2Cl2 the second interaction seems to involve simultaneously the N-7(A) and the N-1(G) and N-3(C) sites. This latter intercrosslink between guanine and cytosine obviously liberates protons and the decrease of pH is related in this case to the trans effect of the platinum compounds. The first two platinum atoms in the reaction of K2PtCl4] or the Zeise salt, K[Pt(C2H4)Cl3] with DNA are fixed on the G-C pairs. A maximum of six platinum atoms per (AT + GC) unit were fixed in this case. Preliminary experiments with a DNA extracted from bacteria Micrococcus lysodeikticus (72% GC) give similar results.  相似文献   

4.
The molybdenum hydride complexes Mo(PMe3)5H2 and Mo(PMe3)4H4 are capable of cleaving the C-S bonds of thiophene, benzothiophene and dibenzothiophene. For example, Mo(PMe3)5H2 reacts with thiophene to give the η5-thiophene and butadiene-thiolate complexes, (η5-C4H4S)Mo(PMe3)3 and (η5-C4H5S)Mo(PMe3)22-CH2PMe2). These complexes are also obtained from the reaction between Mo(PMe3)4H4 and thiophene under photochemical conditions, whereas at elevated temperatures thiophene is desulfurized to liberate but-1-ene. Similarly, Mo(PMe3)4H4 desulfurizes benzothiophene at elevated temperatures to liberate ethylbenzene, while the arylthiolate complex Mo(PMe3)4(SC6H4Et)H3 is obtained photochemically. Furthermore, Mo(PMe3)4H4 cleaves the C-S bond of dibenzothiophene to give [η61-C6H5C6H4S]Mo(PMe3)2H.  相似文献   

5.
Reactions of alkanolamines [R1R2NXOH; R1 = H, CH3, C2H5; R2 = H, CH3, C2H5 and X = -CH2CH2-, -CH2CH2CH2-, -CH2CHCH3, -C6H4CH2CH2-] with aluminium isopropoxide in different molar ratios (1 to 3) yield compounds of the type Al(OPri)3?n(OXNR1R2)n, where ‘n’ can be 1, 2 and 3. Most of the derivatives are distillable liquids, soluble in common organic solvents and susceptible to hydrolysis even by atmospheric moisture. The new derivatives are characterized by elemental analysis, IR and 1H NMR spectra. Molecular weight measurements of Al(OPri)3?n(OXNR1R2)n reveal them to be tetrameric in nature.  相似文献   

6.
《Inorganica chimica acta》1986,121(2):213-217
Treatment of [IrCl(C2H4)4] with K(C9H7) (C9H7 =indenyl) gives [Ir(C2H4)2(η-C9H7)]. This compound is converted quantitatively into [Ir(CO)2(η-C9H7)] by treatment with carbon monoxide. By reacting together these two iridium complexes [Ir2(μ-CO)(CO)2(ηC9H7)2] has been obtained. The compound [Ir(CO)2(η-C9H7)] reacts with [Pt(C2H4)2{P(cyclo-C6H11)3}] to give the complex [Ir2Pt(CO)3{P(cyclo-C6H11)3}(η-C9H7)2]. Protonation of the latter affords the salt [Ir2Pt(μ-H)(CO)3{P(cyclo-C6H11)3}(μ-C9H7)2] [BF4]. The main features of the molecular structure of these complexes have been established by IR and NMR spectroscopy.  相似文献   

7.
Benzophenone imine [M(η1-NHCPh2)(CO)nP5-n]BPh4 [M = Mn, Re; n = 2, 3; P = P(OEt)3, PPh(OEt)2, PPh2OEt, PPh3] complexes were prepared by allowing triflate M(κ1-OTf)(CO)nP5-n compounds to react with an excess of the imine. Hydride-imine [MH(η1-NHCPh2)P4]BPh4 (M = Ru, Os), triflate-imine [Os(κ1-OTf)(η1-NHCPh2)P4]BPh4 and bis(imine) [Ru(η1-NHCPh2)2P4](BPh4)2 [P = P(OEt)3] derivatives were also prepared. The complexes were characterized spectroscopically (IR, 1H, 31P, 13C NMR) and a geometry in solution was also established. Hydride-benzophenone imine [IrHCl(η1-NHCPh2)L(PPh3)2]BPh4and [IrHCl(η1-NHCPh2)L(AsPh3)2]BPh4 [L = P(OEt)3 and PPh(OEt)2] complexes were prepared by reacting hydride IrHCl2L(PPh3)2 and IrHCl2L(AsPh3)2 precursors with an excess of imine. Dihydride IrH21-NHCPh2)(PPh3)3 complex was also obtained and a geometry in solution was proposed.  相似文献   

8.
Molecular processes of the action of polycationic peptides that represent polylysine homo- and heterodendrimers on the functional activity of the biogenic amine- and peptide hormone-sensitive adenylyl cyclase signaling system (AC system) in rat myocardium and brains were studied. An intended use of these peptides is that of highly effective polymer carriers for biologically active substances. The polylysine homodendrimers of the third [(NH2)16(Lys)8(Lys)4(Lys)2Lys-Ala-NH2] (I), fourth [(NH2)32(Lys)16(Lys)8(Lys)4(Lys)2Lys-Ala-NH2] (II), and fifth [(NH2)64(Lys)32(Lys)16(Lys)8(Lys)4(Lys)2Lys-Ala-NH2] (III) generations, as well as polylysine heterodendrimers of the fifth generation, [(NH2)64(Lys-Glu)32(Lys-Glu)16(Lys-Glu)8(Lys-Glu)4(Lys-Glu)2Lys-Ala-Ala-Lys(ClAc)-Ala-NH2] (IV), [(NH2)64(Lys-Ala)32(Lys-Ala)16(Lys-Ala)8(Lys-Ala)4(Lys-Ala)2Lys-Ala-Lys(ClAc)-Ala-Ala-NH2] (V) and [(NH2)64(Lys-Gly-Gly)32(Lys-Gly-Gly)16(Lys-Gly-Gly)8(Lys-Gly-Gly)4(Lys-Gly-Gly)2Lys-Gly-Gly-Lys(ClAc)-Ala-Ala-NH2] (VI), interact with the C-terminal regions of α subunits of the heterotrimeric G proteins, preferably of the inhibitor type, and stimulate its activity in respector-independent manner. The most effective G-protein activators were homodendrimers II and III and heterodendrimer V. The polylysine dendrimers disturbed the functional coupling of receptors of biogenic amines and peptide hormones with Gi proteins and, to a lesser extent, Gs proteins. This was manifested as a decrease in the regulatory effects of the hormones on AC activity and the GTP binding of the G protein, as well as by a decrease in the affinity of receptors to agonists in the presence of polylysine dendrimers, which is a consequence of the dissociation of the receptor-G protein complex. It has also been shown that, based on their molecular mechanisms and selectivity of action on G proteins, polylysine dendrimers are similar to mastoparan and melittin, which are natural toxins of insect venom.  相似文献   

9.
Large ribonucleoprotein subparticles were recovered upon ribonuclease digestion of the 50 S ribosomal subunits of Escherichia coli, partially deproteinized by LiCl. Both their RNA and their protein compositions were analysed. The subunits, treated with LiCl at a concentration of 5.5 m, released an homogeneous subparticle containing proteins L3, L4, L13, L17, L22 and L29, about 70% of the 13 S fragment of 23 S RNA and about 50% of the 18 S one. Slightly larger species of subparticles were obtained from 50 S subunits treated with LiCl at concentrations between 3 m and 5 m; they contained in addition proteins L20, L21 and L23 or L2, L14, L20, L21 and L23 and a few small 23 S RNA fragments. No large subparticle was recovered from the 6 m-LiCl-treated 50 S subunits which contain only proteins L3, L13 and L17. These LiCl subparticles were compared with those obtained from intact, unfolded and sodium doecyl sulphatetreated 50 S subunits.These studies reveal that in the presence of 0.10 m-magnesium acetate there is a very compact area within 50 S subunits consisting of proteins L3, L4, L13, L17, L22 and L29 and of about 60% of 23 S RNA; this area probably has an essential structural role. The results also show that 23 S RNA has a more folded conformation when within the 50 S subunit than when isolated, this conformation being stabilized by some of the 50 S proteins, in particular proteins L4, L22, L20 and L21. Finally these data permit a more definite localization of the primary and/or secondary binding sites of proteins L2, L3, L4, L14, L17, L20, L21 and L22 on 23 S RNA.  相似文献   

10.
The synthesis of a series of lanthanide tetracyanoplatinates containing the auxiliary ligands 1,10′-phenanthroline (phen) or 2,2′-bipyridine (bpy) have been carried out by reaction of Ln3+ nitrate salts with phen or bpy and potassium tetracyanoplatinate in solvent systems containing dimethylsulfoxide and dimethylformamide. The use of these solvents has lead to the isolation of [{Ln(DMSO)2(C12H8N2)(H2O)3}2Pt(CN)4](Pt(CN)4)2·2C12H8N2·4H2O (Ln = Eu (Eu-1), Tb (Tb-1), Yb(Yb-1)), [Ln(DMF)3(C12H8N2)(H2O)2NO3]Pt(CN)4 (Ln = La (La-2), Eu (Eu-2), Tb (Tb-2)), and [Ln(DMF)3(C10H8N2)(H2O)2NO3]Pt(CN)4 (Ln = La (La-3), Sm (Sm-3), Eu (Eu-3), Tb (Tb-3)) in the form of single crystals. Single-crystal X-ray diffraction has been used to investigate their structural features. The use of DMSO versus DMF as the solvent results in markedly different structural features. Eu-1 contains [{Eu(DMSO)2(C12H8N2)(H2O)3}2Pt(CN)4]2+ complex cations where the two Eu3+ centers are linked by a trans-bridging Pt(CN)42− anion to form a dimeric lanthanide complex cation. An additional uncoordinated Pt(CN)42− anion balances charge. Eu-2 and Eu-3 consist of zero-dimensional salts with [Eu(DMF)3(C12H8N2)(H2O)2(NO3)]2+ or [Eu(DMF)3(C10H8N2)(H2O)2(NO3)]2+ complex cations, respectively, and only non-coordinated Pt(CN)42− anions. Photoluminescence measurements illustrate that the Eu3+ and Tb3+ compounds for all three structure types display enhanced emission due to intramolecular energy transfer from the coordinated cyclic amines.  相似文献   

11.
Gibberellins (GAs) in suspensors and embryos of Phaseolus coccineus seeds at the heart stage of embryo development were analyzed by combined gas chromatography-mass spectrometry (GC-MS). From the suspensor four C19-GAs, GA1, GA4, GA5, GA6, and one C20 GA, GA44, were identified. From the embryo, five C19-GAs GA1, GA4, GA5, GA6, GA60 and two C20 GAs, GA19 and GA44 were identified. The data, in relation to previous results, suggest a dependence of the embryo on the suspensor during early stages of development.  相似文献   

12.
Double-stranded synthetic polydeoxynucleotides of the general form poly[d(GnCn)] · poly[d(GnCn)], poly[d(GnC)] · poly[d(GCn)], and poly[d(AnTn)] · poly[d(AnTn)] have been synthesized. When n = 4 or larger, the CD spectra of polymers of the form poly[d(GnCn)] · poly[d(GnCn)] or poly[d(GnC)] · poly[d(GCn)] closely resemble the spectrum of poly[dG] · poly[dC], suggesting that a string of four continguous guanosine residues is sufficient to induce a conformation resembling that of the polypurine · polypyrimidine. With polymers of the form poly[d(AnTn)] · poly[d(AnTn)], however, the CD spectrum only gradually approaches that of poly[dA] · poly[dT].  相似文献   

13.
By the surface modification strategy, a novel high-nuclearity lanthanide complex with a discrete structure, Er26I(μ3-OH)203-O)6(NO3)9(IN)33(OH)3(H2O)33 (noted Er26, HIN = isonicotinic acid), has been prepared under hydrothermal conditions. The magnetic properties of Er26 and two analogue dysprosium assemblies Dy30I(μ3-OH)243-O)6(NO3)9(IN)41(OH)3(H2O)38 (noted Dy26-I) and Dy26I(μ3-OH)203-O)6(NO3)9(IN)31.25(OH)4.75(H2O)41.75 (noted Dy26-II) have been studied. The results show that the slow relaxation of the magnetization is newly found in Dy26-I constructed from {Dy26} and {Dy4} cluster units. The {Dy4} units in Dy26-I, the relative orientation of the complex or the inter-molecular interactions between {Dy26} cores might play an important role in the origin of this magnetic behavior.  相似文献   

14.
A critical point in the V1 sector and entire V1VO complex is the interaction of stalk subunits G (Vma10p) and E (Vma4p). Previous work, using precipitation assays, has shown that both subunits form a complex. In this work, we have analysed the N-terminal segment of subunit G (G1–59) of the V1VO ATPase from Saccharomyces cerevisiae by using nuclear magnetic resonance (NMR) spectroscopy. Analyses of 1H-15N heteronuclear single quantum coherence (HSQC) spectra of G1–59 in the absence and presence of the N-terminal peptides E1–18 and E18–38 as well as the produced and purified C-terminal segment (E39–233) shows specific interactions only with the peptide fragment E18–38. The binding of this peptide occurs via the residues M1, V2, S3, and K5 as well for V22, S23, K24, A25 and R26 of G1–59. The specific E18–38/G1–59 binding has been confirmed by fluorescence correlation spectroscopy data. The E18–38 peptide has been studied by CD spectroscopy and NMR. The 3D structure of this peptide adopts a stable helix-hinge-helix formation in solution. A model structure of the E18–38/G1–59 complex reveals the orientation of E18–38 relative to G1–59 via salt-bridges of the polar residues and van der Waals forces at the very N-terminus of both segments.  相似文献   

15.
V-ATPase (VoV1) converts the chemical free energy of ATP into an ion-motive force across the cell membrane via mechanical rotation. This energy conversion requires proper interactions between the rotor and stator in VoV1 for tight coupling among chemical reaction, torque generation, and ion transport. We developed an Escherichia coli expression system for Enterococcus hirae VoV1 (EhVoV1) and established a single-molecule rotation assay to measure the torque generated. Recombinant and native EhVoV1 exhibited almost identical dependence of ATP hydrolysis activity on sodium ion and ATP concentrations, indicating their functional equivalence. In a single-molecule rotation assay with a low load probe at high ATP concentration, EhVoV1 only showed the “clear” state without apparent backward steps, whereas EhV1 showed two states, “clear” and “unclear.” Furthermore, EhVoV1 showed slower rotation than EhV1 without the three distinct pauses separated by 120° that were observed in EhV1. When using a large probe, EhVoV1 showed faster rotation than EhV1, and the torque of EhVoV1 estimated from the continuous rotation was nearly double that of EhV1. On the other hand, stepping torque of EhV1 in the clear state was comparable with that of EhVoV1. These results indicate that rotor-stator interactions of the Vo moiety and/or sodium ion transport limit the rotation driven by the V1 moiety, and the rotor-stator interactions in EhVoV1 are stabilized by two peripheral stalks to generate a larger torque than that of isolated EhV1. However, the torque value was substantially lower than that of other rotary ATPases, implying the low energy conversion efficiency of EhVoV1.  相似文献   

16.
Summary Extracts of corpora cardiaca from two members of the family Tenebrionidae,Zophobas rugipes andTenebrio molitor, from one member of the Chrysomelidae,Leptinotarsa decemlineata, and from three members of the Scarabaeidae,Pachnoda marginata, P. sinuata andMelolontha hippocastani, were assayed for adipokinetic and hypertrehalosaemic activity in acceptor locusts (Locusta migratoria) and cockroaches (Periplaneta americana), respectively. All corpus cardiacum material tested, except that from the cockchafer,M. hippocastani, gave positive bioassay results. Biological activities of corpus cardiacum extracts from all species investigated can be resolved on reversed-phase high performance liquid chromatography (RP-HPLC). Gland extracts from the two tenebrionid species each show a single peak of biological activity associated with a single peak of UV absorbance having an identical retention time in both species. The two biologically active fractions from the corpora cardiaca of the potato beetle,L. decemlineata, coelute with exogenous (synthetic) hypertrehalosaemic hormones I and II of the American cockroach. The two species of the genusPachnoda contain two active compounds in their glands; compound I of each species is more abundant and elutes just ahead of the (synthetic) hypertrehalosaemic hormone of the cockroachBlaberus discoidalis. The gland material ofM. hippocastani exhibits and absorbance peak with the same retention time as the major peak from thePachnoda-species; however, this peak material does not elicit biological activity in the assays used here. After fractionation by RP-HPLC the main biologically active compounds were subjected to amino acid analyses. All factors are peptidic and contain 8 amino acid residues. The peptides from the tenebrionid species have the amino acid residues Asx(2), Glx(1), Ser(1), Pro(1), Leu(1), Phe(1) and Trp(i), whereas the main peptide from corpora cardiaca ofP. marginata contains the residues Asx(2), Glx(1), Ser(1), Pro(1), Tyr(1), Leu(1) and Trp(1). Amino acid composition analyses of the two active fractions fromL. decemlineata reveal the residues Asx(2), Glx(1), Ser(1), Pro(1), Val(1), Phe(1) and Trp(1) for compound I and Asx(1), Glx(1), Thr(2), Pro(1), Leu(1), Phe(1) and Trp(1) for compound II.  相似文献   

17.
Large-conductance calcium and voltage-dependent potassium (BKCa) channel is an important determinant of vascular tone. It is activated by hydrogen peroxide (H2O2) which occurs in various physiological and pathological processes. However, the regulation mechanism is not fully understood. In the present study, the mSlo in the presence or absence of hβ1 were cotransfected with the PTENwt, PTENC124S, PTENG129E in HEK 293 cells. Typical BKCa channel currents could be recorded in cell-attached configurations. We found that PTENwt reduced the H2O2-induced BKCa channel activation during the initial 10 min treatment. In contrast, coexpression with catalytically inactive PTENC124S/PTENG129E mutants that lack lipid phosphatase activity produced no regulation on the H2O2-induced BKCa channel activation. These results demonstrated that PTEN regulated the H2O2-induced BKCa channel activation through phosphatidylinositol 3-phosphatse. However, the inhibitory effect of PTEN on the H2O2-induced BKCa channel activation was attenuated when cells were treated with H2O2 at concentrations higher than 100 μM or at 100 μM for long-term treatment. In addition, the p-AKT expression level in PTENwt overexpressing cells was lower than that in control cells, and the increase of cytoplasmic free calcium concentration ([Ca2+]i) induced by H2O2 was also inhibited. These findings may elucidate a new mechanism for H2O2-induced BKCa channel activation and provide some evidences for the role of PTEN on vasodilation induced by H2O2.  相似文献   

18.
Recognizing the physiological diversity of different plant organs, studies were conducted to investigate the distribution of endogenous gibberellins (GAs) in Brassica (canola or oilseed rape). GA1 and its biosynthetic precursors, GA20 and GA19, were extracted, chromatographically purified, and quantified by gas-chromatography-selected ion monitoring (GC-SIM), using [2H2]GAs as internal standards. In young (vegetative) B. napus cv. Westar plants, GA concentrations were lowest in the roots, increased acropetally along the shoot axis, and were highest in the shoot tips. GA concentrations were high but variable in leaves. GA1 concentrations also increased acropetally along the plant axis in reproductive plants. During early silique filling, GA1 concentrations were highest in siliques and progressively lower in flowers, inflorescence stalks (peduncles plus pedicels), stem, leaves, and roots. Concentrations of GA19 and GA20 showed similar patterns of distribution except in leaves, in which concentrations were higher, but variable. Immature siliques were qualitatively rich in endogenous GAs and GA1, GA3, GA4, GA8, GA9, GA17, GA19, GA20, GA24, GA29, GA34, GA51, and GA53 were identified by GC-SIM. In whole siliques, GA19, GA20, GA1, and GA8 concentrations declined during maturation due to declining levels in the maturing seeds; their concentrations in the silique coats remained relatively constant and low. These studies demonstrate that GAs are differentially distributed in Brassica with a general pattern of acropetally increasing concentration in shoots and high concentration in actively growing and developing organs.  相似文献   

19.
为探究岩溶植物的光合生理适应机制,采用Li-6400XT便携式光合作用测量系统,对广西平果市岩溶区8种适生植物的叶片净光合速率(Pn)、气孔导度(Gs)、胞间CO2浓度(Ci)、蒸腾速率(Tr)、水分利用效率(WUE)和气孔限制值(Ls)等光合特征参数进行了测定分析。结果表明:(1)6个光合特征参数在种内和种间均存在不同程度的变异,并且种内变异均大于种间变异。(2)Gs和Tr的变化主要来源于种间变异(46.72%~49.76%),而Pn、Ci、WUE和Ls变化主要来源于种内变异(48.66%~64.50%)。在生活型水平上,Pn、Gs和Tr的种内变异表现为常绿植物小于落叶植物,而Ci、WUE和Ls则相反。(3)各参数的种间变异均表现为落叶植...  相似文献   

20.
Antagonistic capability of Trichoderma harzianum was improved through UV-irradiation. Four different type of mutants, T. harzianum - Ma (Th-Ma), T. harzianum - Mb(Th-Mb), T. harzianum - Mc (Th-Mc), T. harzianum - Md (Th-Md) of T. harzianum and the parent strain (Th-P) were selected for further studies. Th-Ma and Th-Mb showed more antagonistic capability against Macrophomina phaseolina than its parent strain Th-P in dual culture. Biochemical analysis of these four mutants and the parent strain showed that Th-Ma releases higher level of two lytic enzymes i.e. chitinases and cellulases and Th-Mb produces more β-1,3-glucanase activity than the parent strain. Culture filtrate of Th-Ma also showed antifungal properties. Study of the competitive saprophytic ability (CSA) of these four mutants and the parent strain were also made. Th-Ma exhibited higher CSA than the parental isolate while Th-Md had less CSA than all other mutants and the parent strain of T. harzianum.  相似文献   

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