Luminescence properties of a novel red phosphor 6LaPO4–3La3PO7–2La7P3O18:Eu3+

Eu³⁺‐doped 6LaPO₄–3La₃PO₇–2La₇P₃O₁₈ red luminescent phosphors were synthesized by co‐deposition and high‐temperature solid‐state methods and its polyphase state was confirmed by X‐ray diffraction analysis. Transmission electron microscopy showed the grain morphology as a mixture of rods and spheres. Luminescence properties of the phosphor were investigated and its red emission parameters were evaluated as a function of Eu³⁺ concentration (3.00–6.00 mol%). Excitation spectra of 6LaPO₄–3La₃PO₇–2La₇P₃O₁₈:Eu³⁺ showed strong absorption bands at 280, 395, and 466 nm, while the luminescence spectra exhibited prominent red emission peak centred at 615 nm (⁵D₀→⁷F₂) in the red region. CIE chromaticity coordinates of the 6LaPO₄–3La₃PO₇–2La₇P₃O₁₈:5%Eu³⁺ phosphor were (0.668, 0.313) in the red region, and defined its potential application as a red phosphor.     

Synthesis of AZT analogues: 7-(3-azido-2hydroxypropyl)-, 7-(3-amino-2-hydroxypropyl)-, 7-(3-triazolyl-2-hydroxypropyl)theophyllines

Nucleophilic displacement of the tosyloxy group in 7-(2-hydroxy-3-p-toluenesulfonyloxypropyl)theophylline (1) with azide anion afforded 7-(3-azido-2-hydroxypropyl)theophylline (2). Reduction of the 3-azido group in 2 with Ph₃P/Py/NH₄OH afforded the 3-amino derivative 4, alternatively obtained by regioselective amination of 7-(2,3-epoxypropyl)theophylline (3). Selective acetylation of 4 gave the N-acetyl derivative 5. 1,3-Dipolar cycloaddition of the azide group in 2 with N¹-propargyl thymine (6) afforded the regioisomeric triazole 7.     

Structures, dynamic behaviour in solution and cross-coupling reactions of the α-palladiated (η-alkylarene)tricarbonylchromium complexes containing a palladium-chromium bond

Structures of the complexes (η³-C₃H₅)Pd(μ-η^6:1-CH₂PhCr(CO)₃ and (η³-C₃H₅)Pd[μ-η^6:1-CH(Ph)Ph]Cr(CO)₃ in solution were evaluated by NMR (¹H and ¹³C) and IR spectroscopy. The dynamic behaviour of the complexes was investigated. Quick rotation (on the NMR time scale) of the tricarbonylchromium groups around the axis passing through the centre of the η⁶-coordinated phenyl ring and the chromium atom takes place at room temperature and becomes slow on cooling. The η³-allylic ligand was proved to undergo no dynamic changes in solution. Unlike the solid state, the semi-bridging carbonyl groups between chromium and palladium atoms are absent or very weak in solution. Cross-coupling reactions of the complexes with organohalides are described.     

Photoluminescence properties of a new orange–red‐emitting Sm3+–La3SbO7 phosphor

The antimonate compound La₃SbO₇ has high chemical stability, lattice stiffness and thermal stability. Orange–red‐emitting antimonate‐based phosphors La₃SbO₇:xSm³⁺ (x = 0.02, 0.05, 0.08, 0.10, 0.15, 0.20 and 0.25) were synthesized. The phase structure and photoluminescence properties of these phosphors were investigated. The emission spectrum obtained on excitation at 407 nm contained exclusively the characteristic emissions of Sm³⁺ at 568, 608, 654 and 716 nm, which correspond to the transitions from ⁴G_5/2 to ⁶H_5/2, ⁶H_7/2, ⁶H_9/2 and ⁶H_11/2 of Sm³⁺, respectively. The strongest emission was located at 608 nm due to the ⁴G_5/2→⁶H_7/2 transition of Sm³⁺, generating bright orange–red light. The critical quenching concentration of Sm³⁺ in La₃SbO₇:Sm³⁺ phosphor was determined as 10% and the energy transfer between Sm³⁺ was found to be through an exchange interaction. The International Commission on Illumination chromaticity coordinates of the La₃SbO₇:0.10Sm³⁺ phosphors are located in the orange–red region. The La₃SbO₇:Sm³⁺ phosphors may be potentially used as red phosphors for white light‐emitting diodes. Copyright © 2015 John Wiley & Sons, Ltd.     

Polyester Biosynthesis Characteristics of Pseudomonas citronellolis Grown on Various Carbon Sources, Including 3-Methyl-Branched Substrates

Forty-two different carbon sources were tested for the polyester synthesis of a citronellol-utilizing bacterium, Pseudomonas citronellolis (ATCC 13674). These included linear C₂ to C₁₀ monocarboxylic acids, C₃ to C₁₀ dicarboxylic acids, saccharides, α,ω-diols, hydrocarbons, and 3-methyl-branched substrates such as 3,7-dimethyl-6-octen-1-ol (citronellol), 3-methyl-n-valerate, 3-methyl-1-butanol, and 3-methyladipate. Isolated polymers were characterized by gas chromatography, infrared spectroscopy, ¹H- or ¹³C-nuclear magnetic resonance spectroscopy, ¹H-¹³C heteronuclear correlation spectroscopy (¹H-¹³C COSY), ¹H-¹H homonuclear COSY, and differential scanning calorimetry. Polyesters from nine monocarboxylic acids and two related carbon sources could be metabolically divided into three groups. The first group of C₂ to C₄ carbon sources resulted in copolyesters composed of 61 to 70 mol% 3-hydroxydecanoate, 23 to 33 mol% 3-hydroxyoctanoate, 3.6 to 9.0 mol% 3-hydroxy-5-cis-dodecenoate, and 1.8 to 2.6 mol% 3-hydroxy-7-cis-tetradecenoate. Carbon sources in group II (C₇ to C₁₀) produced copolyesters composed of 3-hydroxyacid monomer units with the same number of carbon atoms as the substrate (major constituent) and monomer units with either two less or two more carbons. Negligible amounts of 3-hydroxy-5-cis-dodecenoate and 3-hydroxy-7-cis-tetradecenoate were detected in copolyesters from this group. Copolyesters from group III (C₅ and C₆) had a monomer unit distribution that could be said to be between those of groups I and II. In addition, a novel copolyester, poly(3-hydroxy-7-methyl-6-octenoate-co-3-hydroxy-5-methylhexanoate), was synthesized when grown on citronellol. The ¹H-¹³C heteronuclear COSY spectrum for monomer unit II revealed that both methylene and isopropyl groups, proximately connected in series to a single chiral center, had magnetically diastereotopic natures.     

Aerosol-assisted chemical vapour deposition (AACVD) of silver films from triorganophosphine adducts of silver carboxylates, including the structure of [Ag(O2CC3F7)(PPh3)2]

Silver carboxylates [Ag(O₂CR): R=Me, ^tBu, 2,4,6-Me₃C₆H₂], fluorocarboxlyates [Ag(O₂CR_f): R_f=C₃F₇, C₆F₁₃, C₇F₁₅] and their phosphine adducts [Ag(O₂CR)·nPR₃′: R=Me, ^tBu, 2,4,6-Me₃C₆H₂, R′=Me, Ph, n=2; R=Me, R′=Me, n=3; Ag(O₂CR_f).2PPh₃, R_f=C₃F₇, C₆F₁₃, C₇F₁₅] have been synthesised, characterised spectroscopically and used as precursors in the aerosol-assisted chemical vapour deposition of silver films. All the phosphine adducts produced films, though in general PMe₃ adducts, proved more successful than PPh₃ analogues. The fluoro-carboxylates and their PPh₃ adducts all generated silver films, though the growth rate for the adducts was lower. All these latter films showed carbon impurities while fluorine was also evident in most cases. The X-ray structure of AgO₂CC₃F₇·2PPh₃ is also reported.     

Novel reaction of succinyl coenzyme A (Succinyl-CoA) synthetase: activation of 3-sulfinopropionate to 3-sulfinopropionyl-CoA in Advenella mimigardefordensis strain DPN7T during degradation of 3,3'-dithiodipropionic acid

The sucCD gene of Advenella mimigardefordensis strain DPN7^T encodes a succinyl coenzyme A (succinyl-CoA) synthetase homologue (EC 6.2.1.4 or EC 6.2.1.5) that recognizes, in addition to succinate, the structural analogues 3-sulfinopropionate (3SP) and itaconate as substrates. Accumulation of 3SP during 3,3′-dithiodipropionic acid (DTDP) degradation was observed in Tn5::mob-induced mutants of A. mimigardefordensis strain DPN7^T disrupted in sucCD and in the defined deletion mutant A. mimigardefordensis ΔsucCD. These mutants were impaired in growth with DTDP and 3SP as the sole carbon source. Hence, it was proposed that the succinyl-CoA synthetase homologue in A. mimigardefordensis strain DPN7^T activates 3SP to the corresponding CoA-thioester (3SP-CoA). The putative genes coding for A. mimigardefordensis succinyl-CoA synthetase (SucCD_Am) were cloned and heterologously expressed in Escherichia coli BL21(DE3)/pLysS. Purification and characterization of the enzyme confirmed its involvement during degradation of DTDP. 3SP, the cleavage product of DTDP, was converted into 3SP-CoA by the purified enzyme, as demonstrated by in vitro enzyme assays. The structure of 3SP-CoA was verified by using liquid chromatography-electrospray ionization-mass spectrometry. SucCD_Am is Mg²⁺ or Mn²⁺ dependent and unspecific regarding ATP or GTP. In kinetic studies the enzyme showed highest enzyme activity and substrate affinity with succinate (V_max = 9.85 ± 0.14 μmol min⁻¹ mg⁻¹, K_m = 0.143 ± 0.001 mM). In comparison to succinate, activity with 3SP was only ca. 1.2% (V_max = 0.12 ± 0.01 μmol min⁻¹ mg⁻¹) and the affinity was 6-fold lower (K_m = 0.818 ± 0.046 mM). Based on the present results, we conclude that SucCD_Am is physiologically associated with the citric acid cycle but is mandatory for the catabolic pathway of DTDP and its degradation intermediate 3SP.     

Isorhamnetin3-(2,6-dirhamnosylgalactoside)-7-rhamnoside and 3-(6-rhamnosylgalactoside)-7-rhamnoside from Rhazya stricta

Robinin and two novel glycosides: isorhamnetin 3-(6-rhamnosylgalactoside)-7-rhamnoside and 3-(2,6-dirhamnosylgalactoside)-7-rhamnoside were isolated from a leaf extract of Rhazya stricta. Naringinase catalysed hydrolysis of both glycosides removed the rhamnose from the 7-hydroxyl. The product isorhamnetin 3-(2,6-dirhamnosylgalactoside) was shown by ¹H NMR to be identical with a glycoside previously isolated from Primula veris.     

Biosynthetic Origin of Gibberellins A(3) and A(7) in Cell-Free Preparations from Seeds of Marah macrocarpus and Malus domestica

Cell-free preparations from seeds of Marah macrocarpus L. and Malus domestica L. catalyzed the conversion of gibberellin A₉ (GA₉) and 2,3-dehydroGA₉ to GA₇; GA₉ was also metabolized to GA₄ in a branch pathway. The preparation from Marah seeds also metabolized GA₅ to GA₃ in high yield; GA₆ was a minor product and was not metabolized to GA₃. Using substrates stereospecifically labeled with deuterium, it was shown that the metabolism of GA₅ to GA₃ and of 2,3-dehydroGA₉ to GA₇ occurs with the loss of the 1β-hydrogen. In cultures of Gibberella fujikuroi, mutant B1-41a, [1β,2β-²H₂]GA₄, was metabolized to [1,2-²H₂]GA₃ with the loss of the 1α- and 2α-hydrogens. These results provide further evidence that the biosynthetic origin of GA₃ and GA₇ in higher plants is different from that in the fungus Gibberella fujikuroi.     

Development of potent anti-infective agents from Silurana tropicalis: Conformational analysis of the amphipathic,alpha-helical antimicrobial peptide XT-7 and its non-haemolytic analogue [G4K]XT-7

Peptide XT-7 (GLLGP⁵LLKIA¹⁰AKVGS¹⁵NLL.NH₂) is a cationic, leucine-rich peptide, first isolated from skin secretions of the frog, Silurana tropicalis (Pipidae). The peptide shows potent, broad-spectrum antimicrobial activity but its therapeutic potential is limited by haemolytic activity (LC₅₀ = 140 µM). The analogue [G4K]XT-7, however, retains potent antimicrobial activity but is non-haemolytic (LC₅₀ > 500 µM). In order to elucidate the molecular basis for this difference in properties, the three dimensional structures of XT-7 and the analogue have been investigated by proton NMR spectroscopy and molecular modelling. In aqueous solution, both peptides lack secondary structure. In a 2,2,2-trifluoroethanol (TFE-d₃)-H₂O mixed solvent system, XT-7 is characterised by a right handed α-helical conformation between residues Leu³ and Leu¹⁷ whereas [G4K]XT-7 adopts a more restricted α-helical conformation between residues Leu⁶ and Leu¹⁷. A similar conformation for XT-7 in 1,2-dihexanoyl-sn-glycero-3-phosphocholine (DHPC) micellular media was observed with a helical segment between Leu³ and Leu¹⁷. However, differences in side chain orientations restricting the hydrophilic residues to a smaller patch resulted in an increased hydrophobic surface relative to the conformation in TFE-H₂O. Molecular modelling of the structures obtained in our study demonstrates the amphipathic character of the helical segments. It is proposed that the marked decrease in haemolytic activity produced by the substitution Gly⁴ → Lys in XT-7 arises from a decrease in both helicity and hydrophobicity. These studies may facilitate the development of potent but non-toxic anti-infective agents based upon the structure of XT-7.     

A Novel (S)-6-Hydroxynicotine Oxidase Gene from Shinella sp. Strain HZN7

Nicotine is an important environmental toxicant in tobacco waste. Shinella sp. strain HZN7 can metabolize nicotine into nontoxic compounds via variations of the pyridine and pyrrolidine pathways. However, the catabolic mechanism of this variant pathway at the gene or enzyme level is still unknown. In this study, two 6-hydroxynicotine degradation-deficient mutants, N7-M9 and N7-W3, were generated by transposon mutagenesis. The corresponding mutant genes, designated nctB and tnp2, were cloned and analyzed. The nctB gene encodes a novel flavin adenine dinucleotide-containing (S)-6-hydroxynicotine oxidase that converts (S)-6-hydroxynicotine into 6-hydroxy-N-methylmyosmine and then spontaneously hydrolyzes into 6-hydroxypseudooxynicotine. The deletion and complementation of the nctB gene showed that this enzyme is essential for nicotine or (S)-6-hydroxynicotine degradation. Purified NctB could also convert (S)-nicotine into N-methylmyosmine, which spontaneously hydrolyzed into pseudooxynicotine. The kinetic constants of NctB toward (S)-6-hydroxynicotine (K_m = 0.019 mM, k_cat = 7.3 s⁻¹) and nicotine (K_m = 2.03 mM, k_cat = 0.396 s⁻¹) indicated that (S)-6-hydroxynicotine is the preferred substrate in vivo. NctB showed no activities toward the R enantiomer of nicotine or 6-hydroxynicotine. Strain HZN7 could degrade (R)-nicotine into (R)-6-hydroxynicotine without any further degradation. The tnp2 gene from mutant N7-W3 encodes a putative transposase, and its deletion did not abolish the nicotine degradation activity. This study advances the understanding of the microbial diversity of nicotine biodegradation.     

Investigation of PGM13, PGM16, and PGM17 variants by isoelectric focussing. Evidence for new subtypes of the PGM 1 3 and PGM 1 7 alleles

Summary A total of 345 haemolysates previously phenotyped by starch gel electrophoresis and known to contain the products of the PGM ₁ ³ , PGM ₁ ⁶ , and PGM ₁ ⁷ alleles have been analyzed by thin layer polyacrylamide gel isoelectric focussing in the pH range 5–7. Two common subtypes, 3+and 3-, of the PGM ₁ ³ allele have been found in a number of Pacific populations. A single form of the PGM ₁ ⁷ allele was observed in the Western Caroline Islands. In contrast, one of two Indian PGM₁7 variants focussed to a different position when compared with the form found at polymorphic frequency in the Western Caroline Islands. Only one type of the PGM ₁ ⁶ allele was detected during the present investigation.     

Synthesis and preliminary biological evaluation of [11C]methyl (2-amino-5-(benzylthio)thiazolo[4,5-d]pyrimidin-7-yl)-d-leucinate for the fractalkine receptor (CX3CR1)

The reference standard methyl (2-amino-5-(benzylthio)thiazolo[4,5-d]pyrimidin-7-yl)-d-leucinate (5) and its precursor 2-amino-5-(benzylthio)thiazolo[4,5-d]pyrimidin-7-yl)-d-leucine (6) were synthesized from 6-amino-2-mercaptopyrimidin-4-ol and BnBr with overall chemical yield 7% in five steps and 4% in six steps, respectively. The target tracer [¹¹C]methyl (2-amino-5-(benzylthio)thiazolo[4,5-d]pyrimidin-7-yl)-d-leucinate ([¹¹C]5) was prepared from the acid precursor with [¹¹C]CH₃OTf through O-[¹¹C]methylation and isolated by HPLC combined with SPE in 40–50% radiochemical yield, based on [¹¹C]CO₂ and decay corrected to end of bombardment (EOB). The radiochemical purity was >99%, and the specific activity (SA) at EOB was 370–1110 GBq/μmol with a total synthesis time of ～40-min from EOB. The radioligand depletion experiment of [¹¹C]5 did not display specific binding to CX₃CR1, and the competitive binding assay of ligand 5 found much lower CX₃CR1 binding affinity.     

Structural,morphological, and optical characteristics of Gd2Si2O7:Dy3+ nanophosphors for WLEDs

Yellowish-white light-emitting Gd_2-xSi₂O₇:xDy³⁺ (x = 1–5 mol%) nanophosphors were prepared using a solution combustion synthesis method. Fluorescence spectrophotometry and X-ray diffraction measurements were performed to scrutinize the optical performances and phase recognition of the designated nanophosphors. The outcomes specified that the prepared phosphors were crystallized into a triclinic phase with a P-1 space group. As the concentration of Dy³⁺ ions was increased, the unit-cell volume decrease proportionally due to the replacement of large-sized Gd³⁺ by small-sized Dy³⁺ ions. Under ultraviolet excitation at 349 nm, emission spectra consisted of two pronounced emission lines at ~482 nm (blue line), ~578 nm (yellow line), and a relatively weaker emission at ~670 nm (red line) due to ⁴F_9/2→⁶H_15/2, ⁴F_9/2→⁶H_13/2, and ⁴F_9/2→⁶H_11/2 intraconfigurational transitions of Dy³⁺ ions, respectively. The evidence about the site symmetry around Dy³⁺ ions was examined by considering the ratio of yellow-to-blue emission intensity. The observed critical distance (R_c) value was ~20.56 Å (≫5 Å), which signified that energy transfer primarily occurred due to multipolar interaction. The obtained coordinates were close to the white region of the Commission Internationale de l'Éclairage chromaticity diagram, which marked a significant milestone in the development of white light-emitting diodes.     

Development of selective inhibitors for the treatment of rheumatoid arthritis: (R)-3-(3-(Methyl(7H-pyrrolo[2,3-d]pyrimidin-4-yl)amino)pyrrolidin-1-yl)-3-oxopropanenitrile as a JAK1-selective inhibitor

A series of 3(R)-aminopyrrolidine derivatives were designed and synthesized for JAK1-selective inhibitors through the modification of tofacitinib’s core structure, (3R,4R)-3-amino-4-methylpiperidine. From the new core structures, we selected (R)-N-methyl-N-(pyrrolidin-3-yl)-7H-pyrrolo[2,3-d]pyrimidin-4-amine as a scaffold for further SAR studies. From biochemical enzyme assays and liver microsomal stability tests, (R)-3-(3-(methyl(7H-pyrrolo[2,3-d]pyrimidin-4-yl)amino)pyrrolidin-1-yl)-3-oxopropanenitrile (6) was chosen for further in vivo test through oral administration. Compound 6 showed improved selectivity for JAK1 compared to that of tofacitinib (IC₅₀ 11, 2.4?×?10², 2.8?×?10³, and 1.1?×?10²?nM for JAK1, JAK2, JAK3, and TYK2, respectively). In CIA and AIA model tests, compound 6 exhibited similar efficacy to tofacitinib citrate.     

Methylation of DNA by 3H-14C-methyl-labelled N-methyl-N-nitrosourea--evidence for transfer of the intact methyl group

The following products have been isolated from methyl-labelled N-methyl-N-nitrosourea (MNUA) and DNA after reaction at pH 8: 1-, 3-, 7-methyladenines, 3-methyldeoxycytidine, 3-, 7- and O⁶-methylguanines, 3- and O⁴-methylthymidines. Comparison of C³H₃ and ¹⁴CH₃ labelling showed that the ratio ${}^3\text{H}{}^{14}\text{C}$ in the products was the same and equal to that in the original reagents, in accord with the concept that the methyl group is transferred intact, and not via diazomethane. In some cases, most notably with O⁶-methyldeoxyguanosine, the ³H-labelled products were found to elute from Dowex 50 (NH₄⁺ form) slightly ahead of ¹⁴C-labelled or unlabelled products.     

Synthesis,GluN2B affinity and selectivity of benzo[7]annulen-7-amines

Due to their beneficial side effect profile, NMDA receptor antagonists interacting selectively with the allosteric ifenprodil binding site of the GluN2B subunit are of major interest for the treatment of neurological and neurodegenerative disorders. A series of benzo[7]annulen-7-amines 6 was designed by conformational restriction of ifenprodil (1). At first the benzo[7]annulen-7-one 11 was prepared in a three-step synthesis comprising of a double Knoevenagel condensation of phthalaldehyde (7) with dimethyl 3-oxoglutarate (8), hydrogenation of 9 and saponification/decarboxylation of 10. Reductive amination of the ketone 11 with primary amines and NaBH(OAc)₃ led to the secondary amines 6a–d, cis-6h and trans-6i. The tertiary amines 6e–g were obtained by S_N2-substitution of the nosylate 13. Although H-bond forming substituents in 2- and 5-position are missing, the amines 6 exhibit high affinity towards GluN2B containing NMDA receptors. A distance of four to five bond lengths between the basic amino moiety and the phenyl ring in the side chain appears to be optimal for high GluN2B affinity. The phenylcyclohexylamine cis-6h and the 4-benzylpiperidine 6g show the highest GluN2B affinities (K_i = 2.3 nM and 2.9 nM, respectively). With respect to selectivity against the PCP binding site, σ₁ and σ₂ receptors the phenylpiperazine 6f is the most promising GluN2B antagonist.     

Luminescent properties of novel red‐emitting M7Sn(PO4)6:Eu3+ (M = Sr,Ba) for light‐emitting diodes

Novel red‐emitting phosphors, Eu³⁺‐activated M₇Sn(PO₄)₆ (M = Sr, Ba), were synthesized at 1200°C by conventional solid‐state reaction method. The luminescent properties of M₇Sn(PO₄)₆:Eu³⁺ (M = Sr, Ba) phosphors were investigated, and the critical concentration of the activator (Eu³⁺) concentration were found to be 0.175 mol and 0.21 mol per formula unit for Sr_7‐xSn(PO₄)₆:xEu³⁺ and Ba_7‐xSn(PO₄)₆:xEu³⁺, respectively. These phosphors presented red luminescence under the excitation of 395 or 465 nm, perfectly matching with the emissions wavelength of near‐ultraviolet (UV) light‐emitting diodes (LEDs) and InGaN blue LED.     

Nucleoside complexing. A13C NMR spectroscopic investigation of the metal binding sites in 7-methylguanosine, 7-methylinosine and some related new synthetic betains

Once deprotonated, both the N1 and O6 positions of 6-oxopurine nucleosides become important metal binding sites. In a continuation of our studies of metal binding to 6-oxopurines alkylated at N7 and deprotonated at N1, we have carried out a¹³C NMR spectroscopic study of the binding of various metal species including hard metal species (Sr, Ba, La, Pr), intermediate metal species (Zn, Cd, Pb), and soft metal species (Pt, Hg). A detailed study was not possible with HgCl₂ since mercuration occurred readily at C8. The¹³C NMR shift patterns for the O6 resonance of 7-methylguanosine, 7-methylinosine, 2-dimethylamino-7,9-dimethylhypoxanthinium betain, 2-diethylamino-7-methyl-9-propylhypoxanthinium and betain and ethylamino and 6 thio analogs of the latter betain suggest that metal species of intermediate ‘softness’ prefer endocyclic N1 binding over exocyclic O6 a larger extent than they prefer endocyclic N3 binding over exocyclic O2 binding in cytosine derivatives. Most dramatically, the presence of a dialkylamino group ortho to the endocyclic binding site does not appear to prevent N binding in the betains whereas such binding is greatly, if not completely, prevented to cytosine derivatives. In particular, the complex cis-[Pt(Me₂SO)₂Cl₂] forms a complex with 2-dimethylamino-7,9-dimethyl-hypoxanthinium betain with an upfield shift characteristic of endocyclic N binding. The hard metal salts, Ba(NO₃)₂ and Pr(NO₃)₃ interacted weakly, if at all, with 2-diethylamino-7-methyl-9-propyl-6-thiopurinium betain whereas the nitrate salts of Zn, Cd and Pb gave pronounced upfield shifts of C6. This result is consistent with coordination at the exocyclic S.The compound, 2-dimethylamino-9-methylhypoxanthine, was prepared starting from 5-amino-4,6-dihydroxy-2-dimethylaminopyrimidine. This 5-aminopyrimidine derivative and methyl isothiocyanate were converted to N-(4,6-dihydroxy-2-dimethylamino-5-pyrimidinyl)-N′-methylthiourea which was then converted to 2-dimethylamino-6-hydroxy-9-methyl-8-purinethiol with hot hydrochloric acid. Raney nickel desulfurization in a basic solution gave 2-dimethylamino-9-methylhypoxanthine.The related compounds, 2-ethylamino-9-propyl- and 2-diethylamino-9-propylhypoxanthine, were prepared from 4,6-diamino-2-methylmercapto-5-nitrosopyrimidine. Treatment of this pyrimidine with dimethyl-, ethyl- and diethyl-amine led to the initial intermediate 2-alkyl-amino-4,6-diamino-5-nitrosopyrimidines. Treatment of these pyrimidines with sodium hydrosulfite, formic acid and formamide in one flask gave the mixture of corresponding 2-alkyl-aminoadenines and 2-alkylamino-6-formamido-purines. The latter compounds were successfully converted to the desired 2-alkylaminoadenines by alkali treatment. Alkylation with alkyl halides at the 9-positions of these adenine derivatives and subsequent deamination with nitrous acid gave 2-dimethylamino-9-methyl-, 2-ethylamino-9-propyl- and 2-ethylamino-9-propylhypoxanthines.These hypoxanthines were further methylated at their 7-position to give the corresponding hypoxanthinium betains.2-Diethylamino-7-methyl-9-propyl-6-thiopurinium betain was prepared by the methylation at the 7-position of 2-diethylamino-9-propylhypoxanthine followed by 6-chlorination and, then, by treatment with thiourea.