Artificial Caries Lesion Characteristics after Secondary Demineralization with Theobromine-Containing Protocol

Developing artificial caries lesions with varying characteristics is needed to adequately study caries process in vitro. The objective of this study was to investigate artificial caries lesion characteristics after secondary demineralization protocol containing theobromine and fluoride. Sixty bovine enamel slabs (4 × 3 mm) were demineralized using a Carbopol-containing protocol for 6 days. A baseline area (2 × 3 mm) was protected with acid-resistant nail varnish, after which specimens were exposed for 24 h to a secondary demineralization protocol containing acetic acid plus one of four fluoride/theobromine combinations (n = 15): theobromine (50 or 200 ppm) and fluoride (0 or 1 ppm). Specimens were sectioned and analyzed using transverse microradiography for changes in mineral content, lesion depth, and surface layer mineralization. Data was analyzed using paired t-test and analysis of variance followed by Bonferroni test at 0.05 significance level. After secondary demineralization, fluoride-containing groups had significantly deeper lesions (p = 0.002 and 0.014) compared to the group with 0 ppm fluoride and 50 ppm theobromine. Mineral content and lesion depth were significantly different compared to baseline for all groups. Theobromine did not show an added effect on mineral uptake. Theobromine-containing groups exhibited particularly deep lesions with a more uniform mineral profile in the presence of fluoride.     

Supramolecular networks supported by the anion…π linkage of Keggin‐type heteropolyoxotungstates

Anion…π interactions are newly recognized weak supramolecular forces which are relevant to many types of electron‐deficient aromatic substrates. Being less competitive with respect to conventional hydrogen bonding, anion…π interactions are only rarely considered as a crystal‐structure‐defining factor. Their significance dramatically increases for polyoxometalate (POM) species, which offer extended oxide surfaces for maintaining dense aromatic/inorganic stacks. The structures of tetrakis(caffeinium) μ₁₂‐silicato‐tetracosa‐μ₂‐oxido‐dodecaoxidododecatungsten trihydrate, (C₈H₁₁N₄O₂)₄[SiW₁₂O₄₀]·3H₂O, (1), and tris(theobrominium) μ₁₂‐phosphato‐tetracosa‐μ₂‐oxido‐dodecaoxidododecatungsten ethanol sesquisolvate, (C₇H₉N₄O₂)₃[PW₁₂O₄₀]·1.5C₂H₅OH, (2), support the utility of anion…π interactions as a special kind of supramolecular synthon controlling the structures of ionic lattices. Both caffeinium [(HCaf)⁺ in (1)] and theobrominium cations [(HTbr)⁺ in (2)] reveal double stacking patterns at both axial sides of the aromatic frameworks, leading to the generation of anion…π…anion bridges. The latter provide the rare face‐to‐face linkage of the anions. In (1), every square face of the metal–oxide cuboctahedra accepts the interaction and the above bridges yield flat square nets, i.e. {(HCaf⁺)₂[SiW₁₂O₄₀]^4?}_n. Two additional cations afford single stacks only and they terminate the connectivity. Salt (2) retains a two‐dimensional (2D) motif of square nets, with anion…π…anion bridges involving two of the three (HTbr)⁺ cations. The remaining cations complete a fivefold anion…π environment of [PW₁₂O₄₀]^3?, acting as terminal groups. This single anion…π interaction is influenced by the specific pairing of (HTbr)⁺ cations by double amide‐to‐amide hydrogen bonding. Nevertheless, invariable 2D patterns in (1) and (2) suggest the dominant role of anion…π interactions as the structure‐governing factor, which is applicable to the construction of noncovalent linkages involving Keggin‐type oxometalates.     

ADDUCTS OF THEOBROMINE WITH 3d METAL PERCHLORATES

Abstract

Adducts of theobromine (tbH) with 3d metal perchlorates (Mⁿ⁺ = Cr^3-. Mn²⁺, Fe²⁺, Fe³⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn^2- I here prepared by refluxing mixtures of the Iigand and a metal salt in ethyl acetate-triethyl orthoformate. The new complexes invariably involve 2: 1 molar ratios of tbH to metal ion and are apparently monomeric with terminal tbH ligands binding riaa ring nitrogen (N9 or Nl). The Mn²⁺, Cu²⁺ and Zn^2- complexes are distorted tetrahedral, involving tuo tbH and two unidentate perchlorato ligands in the first coordination sphere of the metal ion. The remaining metal(II) complexes (Fe, Co, Ni) were obtained as monohydrates. These compounds are pentacoordinated of the [M(tbH)₂(OClO₃)₂(OH₂)] type, containing one aqua ligand in addition to the tbH and perchlorato ligands. The Cr³⁺ and Fe³⁺ complexes are low-symmetry hexacoordinated, with two tbH ligands. two unidentate and one bidentate chelating perchlorate Iigands.     

Thermal properties of zinc butyrate complex compounds

The new zinc(II) complexes of general formula Zn(CH₃CH₂CH₂COO)₂· nL (whereL = caffeine, nicotinamide, theobromine;n=1 or 2) were prepared and identified.Thermal properties of these compounds were investigated by thermal analysis (TG/DTG, DTA, DSC/DDSC).Gaseous products of thermal decomposition were detected by IR spectroscopy and Mass spectroscopy. Final products of thermal decomposition were determined by X-ray powder diffraction patterns.This work was supported by the Slovak Ministry of Education Grant No. 1/3230/96. This financial support is gratefully acknowledged.     

How Climatic Seasons of the Amazon Biome Affect the Aromatic and Bioactive Profiles of Fermented and Dried Cocoa Beans?

In addition to the vast diversity of fauna and flora, the Brazilian Amazon has different climatic periods characterized by periods with greater and lesser rainfall. The main objective of this research was to verify the influence of climatic seasons in the Brazilian Amazon (northeast of Pará state) concerning the aromatic and bioactive profiles of fermented and dried cocoa seeds. About 200 kg of seeds was fermented using specific protocols of local producers. Physicochemical analyzes (total titratable acidity, pH, total phenolic compounds, quantification of monomeric phenolics and methylxanthines) and volatile compounds by GC-MS were carried out. We observed that: in the summer, the highest levels of aldehydes were identified, such as benzaldehyde (6.34%) and phenylacetaldehyde (36.73%), related to the fermented cocoa and honey aromas, respectively; and a total of 27.89% of this same class was identified during winter. There were significant differences (p ≤ 0.05, Tukey test) in the profile of bioactive compounds (catechin, epicatechin, caffeine, and theobromine), being higher in fermented almonds in winter. This study indicates that the climatic seasons in the Amazon affect the aromatic and bioactive profiles and could produce a new identity standard (summer and winter Amazon) for the cocoa almonds and their products.     

An Overview of Molecular Spectroscopic Studies on Theobromine and Related Alkaloids

Abstract: An overview of the recent molecular spectroscopic work on the methylxanthine alkaloid theobromine and its two closely related relatives, caffeine and theophylline, is presented. The role of molecular spectroscopy in studies of the coordination chemistry of these methylxanthine compounds is also briefly discussed.     

可可碱、咖啡因、茶碱的滤纸基质室温燐光测定

以快速定量滤纸为基质 ,用KI NaAc为重原子微扰剂 ,建立了测定痕量可可碱、咖啡因、茶碱的滤纸基质室温磷光 (PS RTP)分析法。该法取样量少 ,线性范围宽 ,可可碱、咖啡因、茶碱的线性范围分别为 14 4～5 76 ;5 .4 4～ 6 99;7.2 1～ 36 0ng/斑点 ;检出限分别为 1 14、0 78、1 80ng/斑点。该方法用于巧克力中可可碱、茶叶中咖啡因、氨茶碱药片中茶碱的测定 ,操作简便快速 ,选择性好。标准回收率在 92 8%～ 10 6 %之间 ;相对标准偏差RSD <5 %     

The study of new zinc(II) aliphatic carboxylate complex compounds by methods of thermal analysis

Four new complex compounds were prepared by the reaction of zinc bromobutyrate and organic ligands. The general formula of the synthetized complex compounds are (2-Brbut)₂ZnL and (4-Brbut)₂ZnL₂nH₂O (but=butyrate, L=theobromine (tbr), theophylline (tph), methyl-3-pyridyl carbamate (mpc), n=0-1). The compounds were characterized by chemical analysis and IR spectroscopy. The thermal behaviour of the zinc(II) complexes was studied by thermal analysis. Thermal decomposition in the case of hydrated compounds starts with the release of water molecules. Then molecules of organic ligands and the bromobutyrate anion are released and decomposed. CH₃CH₂CH=O, CO, CH₂=CHCH=O, CH₂O and ZnBr₂ were found as gaseous products of thermal decomposition during heating up to 700°C. IR, mass spectroscopy, X-ray powder diffraction and chemical analysis were used for the determination of solid and gaseous intermediates and products of the thermal decomposition.This revised version was published online in November 2005 with corrections to the Cover Date.     

高效液相色谱法同时测定多种食品添加剂

 采用反相高效液相色谱法 ,一次进样、同时测定食品中的人工合成甜味剂 (糖精钠、安赛蜜、甜味素 )、防腐剂(苯甲酸、山梨酸 )、咖啡因、可可碱和茶碱。以AlltechEconosphereC18柱 (15 0mm× 4 6mmi.d .,3μm)为分离柱 ,10mmol/LNaH2 PO4 (pH 4 0 0 ) 乙腈 (体积比为 90∶10 )为流动相 ,采用二极管阵列检测器进行检测。整个分离过程在 2 3min内完成。样品平均加标回收率为 78 5 %～ 10 7 2 %。     

Thermal study of zinc(II) salicylate complex compounds with bioactive ligands

Five new complex compounds of general formula Zn(Hsal)_2·L₂·nH₂O (where Hsal=OHC₆H₄COO^-, L=thiourea (tu), nicotinamide (nam), caffeine (caf), theobromine (tbr), n=2-4), were prepared and characterized by chemical analysis, IR spectroscopy and studied by methods of thermal analysis (TG/DTG, DTA). It was found that the thermal decomposition of hydrated compounds starts with the release of water molecules. During the thermal decomposition of anhydrous compounds the release of organic ligands take place followed by the decomposition of salicylate anion. Zinc oxide was found as the final product of the thermal decomposition heated up to 800°C. RTG powder diffraction method, IR spectra and chemical analysis were used for the determination of products of the thermal decomposition. This revised version was published online in August 2006 with corrections to the Cover Date.