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Reactions of 1-naphthols with pi-acceptor p-benzoquinones: oxidative aryl coupling vs. non-oxidative electrophilic arylation.

We investigated the reactions of various 1-naphthols (NPOHs; 1) with p-benzoquinones (Qs), such as 1,4-benzoquinone (BQ) and p-chloranil (CA), as pi-electron acceptors. With electron-rich NPOHs 1a-c, oxidative biaryl coupling and subsequent dehydrogenation reaction took place selectively to give the corresponding 2,2'-binapthyl-1,1'-quinones 3a-c in excellent yield. In the case of electron-deficient NPOHs 1e, f, two different types of reactions occurred in the presence of SnCl4 and ZrO2 under similar conditions: SnCl4 mediated oxidative dimerization and trimerization of NPOH, while ZrO2 promoted electrophilic arylation of Qs with NPOH. The resulting products 3 would be useful synthetic intermediates for naturally occurring diosindigo B, biramentaceone and violet-quinone.

Benzoquinones↗

99Tcm-citrate: a new bone imaging radiopharmaceutical.

99Tcm-citrate has been shown to incorporate irreversibly in the skeleton with a biodistribution different to that on a conventional bone scan. The aims of this study were to confirm the bone-imaging properties of 99Tcm-citrate, to identify the variabilities influencing its skeletal uptake, to compare its uptake in bone with that of 99Tcm-MDP and to assess its possible role in bone scintigraphy. Appropriate animal and human studies (n = 45) were conducted. The 3 h lesion-to-bone ratio of 99Tcm-citrate was compared with that of 99Tcm-MDP in more than 150 lesions, including osteoblastic sites (Group A), lesions undergoing treatment or healing (Group B), and degenerative or old healed lesions (Group C). The uptake ratio was classified as concordant (< 20% variation), mildly discordant (20-50% variation) or significantly discordant (> 50% variation). Animal experiments showed most bone uptake of 99Tcm-citrate when prepared at a pH of 6.0-6.5. The two radiopharmaceuticals appeared to compete for bone uptake, suggesting related but different sites of bone accumulation. The 99Tcm-citrate/99Tcm-MDP uptake ratio in Group A was concordant (mean +/- S.D. = 0.92 +/- 0.15), while Group C lesions had a significantly lower 99Tcm-citrate/99Tcm-MDP uptake ratio (0.34 +/- 0.24, P < 0.01). A comparison of Group B lesions showed wide variation in intensity and area of involvement in many lesions (uptake ratio < 0.5 or > 1.5 in 13 of 30 sites). We conclude that 99Tcm-citrate has a different site of bone localization than phosphonates, possibly in the organic matrix. Although its skeletal uptake is lower than that of 99Tcm-MDP, it may have better specificity in differentiating osteoblastic from degenerated or healed bony lesions, and therefore be useful in predicting healing of bone secondaries, fractures or osteomyelitic lesions.

Adult↗

Surface geometry of three packable and one hybrid composite after polishing.

This study evaluated the surface quality of four composite materials after polishing with six different polishing techniques. Eighty specimens were made using three packable composites (Definite/Degussa, SureFil/ Dentsply and Solitaire/Heraeus-Kulzer) and one hybrid composite (Herculite XRV/Kerr). Five specimens of each material were polished using flexible Sof-Lex discs. The remaining 75 specimens of each composite were prepared using three finishing protocols: a single 30 microm diamond (n = 25), two finishing diamonds (30/20 microm; n = 25) and a 30 microm diamond followed by a tungsten carbide finishing bur (n = 25). Final polishing of each of the three finishing groups was accomplished with SuperBuff, Diafix-oral, OneGloss, Astropol and HaWe Composite Polishers (n = 5, each). Surface roughness was evaluated quantitatively by laser-stylus profilometry. Average roughness (R(a)) was calculated; statistical analysis of the data was performed with two-way ANOVA and Scheffé post-hoc tests. The polished surfaces were examined qualitatively by SEM. The results showed significant effects on surface roughness from the different composites (p = 0.011) and polishing systems (p < 0.001). After polishing, the Solitaire surfaces (R(a) = 0.72 microm) were smoother than Definite (R(a) = 0.87 microm) and SureFil (R(a) = 0.89 microm) and significantly smoother than Herculite (R(a) = 0.92 microm; p = 0.011). Three of the polishing methods (SuperBuff, Diafix-oral and Astropol) achieved lower R(a)-values than Sof-Lex discs. The polishing quality of the one-step systems SuperBuff and Diafix-oral was strongly affected by the initial finishing protocol.

Aluminum Oxide↗

An in vitro study to compare 99mTc-stannous colloids and 99mTc-HMPAO for labelling human leukocytes.

AIM: Aim of the present study was to compare in vitro the labelling efficiency (LE) and cell viability (TBE) of autologous leukocytes labelled with (99m)Tc-SnF(2) and (99m)Tc-HMPAO, and to evaluate the quantity and quality of spontaneously released (99m)Tc (SR) from labelled cells at several time points after labelling. METHODS: A total of 14 patients with different diseases and 18 normal subjects were included in this study. A blood sample was collected from each patient; purified autologous leukocytes were divided into 2 samples and labelled with (99m)Tc-SnF(2) and (99m)Tc-HMPAO. LE was evaluated at the end of labelling and TBE and SR were evaluated at 10 min and 1 h, 2 h and 4 h after labelling. RESULTS: LE of (99m)Tc-SnF(2)-WBC was higher than (99m)Tc-HMPAO-WBC (61.2+/-18.7% and 43.3+/-11.3; p<0.0001) and we found an inverse correlation between blood glucose and labelling efficiency for both methods (p=0.02). Minimal differences were also observed between 2 methods after 10 min and 1 h, as far as the cell viability is concerned. The percentage of radioactivity spontaneously released from (99m)Tc-SnF(2)-WBC was significantly higher compared to (99m)Tc-HMPAO-WBC at each time point. Radioactivity released from labelled cells was predominantly (99m)Tc-SnF(2) and (99m)Tc-HMPAO with few free (99m)Tc (<20%). CONCLUSION: Both radiopharmaceuticals are not toxic for WBC. Labelling with (99m)Tc-SnF(2) give a higher LE than with (99m)Tc-HMPAO; however, radiolabelled colloids are more released from labelled cells over a period of 4 h. While (99m)Tc-HMPAO is physiological excreted into gastrointestinal tract, (99m)Tc-SnF(2) can be re-uptaken in vivo by reticulo-endothelial cells of liver and spleen. These findings suggest that (99m)Tc-SnF(2)-WBC might be better than (99m)Tc-HMPAO-WBC for studying inflammatory bowel diseases.

Cells, Cultured↗

Importance of cholescintigraphy and inferior vena cava flow studies in the differential diagnosis of hepatocellular carcinoma.

In order to assess the usefulness of inferior vena cava flow studies and cholescintigraphy complementary to the routine static liver scintigraphy in the differential diagnosis of hepatocellular carcinoma (HCC), we studied 37 patients with a proven diagnosis of HCC and 11 patients with a liver abcess or cyst. The procedure followed was 1) a 99mTc-colloid flow study of the inferior vena cava (IVC) and iliac veins followed by static liver imaging and 2) cholescintigraphy using a dynamic acquisition mode to determine the perfusion as well as the concentration/excretion of the liver and pathological area. The hepatic perfusion index (HPI) was calculated by the "slope" method of Sarper et al.: Radiology 141:179-184 (1981) and the "area" method of Biersack et al.: Fortschritte auf dem Gebiete der Rontgenstrahlen und der Nuklear medizin. Erganzungsband 126:47-52 (1977). The results were compared with data previously collected in patients without liver disease (control) and other liver pathologies.

Carcinoma, Hepatocellular↗

Radionuclide measurement of liquid and solid gastric emptying in normal subjects in Singapore.

Scintigraphic methods for liquid and solid gastric emptying were utilised to study normal patterns in 21 volunteers. Of these, 19 had solid emptying studies and 14 had liquid emptying studies. The liquid study lasted 1/2 hour, while the solid study was for 1 hour. The gastric emptying half-time (T 1/2), as well as percentage retention at 15 minutes (liquids), and at 60 minutes (for solids) were noted. The time-activity curves were also corrected for tissue attenuation. Results indicated normal average liquid emptying T 1/2 to be 14.2 minutes, while that for solids was 116 minutes.

Adult↗

New Fluorinated Stannic Compounds as Precursors of F-Doped SnO(2) Materials Prepared by the Sol-Gel Route.

Dialkoxydi(beta-diketonate)tin(IV) compounds react either with difluorodi(beta-diketonate)tin(IV) or with butanoyl fluoride to yield novel tin complexes Sn(OR(1))F(R(2)COCHCOR(2))(2) 1 (R(1) = tert-amyl, isopropyl, ethyl; R(2) = methyl, tert-butyl). Multinuclear (1)H, (13)C, (19)F, and (119)Sn NMR spectroscopic characterization showed that complexes 1 are octahedral in solution with a cis configuration for the fluorine and the alkoxide group. Kinetics of configurational rearrangements were studied by variable-temperature (13)C NMR spectroscopy. The hydrolytic behavior of 1 was determined for different hydrolysis ratios h = [H(2)O]/[1]. For R(1) = tert-amyl, a dimeric fluorinated species was mainly obtained for h = 0.5, and addition of 2 mol equiv of water led to a fluorinated stannic oxopolymer soluble in CH(3)CN. In the latter case, the powder obtained after solvent elimination and treatment in air at 550 degrees C consisted of crystalline SnO(2) cassiterite particles containing the required amount (3 mol %) of doping fluorine and exhibiting electronic conductivity comparable to that of Sn-doped In(2)O(3). Complexes 1 are the first precursors of F-doped SnO(2) materials prepared by the sol-gel route.

Journal Article↗

Self-assembly of diorganotin(IV) moieties and 2-pyrazinecarboxylic acid: syntheses, characterizations and crystal structures of monomeric, polymeric or trinuclear macrocyclic compounds.

A series of diorganotin(IV) compounds of the type [R(2)Sn(pca)Cl](3)(R = CH(3); (n)Bu; C(6)H(5); C(6)H(5)CH(2); Hpca = 2-pyrazinecarboxylic acid), R(2)Sn(pca)(2)(mH(2)O)xnH(2)O (m= 1: R = CH(3), n= 2, R =(n)Bu, n= 0; m= 0, n= 0: R =(n)Bu, C(6)H(5), C(6)H(5)CH(2)) and (Et(3)NH)(+)[R(2)Sn(pca)(2)Cl](-)xmH(2)O (m= 0: R = CH(3), (n)Bu, C(6)H(5)CH(2); m= 1: R = C(6)H(5)) have been obtained by reactions of 2-pyrazinecarboxylic acid with diorganotin(iv) dichloride in the presence of sodium ethoxide or triethylamine. All compounds were characterized by elemental, IR and NMR spectra analyses. Except for compounds, and, the others were also characterized by X-ray crystallography diffraction analyses, which revealed that compounds and were trinuclear macrocyclic structures with six-coordinate tin(IV) atoms, compounds and were monomeric structures with seven-coordinate tin(IV) atoms, compounds and were polymeric chain structures with seven-coordinate tin(IV) atoms and compounds and were stannate with seven-coordinate tin(IV) atoms.

Journal Article↗

Scintigraphic quantitation of gastrointestinal motor activity and transport: oesophagus and stomach.

For the recognition and characterisation of oesophageal motor disorders, manometry represents the most reliable tool but yields no information on bolus transport. The transport can be quantitated by radionuclide techniques. The patient is positioned supine beneath a gamma-camera and instructed to swallow a radiolabelled bolus in a single gulp. Using a marker over the cricoid and the activity in the stomach as landmarks, regions of interest are drawn representing the upper, middle and lower third of the oesophagus and the gastric fundus. Activity-time curves enable one to recognise the clearance patterns in these regions. In combination, manometric and radionuclide transit studies recognise a higher number of motor disorders than either procedure alone. Radionuclide methods also are the most reliable and sensitive to quantitate gastric emptying. Procedure, meal size and composition as well as patient position must be standardised and correction techniques applied. The emptying of solid and liquid meal constituents can be evaluated concomitantly. Solids start to empty only after a lag phase of varying extent. With semi-solid meals, which are emptied at the same rate as solid meals of identical composition in the postlag phase, the recording time can be considerably shorter. Besides gastric emptying, the amplitude, frequency and propagation velocity of antral contractions can be recorded using serial images of short frame time and specially devised analytic techniques.

Colloids↗

Gel-chromatographic analysis of 99mTc-labeled human serum albumin prepared with Sn(II) as the reductant.

The labeling of human serum albumin (HSA) with 99mTc using Sn(II) as the reductant has been reinvestigated in view of the possibility of formation of Sn-Tc colloids. Preparations of 99mTc-HSA and mixtures of 99mTc-TcO-4 with Sn(II)Cl2 have been analyzed by means of gel chromatography using various gel matrices and eluents. No Sn-Tc colloids could be eluded from samples of 99mTc-HSA preparations. The percentage of labeling was about 90%. A comparative investigation of a number of gel-chromatographic systems for the detailed analysis of 99mTc-HSA has been made. It is found that a long column with Sephadex G-200 gives the best results.

Chromatography, Gel↗

Effect of an extract of cauliflower (leaf) on the labeling of blood elements with technetium-99m and on the survival of Escherichia coli AB1157 submitted to the treatment with stannous chloride.

The labeling of red blood cells (RBC) with technetium-99m (99mTc) depends on a reducing agent and stannous chloride (SnCl(2)) and is widely utilized. This labeling may also be altered by drugs, and SnCl(2) reduces the survival of Escherichia coli cultures. Cauliflower (Brassica oleracea L. var. botrytis) is used in folk medicine and we evaluated its influence on (i) the labeling of blood elements with 99mTc, and (ii) on the survival of an E. coli strain. Blood was withdrawn from rats that drank the extract of cauliflower (15 days). Blood was incubated with SnCl(2) and with 99mTc, as sodium pertechnetate, centrifuged and plasma (P) and RBC were isolated. Samples of P and RBC were also precipitated, centrifuged and soluble and insoluble fractions isolated. E. coli culture was treated with SnCl(2) in the presence of cauliflower. The extract of cauliflower did not alter the fixation of 99mTc on blood fractions; however, it abolished the lethal effect of SnCl(2) on the E. coli culture. We suggest that the substances present in the extract of cauliflower probably, would have redox property with different mechanisms of action. The oxidant action of the substances of the extract would not be strong enough to oxidise the stannous ions altering the 99mTc-labeling. However, the referred substances could oxidise these ions sufficiently to protect the E. coli culture against the lethal effect of the stannous ion.

Animals↗

Phosphine-containing HYNIC derivatives as potential bifunctional chelators for (99m)Tc-labeling of small biomolecules.

Two prototype phosphine-containing HYNIC chelators, HYNIC-Kp-DPPB and HYNIC-Ko-DPPB (HYNIC = 6-hydrazinonicotinamide; K = lysine; and DPPB = diphenylphosphine-benzoic acid), have been synthesized and characterized by NMR ((1)H, (13)C, and (31)P) and LC-MS. Macrocyclic (99m)Tc complexes, [(99m)Tc(HYNIC-Ko-TPPB)(tricine)] and [(99m)Tc(HYNIC-Kp-DPPB)(tricine)], were prepared by reacting the phosphine-containing HYNIC chelator with (99m)TcO(4)(-) in the presence of excess tricine and stannous chloride. Results from this study clearly demonstrated that both HYNIC-Kp-DPPB and HYNIC-Ko-DPPB are able to form highly stable macrocyclic (99m)Tc complexes, [(99m)Tc(HYNIC-Ko-TPPB)(tricine)] and [(99m)Tc(HYNIC-Kp-DPPB)(tricine)], when tricine is used as the coligand. Radio-HPLC data suggest that the complex [(99m)Tc(HYNIC-Kp-DPPB)(tricine)] exists as only one detectable isomer in solution while the complex [(99m)Tc(HYNIC-Ko-DPPB)(tricine)] has three isomers. It was also found that three isomers of [(99m)Tc(HYNIC-Ko-DPPB)(tricine)] interconvert at elevated temperatures, suggesting that the presence of these isomers might be due conformational changes in the macrocyclic Tc chelate. The LC-MS data for both macrocyclic (99m)Tc complexes are completely consistent with the proposed composition. The phosphine-containing HYNIC chelators described in this study may have the potential as bifunctional chelators for (99m)Tc labeling of small biomolecules.

Chromatography, High Pressure Liquid↗

Arteriovenous shunting of microspheres in patients with colorectal liver metastases: errors in assessment due to free pertechnetate, and the effect of angiotensin II.

In patients receiving locoregional therapy for liver metastases degradable microspheres are being increasingly used in an attempt to improve cytotoxic delivery to the tumour. However, counterproductive arteriovenous shunting through the liver following intrahepatic arterial injection can occur, leading to deposition in the lung. Measurement of the degree of shunting is important in the monitoring of this kind of therapy. In this study we describe the use of technetium-labelled microspheres of serum albumin (99Tcm MSA) to measure baseline shunting during hepatic arterial perfusion scintigraphy in five patients with liver metastases of colorectal origin, and assess the significance of the values obtained for relative lung uptake (RLU) which we define as: RLU = Activity in lung field/Activity in liver + lung fields X 100%. We found that shunting was less than 5% in all cases, zero shunting occurring in 14 of the 16 patients studied. The sources of error in this technique have been assessed, the most important being the presence of free pertechnetate in the injectate. The use of Boots 10 ml vials and glass syringes respectively to dispense and administer this radiopharmaceutical reduces this error to a small predictable level. In our small group of patients, we found no evidence to suggest that use of the vasoactive agent angiotensin II significantly increases baseline shunting in patients with colorectal liver tumour.

Angiotensin II↗

Radiolabelling of egg meals for gastric emptying studies: a comparison of 99mTc sulfur and 99mTc stannous colloids.

OBJECTIVES: To establish whether 99mTc stannous (Tc-Sn) colloid is a suitable alternative to 99mTc sulfur (Tc-S) colloid for gastrointestinal studies, we compared the per cent binding to egg solids (%BS) and radiochemical purity (RCP) of both colloids in digesting media. METHODS: Egg white and yolk containing colloids were cooked separately and mashed. Samples of 4-5 g were digested over 2-3 h (37 degrees C) in excess simulated gastric juice (SGJ: 15 ml of 0.1 M HCl and 0.5 g.l-1 pepsin) or water, centrifuged, imaged with a gamma camera and the %BS computed. RCP was determined in aspirates taken from these preparations and from solutions of colloid added directly to SGJ. RESULTS: The %BS in egg white after 3 h in SGJ for both colloids were similar: Tc-Sn, 62+/-8 (n=12); Tc-S, 61+/-6 (n=8), but markedly lower than 95% (the often quoted literature value). Egg yolk was digested more rapidly than egg white: %BS after 2 h in SGJ for Tc-Sn colloid was 55+/-10 (n=5) in the yolk, compared to 77+/-4 (n=5) in the white (P<0.01). The RCP for Tc-S colloid alone in SGJ was >94% over 3 h but for Tc-Sn colloid was as low as 14%. For egg white, the RCP in SGJ was 91-96% for Tc-S and 80-91% for Tc-Sn. For egg yolk the RCPs in SGJ were similar for both colloids (>90%). The RCP in water digesting egg white or yolk containing either colloid was always lower than in the corresponding SGJ aspirates, indicating a leakage of small amounts of non-colloidal 99mTc. CONCLUSIONS: Although 99mTc-Sn almost completely dissociates in SGJ, once cooked in egg it is digested similarly to 99mTc-S. Variations in the size of digesting egg fragments and in SGJ composition can reconcile the lower %BS values obtained with previously reported higher results. 99mTc-Sn colloid cooked in egg appears suitable for gastrointestinal studies.

Eggs↗