An improved synthesis of S-benzoyl mercaptoacetyltriglycine as BFCA and the labeling of IgG with carrier-free 188Re

S-benzoyl mercaptoacetyltriglycine (S-Bz-MAG₃) was synthesized and labeled with carrier-free ¹⁸⁸Re. The overall yield of S-Bz-MAG₃ is higher than those published in the literature. Dependence of the labeling yield of ¹⁸⁸Re-MAG₃ upon concentration of reducing agent, pH, reaction time, and other parameters was examined and optimum conditions were obtained. The labeling yield of ¹⁸⁸Re-MAG₃ was more than 98%. The concentration procedure was succeeded with Sep-Pak C18 column to obtain highly concentrated ¹⁸⁸Re-MAG₃. The experimental conditions of labeling of IgG with carrier free ¹⁸⁸Re via S-Bz-MAG₃ as a bifunctional chelating agent (BFCA) by pre-radiolabeling of the chelate was studied. The conjugation conditions were optimized. The stability of ¹⁸⁸Re-MAG₃-IgG in vitro was high. The results of this studiy may be useful for ¹⁸⁸Re labeling of MAbs for radioimmunotherapy.     

Studies on the preparation of186ReDTPA complexes using low specific activity186Re for antibody labeling

¹⁸⁶Re is considered as Therapy Isotope and can be used in radioimmunotherapy. The radiation characteristics of this isotope are ideal for therapy. Generally metallic radionuclides are labeled to antibodies through bifunctional chelating agents, such as DTPA (diethylenetetraaminepentaacetic acid). A study has been carried out on the complexation of DTPA with¹⁸⁶Re using low specific activity¹⁸⁶Re. This was carried out to evaluate various parameters which are involved in the complex formation including methods of processing of raw material¹⁸⁶Re. Stannous chloride was used as the reducing agent for the reduction of rhenium. Different labeling conditions such as pH, time, temperature and concentration of reducing agent were all studied for complex formation. The complex was characterized by paper electrophoresis, paper chromatography and gel column chromatography.     

An improved protocol for the preparation of 3-pyridyl- and some arylboronic acids

3-Pyridylboronic acid was prepared in high yield and bulk quantity from 3-bromopyridine via a protocol of lithium-halogen exchange and "in situ quench". This technique was further studied and evaluated on other aryl halides in the preparation of arylboronic acids.     

Electrophoretic separation of carrier-free radionuclides

The electrophoretic separation of radioactive rare earths on Cellogel in α-hydroxyisobutyric acid is described. Minute amounts of radioactive daughter nuclides are separated from the neutron-irradiated rare earth target materials, the ratio of the substances being 10⁵∶1 to 10⁷∶1. The suggested method is simple, rapid and suitable for analytical purposes.     

A generator for preparation of carrier-free224Ra

The construction of a dynamic generator for the separation of carrier-free²²⁴Ra is described. The mother²²⁸Th was extracted on the top of the column with di-(2-ethylhexyl)phosphoric acid on hydrophobized Chromosorb W DMCS. The function of the generator was checked during 6 months by measuring the decontamination of²²⁴Ra from²²⁸Th. Simultaneously the yield of²²⁴Ra was determined as a function of the HCl concentration and of the means of milking. The best results were obtained with 0.01–0.1M HCl; the yield was about 75% of the theoretical value, and the²²⁴Ra contained less than 0.01% of²²⁸Th.     

A rapid carrier-free separation method for divalent rare earths

A separation of carrier-free divalent rare earths by electrolytic reduction and amalgamation is described. The separation is carried out in a water-jacketed cell, 1 cm diameter by 10 cm long, fitted with a stopcock at the bottom. The cell utilizes a Pt anode and Hg cathode. The electrolyte used is potassium citrate-rare earth acetate at a concentration of 10 mg rare earth oxide per ml. The decontamination factor observed for Lu in a typical separation for Yb is ≥10⁴. Sm, Eu, and Yb are all amalgamated if present in the sample. For the present study, the parameters have been evaluated primarily for the case of Yb. A current of 100 mA is applied to 0.5 ml of electrolyte containing 1–1000 μg of Yb(III) for 5 min. The amalgam is decomposed and the Yb recovered by shaking for 1 min with 6M HCl. The overall time required is about 10 min and the yield is reproducible at 84–85%. Under these conditions, the electrolyte may contain up to 3.5 mg of Yb although at 2 mg the yield begins to decrease. The effects of current time, density and electrolyte concentration are discussed. This method has the advantage of being rapid and carrier-free, and the separated rare earth is in a form suitable for further chemical separation if required. Based on work performed under the auspices of the U.S. Atomic Energy Commission.     

Production method of no-carrier-added186Re

No-Carrier-Added¹⁸⁶Re was produced using the¹⁸⁶W(p,n)¹⁸⁶Re nuclear reaction with 13.6 MeV protons on thick targets of 99.79% isotopically enriched¹⁸⁶WO₃. The theoretical excitation functions for producing¹⁸⁶Re, and possible radionuclidic impurities of¹⁸²Re,¹⁸³Re, and¹⁸⁴Re were calculated using the ALICE code. Cross-sections of the¹⁸⁶W(p,n)¹⁸⁶Re reaction were measured up to 20 MeV using the stacked target method with thin foils of natural composition tungsten metal. The experimental and theoretical excitation functions were in good agreement. Targetry used at the TIARA cyclotron, and a radiochemical separation scheme for¹⁸⁶Re are described.     

An improved protocol for Petasis reaction of 2-pyridinecarbaldehydes

A highly efficient and improved method has been developed for Petasis reactions of various 2-pyridinecarbaldehydes with secondary amines and boronic acids under catalyst-free conditions. The desired products are obtained in up to 96% yield in refluxed acetonitrile.     

An improved protocol for the selective hydroaminomethylation of arylethylenes

The hydroaminomethylation of arylethylenes with anilines proceeds under mild conditions in the presence of [Rh(cod)₂BF₄] and dppf as catalyst system to give the corresponding branched amphetamine derivatives in good selectivity and yield.     

186Re/188Re labeled polypeptide microspheres as a potential radiation synovectomy agent

Polypeptide microspheres containing polycysteine crosslinked with polylysine were prepared and radiolabeled with¹⁸⁶Re and¹⁸⁸Re. High labeling yields with the microspheres with both¹⁸⁶Re and¹⁸⁸Re (97%) were obtained, and above 99% retention of radiolabels in water in 24 hours was obtained. Rhenum-186 labeled polycysteine and polylysine microspheres (11 ratio, 20 m as mean diameter) were injected intra-articularly into the rear stifes (knee joints) of normal New Zealand white rabbits. About 87% of injected dose was retained in rabbit stifles and adjacent tissues in 96 hours after injection, while most of the activity lost from the joints was excreted in the urine. Due to its simplicity of preparation and radiolabeling, versatility, and biodegradability, this type of conjugate system may become the therapeutics of choice for radiation synovectomy.     

An improved actinide separation method for environmental samples

This paper presents a rapid method of separation of five actinide elements (Th, U, Np, Pu, and Am) for aqueous media samples. This separation method utilizes the unique chemistries of the actinides at low concentrations^1,2 and the properties of the EIChroM TRU-Resin^TM extraction resin. In order to cleanly recover the five actinides from aqueous samples or solubilized soil samples, the sample is passed through the column twice. The sample is first loaded in an HCl solution with hydrogen peroxide. This allows the Am and most matrix ions to pass through the column. Then the Th is eluted using dilute HCl followed by the Np and Pu which are eluted together with oxalic acid in dilute HCl solution. Finally, the U is eluted with ammonium oxalate solution. A calcium-oxalate coprecipitation is performed on the original load solution containing the Am ions and the dissolved precipitate is then reloaded onto the TRU-Resin^TM column in HNO₃ with ascorbic acid. The procedure requires approximately 1.5 working days for experienced technicians, greatly reduces waste, and generally results in actinide recoveries of 80–100%.     

An improved method to estimate the specific activity of carrier-free radioactive NaI solutions

A modified procedure using thin layer chromatography is described to determine the specific activity of carrier-free radioactive NaI solutions. It gives more accurate results and can be performed within a short time.     

An improved microwave assisted protocol for Yonemitsu-type trimolecular condensation

Due to the presence of the indole ring in a number of bioactive compounds, novel methods for the preparation of polyfunctionalized indole derivatives are of great interest. The combined use of Lewis acid catalysis and microwave irradiation furnished satisfactory results in the Yonemitsu-type trimolecular condensation of indoles with aldehydes and 1,3-dicarbonyl compounds, such as malonates and acetoacetates.     

An improved protocol for ligandless Suzuki-Miyaura coupling in water

Using a reverse order of addition of reagents, PdCl₂ and Pd(OAc)₂ are efficient catalysts for the Suzuki-Miyaura reactions in water. The ligandless and mild conditions, the high stability of the catalytic system, short reaction time and good to excellent yields are important features of this protocol.     

Quantitative separation of carrier-free cerium from fission products

The extraction of Ce (IV) by di-(2-ethylhexyl)-phosphoric acid (HDEHP) has been studied as a function of nitric acid concentration. Using the distribution coefficient data, the optimum conditions for recovery of Ce (IV) from nitric acid medium were arrived at. Under the conditions employed for Ce(IV), a small percentage of Ru was also found to be extracted. Cerium could be selectively stripped from the organic phase with 8M HNO₃/30% H₂O₂ solution. This procedure led to the recovery of¹⁴⁴Ce free of¹⁰⁶Ru. Based on the solvent extraction data, an extraction-chromatographic procedure employing HDEHP (40% w/w) loaded on Amberlite XAD-7 as the stationary phase was developed for the isolation of pure, carrier-free¹⁴⁴Ce from the spent fuel solution.     

An improved procedure for the preparation of 2-isoxazolines

Aldoximes were converted in high yields by N-Chlorosuccinimide into hydroxamic acid chlorides, and corresponding nitrile oxides generated by addition of triethylamine at 40°–50° underwent 1,3-dipolar polar addition to alkenes, giving 2-isoxazolines. The whole procedure could be performed as a one-pot reaction. Oximes with other functions, sensitive to free chlorine could be converted selectively into hydroxamic acid chlorides by this procedure. Isopropylidene glyceraldoxime was added to acrolein diethylacetal thus affording an entrance to carbohydrate synthesis but the stereospecificity of the reaction is low. 2:3, 5:6-Di-O-isopropylidene-D-mannose oxime was converted to the N-hydroximinolactone by treatment with NCS and base.     

An improved large scale procedure for the preparation of N-Cbz amino acids

A simple and scalable method for the preparation of N-Cbz protected amino acids is presented which uses a mixture of aqueous sodium carbonate and sodium bicarbonate to maintain the appropriate pH during the addition of benzyl chloroformate. The method has been extended to other N-protections and is amenable to large scale preparation of an intermediate toward Zofenopril, an ACE inhibitor.     

A simple method for carrier-free separation of77Br from metallic selenium

A simple method was developed for separation of bromine from metallic selenium. This method enables easy preparation of⁷⁷Br by proton bombardment of metallic selenium (enriched⁷⁷Se or⁷⁸Se). The method consists of heating the metallic selenium with H₂O to 300°C in a small autoclave for about three hours. The⁷⁷Br is distilled from the obtained solution after the addition of H₂SO₄+K₂Cr₂O₇. The step also removes the arsenic produced together with the selenium.     

An improved protocol for the RuO4-catalyzed dihydroxylation of olefins

[reaction: see text] Dihydroxylation under ruthenium catalysis provides an easy access to syn-diols, although overoxidation is a common side reaction. Furthermore, the high catalyst loadings offset the lower price of ruthenium compared to osmium. In this paper, we present an improved protocol for the RuO(4)-catalyzed syn-dihydroxylation using only 0.5 mol % catalyst under acidic conditions. A variety of olefins can be hydroxylated in good to excellent yields with only minor formation of side products.