New isolable dialkylsilylene and its isolable dimer that equilibrate in solution.

The new isolable dialkylsilylene 3 bearing a bidentate alkyl substituent was synthesized. Recrystallization of silylene 3 gave yellow crystals of 3 and orange-red crystals of tetraalkyldisilene 4, a dimer of 3. In the solid state, 3 exists as a monomer with a closest distance of 6.745 Å between dicoordinate silicon atoms, while disilene 4 has a remarkably long Si═Si double bond distance of 2.252 Å. An equilibrium between 3 and 4 in solution was observed by NMR and UV-vis spectroscopies, and the thermodynamic parameters of the equilibrium were estimated to be ΔH = -36 ± 3 kJ mol(-1) and ΔS = -170 ± 15 J mol(-1) K(-1). Analysis of the percent buried volume, a measure of the steric demand around the divalent silicon, showed that the flexible steric bulkiness of the alkyl substituent of 3 and 4 allows the reversible dimerization of silylene 3 to disilene 4 and the isolation of both species.

Synthesis of kinetically stabilized 1,2-dihydrodisilenes.

Kinetically stabilized 1,2-dihydrodisilenes were successfully synthesized and isolated by the introduction of sterically protecting bulky aryl groups. These 1,2-dihydrodisilenes exhibit distinct Si═Si double-bond character in both solution and the solid state. The Si-H bonds in these 1,2-dihydrodisilenes exhibit higher s character than those of typical σ(4),λ(4)-hydrosilanes. Moderate heating of these 1,2-dihydrodisilenes in solution resulted in their isomerization to the corresponding trihydrodisilanes, with an intramolecular hydrogen migration as the rate-determining step.

Resolution of protected silaproline for a gram scale preparation.

Silaproline is an analogue of proline, which exhibits similar conformational properties. Moreover, the presence of dimethylsilyl group confers to silaproline a higher lipophilicity as well as an improved resistance to biodegradation. This report describes the comparison of two routes to obtain Fmoc-(L) Sip-OH on the gram scale using chiral HPLC resolution.

Oxalic acid supported Si-18F-radiofluorination: one-step radiosynthesis of N-succinimidyl 3-(di-tert-butyl[18F]fluorosilyl)benzoate ([18F]SiFB) for protein labeling.

N-Succinimidyl 3-(di-tert-butyl[(18)F]fluorosilyl)benzoate ([(18)F]SiFB), a novel synthon for one-step labeling of proteins, was synthesized via a simple (18)F-(19)F isotopic exchange. A new labeling technique that circumvents the cleavage of the highly reactive active ester moiety under regular basic (18)F-labeling conditions was established. In order to synthesize high radioactivity amounts of [(18)F]SiFB, it was crucial to partially neutralize the potassium oxalate/hydroxide that was used to elute (18)F(-) from the QMA cartridge with oxalic acid to prevent decomposition of the active ester moiety. Purification of [(18)F]SiFB was performed by simple solid-phase extraction, which avoided time-consuming HPLC and yielded high specific activities of at least 525 Ci/mmol and radiochemical yields of 40-56%. In addition to conventional azeotropic drying of (18)F(-) in the presence of [K(+)⊂2.2.2.]C(2)O(4), a strong anion-exchange (SAX) cartridge was used to prepare anhydrous (18)F(-) for nucleophilic radio-fluorination omitting the vacuum assisted drying of (18)F(-). Using a lyophilized mixture of [K(+)⊂2.2.2.]OH resolubilized in acetonitrile, the (18)F(-) was eluted from the SAX cartridge and used directly for the [(18)F]SiFB synthesis. [(18)F]SiFB was applied to the labeling of various proteins in likeness to the most commonly used labeling synthon in protein labeling, N-succinimidyl-4-[(18)F]fluorobenzoate ([(18)F]SFB). Rat serum albumin (RSA), apo-transferrin, a ß-cell-specific single chain antibody, and erythropoietin were successfully labeled with [(18)F]SiFB in good radiochemical yields between 19% and 36%. [(18)F]SiFB- and [(18)F]SFB-derivatized RSA were directly compared as blood pool imaging agents in healthy rats using small animal positron emission tomography. Both compounds demonstrated identical biodistributions in healthy rats, accurately visualizing the blood pool with PET.

H2SO4-silica-promoted 'on-column' removal of benzylidene, isopropylidene, trityl and tert-butyldimethylsilyl groups.

H(2)SO(4)-silica-promoted removal of benzylidene, isopropylidene, trityl and tert-butyldimethylsilyl groups from sugar derivatives was accomplished by following an 'on-column' protocol in a virtually waste-free condition.

Comparison of silanization/hydrosilation and organosilanization modification procedures on etched capillaries for electrokinetic chromatography.

Etched capillaries for use in open tubular electrochromatography are modified by silanization/hydrosilation and organosilanization. The migration behavior of both types of capillaries is evaluated with small basic molecules, peptides and proteins. Comparisons of peak symmetry and efficiency are used to measure the effectiveness of the two methods for modifying the etched surface. From this information, the suitability of each method for use with etched capillaries can be determined.

Postsynthesis vapor-phase functionalization of MCM-48 with hexamethyldisilazane and 3-aminopropyldimethylethoxylsilane for bioseparation applications.

MCM-48 was surface modified via vapor-phase reactions with hexamethyldisilazane (CH(3)-MCM-48) and 3-aminopropyldimethylethoxysilane (NH(2)-MCM-48). (29)Si NMR confirmed that the resulting materials contained covalently attached trimethylsilane and 3-aminopropyldimethylsilane moieties, both important functionalities for bioseparation applications. The surface coverage was approximately 1.8 and 0.9 groups per nm(2), respectively. The X-ray diffraction patterns and the narrow pore size distributions obtained from the gas sorption isotherms showed that the modified materials retained the characteristic pore structure of the underlying MCM-48 material. CH(3)-MCM-48 exhibited significantly improved hydrolytic stability over the unmodified MCM-48 under the aqueous conditions tested, whereas NH(2)-MCM-48 appeared to be less stable than the unmodified MCM-48. The decrease in stability is most likely due to the nature of the attachment of the 3-aminopropyldimethylsilane moiety, where the conversion of surface silanol groups is limited by H bonding with the amino end, leading to a 50% lower surface concentration and resulting in an increased likelihood of nucleophilic attack on the silica surface, enhancing the rate of hydrolysis. Hexamethyldisilazane thus appears to be a superior functional group for modifying the MCM-48 surface.

Effect of pedological characteristics on aqueous soil extraction recovery and tert-butyldimethylsilylation yield for gas chromatography-mass spectrometry of nerve gas hydrolysis products from soils.

Detection and identification of alkyl methylphosphonate (RMPA) and methylphosphonate (MPA) are performed to verify the existence of nerve gases by gas chromatography-mass spectrometry (GC-MS) after tert-butyldimethylsilylation (TBDMS). However, it is sometimes difficult to detect RMPA and MPA in soils. This study examines the relationship between the pedological characteristics and the aqueous extraction recoveries and TBDMS derivatization yields of ethyl-, isopropyl- and pinacolyl methylphosphonate and MPA for 21 soil samples. The aqueous extraction recoveries were measured directly by capillary electrophoresis. Andosols showed low extraction recoveries, while Regosols and Fluvisols showed high recoveries. RMPA were extracted with higher recoveries than MPA from all soils. MPA could not be extracted from Andosols. Within the pedological characteristics, phosphate absorption coefficients showed a strong negative correlation with the extraction recoveries of all phosphonates. The levels of RMPA and MPA in aqueous soil extracts were also determined for eight soils by GC-MS after TBDMS. Compared to the aqueous extraction recoveries, the yields of TBDMS derivatives were low. Strong anion exchange led to a significant improvement in derivatization yields. The efficiencies of TBDMS derivatization were inversely correlated with the levels of alkaline earth metals extractable from soils when the three soils that possessed high total carbon were excluded.