Oligomethylene-bridged dinuclear triorganotin triflates and diphenylphosphinates. Ion pairing in the solid state and electrolytic dissociation in solution of [Ph2Sn(CH2)nSnPh2X](O3SCF3) (X = OH, O2PPh2; n = 1-3)

The condensation of [Ph₂(OH)Sn(CH₂)_nSn(OH)Ph₂] (1-3; n = 1-3) with HO₃SCF₃ and HO₂PPh₂ provided [Ph₂Sn(CH₂)_nSnPh₂(OH)](O₃SCF₃) (4-6; n = 1-3) and [Ph₂(O₂PPh₂)Sn(CH₂)_nSn(O₂PPh₂)Ph₂] (10-12; n = 1-3), respectively. The reaction of [Ph₂Sn(CH₂)_nSnPh₂(OH)](O₃SCF₃) (4-6; n = 1-3) with HO₂PPh₂ and NaO₂PPh₂ gave rise to the formation of [Ph₂Sn(CH₂)_nSnPh₂(O₂PPh₂)](O₃SCF₃) (7-9; n = 1-3) and [Ph₂(OH)Sn(CH₂)_nSn(O₂PPh₂)Ph₂] (13-15; _n = 1-3), respectively. In the solid state, compounds 4-9 comprise ion pairs of cationic cyclo-[Ph₂SnCH₂SnPh₂(OH)]₂²⁺, cyclo-[Ph₂Sn(CH₂)_nSnPh₂(OH)]⁺ (n = 2, 3), and cyclo-[Ph₂Sn(CH₂)_nSnPh₂(O₂PPh₂)]⁺ (n = 1-3) and triflate anions. In MeCN, the eight-membered-ring system cyclo-[Ph₂SnCH₂SnPh₂(OH)]₂²⁺ appears to be in equilibrium with the four-membered-ring system cyclo-[Ph₂SnCH₂SnPh₂(OH)]⁺. In contrast, compounds 10-15 show no ionic character. Compounds 1-15 were characterized by multinuclear NMR spectroscopy in solution and in the solid state, IR spectroscopy, conductivity measurements, electrospray mass spectrometry, osmometric molecular weight determinations, and X-ray crystallography (4, 5, 7, and 12).

Identification and expression of natriuretic peptide receptor Type-A and-B mRNA in freshwater and seawater rainbow trout

Natriuretic peptide receptors mediate the physiological response of  natriuretic peptide hormones. One of the natriuretic peptide receptor types is the particulate guanylyl cyclase receptors, of which there are two identified: NPR-A and NPR-B. In fishes, these have been sequenced and characterized in eels, medaka, and dogfish shark (NPR-B only). The euryhaline rainbow trout provides an opportunity to further pursue examination of the system in teleosts. In this study, partial rainbow trout NPR-A-like and NPR-B-like mRNA sequences were identified via PCR and cloning. The sequence information was used in real-time PCR to examine mRNA expression in a variety of tissues of freshwater rainbow trout and rainbow trout acclimated to 35 parts per thousand seawater for a period of 10 days. In the excretory kidney and posterior intestine, real-time PCR analysis showed greater expression of NPR-B in freshwater fish than in those adapted to seawater; otherwise, there was no difference in the expression of the individual receptors in fresh water or seawater. In general, the expression of the NPR-A and NPR-B type receptors was quite low. These findings indicate that NPR-A and NPR-B mRNA expression is minimally altered under the experimental regime used in this study.

Expression of natriuretic peptide receptor mRNA and functional response to atrial natriuretic peptide and C-type natriuretic peptide in rainbow trout (Oncorhynchus mykiss) head kidney leucocytes

The stimulatory effect of vasomodulatory natriuretic peptide hormones on macrophages and peripheral blood leucocytes in mammals is well-established. However, the relationship in lower vertebrates has not been characterised. Expression of atrial natriuretic peptide, ventricular natriuretic peptide and C-type natriuretic peptide-1, and the guanylyl cyclase-linked (GC) natriuretic peptide receptor-A and -B-type receptors (NPR-A and NPR-B, respectively) was determined by PCR from the mRNA of rainbow trout head kidney leucocytes yielding gene fragments with 100% homology to the same respective natriuretic peptide and NPR-A and -B sequences obtained from other rainbow trout tissues. A mixed population of isolated rainbow trout head kidney leucocytes was stimulated in vitro with trout atrial natriuretic peptide (specific NPR-A agonist) and trout C-type natriuretic peptide (NPR-A and -B agonist) as well as the cGMP agonist 8-bromo-cGMP or the GC inhibitor 8-bromo-phenyl-eutheno-cGMP. Respiratory burst was stimulated by trout atrial natriuretic peptide, trout C-type natriuretic peptide-1 and 8-bromo-cGMP in a dose dependant manner with the highest activity as a result of stimulation with trout C-type natriuretic peptide-1 in excess of that achieved by phorbol myristate acetate (PMA). Equimolar concentrations of the inhibitor, inhibited the respiratory burst caused by the natriuretic peptides and 8-bromo-cGMP. The natriuretic peptide receptors on rainbow trout head kidney leucocytes appear to have a stimulatory function with regard to respiratory burst that is activated through a cGMP second messenger pathway and the natriuretic peptides expressed in the head kidney leucocytes may well act in a paracrine/autocrine manner.

Efficient formal synthesis of (±)-hyphodermin B

An efficient formal synthesis of hyphodermin B 1, a metabolite of Hyphoderma radula, has been completed in 15% overall yield. The tricyclic carbon skeleton 3 was rapidly assembled from a novel vinyl enone via a Diels−Alder reaction, followed by dehydrogenation and anhydride formation. Selective reduction of anhydride 3 with LiAlH(t-BuO)3 gave hyphodermin B 1 in 99% yield. The structure of hyphodermin B 1 was confirmed by X-ray crystallographic analysis. The anhydride 3, bearing a γ-carbonyl group, displayed unexpected reactivity with the anhydride carbonyl closest to the γ-ketone being the most electrophilic site. This was confirmed by HF/6-31G* calculations. In the presence of base, 3 underwent a rearrangement to the novel lactone 16.

Dual responsive chemosensors for anions : the combination of fluorescent PET (Photoinduced Electron Transfer) and colorimetric chemosensors in a single molecule

The design and synthesis of two novel fluorescent PET anion sensors is described, based on the principle of ‘fluorophore-spacer-(anion)receptor’. The sensors 1 and 2 employ simple diaromatic thioureas as anion receptors, and the fluorophore is a naphthalimide moiety that absorbs in the visible part of the spectrum and emits in the green. Upon recognition of anions such as F⁻ and AcO⁻ in DMSO, the fluorescence emission of 1 and 2 was ‘switched off’, with no significant changes in the UV–vis spectra. This recognition shows a 1:1 binding between the receptor and the anions. In the case of F⁻, further additions of the anion, gave rise to large changes in the UV–vis spectra, where the λ_max at 455 nm was shifted to 550 nm. These changes are thought to be due to the deprotonation of the 4-amino moiety of the naphthalimide fluorophore. This was in fact found to be the case, using simple naphthalimide derivatives such as 6. Sensors 1 and 2 can thus display dual sensing action; where at low concentrations, the fluorescence emission is quenched, and at higher concentrations the absorption spectra are modulated.

Establishment of HIV-1 latency in resting CD4+ T cells depends on chemokine-induced changes in the actin cytoskeleton

Eradication of HIV-1 with highly active antiretroviral therapy (HAART) is not possible due to the persistence of long-lived, latently infected resting memory CD4+ T cells. We now show that HIV-1 latency can be established in resting CD4+ T cells infected with HIV-1 after exposure to ligands for CCR7 (CCL19), CXCR3 (CXCL9 and CXCL10), and CCR6 (CCL20) but not in unactivated CD4+ T cells. The mechanism did not involve cell activation or significant changes in gene expression, but was associated with rapid dephosphorylation of cofilin and changes in filamentous actin. Incubation with chemokine before infection led to efficient HIV-1 nuclear localization and integration and this was inhibited by the actin stabilizer jasplakinolide. We propose a unique pathway for establishment of latency by direct HIV-1 infection of resting CD4+ T cells during normal chemokine-directed recirculation of CD4+ T cells between blood and tissue.

Ring strain in boroxine rings: computational and experimental considerations

B3LYP/6-311+G(d) calculations indicate that (HBO)₃ (4) and (HBO)₄ (5) possess (zero-point energy corrected) strain enthalpies of 11.4 and 31.6 kJ mol⁻¹, respectively. The absence of eight-membered (RBO)₄ rings is attributed to a combination of ring strain and the lability of the B---O bond. The synthesis, characterization and molecular structure of (PhBO)₃·pyridine (1) are described and chemical phenomena related to the addition of amines to triorganoboroxine rings are rationalized in terms of relief of ring strain in 4.

Hypercoordinated organotin compounds containing sulfur and chlorine. Molcular structures of [(Ph3P)2N]+[S(SnR2Cl)2Cl]- (R=Me, t-Bu)

The reaction of diorganotin sulfides, cyclo-(R₂SnS)_n (R=Me, n-Bu; n=3; R=t-Bu; n=2) with the corresponding diorganotin dichlorides, R₂SnCl₂, provided the tetraorganodistannathianes, (R₂ClSn)₂S (1, R=Me; 2, R=n-Bu; 3, R=t-Bu). ¹H-, ¹³C-, and ¹¹⁹Sn-NMR studies indicate that these compounds are kinetically labile and in equilibrium with the starting materials. Addition of equimolar amounts of [(Ph₃P)₂N]Cl to the reaction mixtures gave the chloride complexes [(Ph₃P)₂N]⁺[S(SnR₂Cl)₂Cl]⁻ (4, R=Me; 5, R=n-Bu; 6, R=t-Bu). Single-crystal X-ray diffraction studies revealed the tin atoms in both 4 and 6 to adopt distorted trigonal bipyramidal configurations with the chlorine atoms occupying the axial positions.

Chiral trialkoxysilanols derived from terpene alcohols. Molecular structures of tris([(1S)-endo]-(-)-bornoxy)silanol and tetrakis((-)-menthoxy)silane

Terpene alcohols (−)-menthol and [(1S)-endo]-(−)-borneol react with SiCl₄ in the presence of base to give (MenO)₃SiCl (1) and (BorO)₃SiCl (2) in high yields. Hydrolysis of 1 yields (MenO)₃SiOH (4) and (MenO)₄Si (3). Hydrolysis of 2 yields only (BorO)₃SiOH (5). The crystal structures of 3 and 5 are reported.

Synthesis and reactivity towards DIBAL-H of Cyclo-Siloxanes cyclo-[R2SiOSi(Ot-Bu)2O]2, cyclo-(t-BuO)2Si(OSiR2)2O, and cyclo-R2Si[Osi(Ot-Bu)2]2O (R=Me, Ph)

The six-, eight- and twelve-membered cyclo-siloxanes, cyclo-[R₂SiOSi(Ot-Bu)₂O]₂ (R = Me (1), Ph (2)), cyclo-(t-BuO)₂Si(OSiR₂)₂O (R = Me (3), Ph (4)), cyclo-R₂Si[OSi(Ot-Bu)₂]₂O (R = Me (5), Ph (6)) and cyclo-[(t-BuO)₂Si(OSiMe₂)₂O]₂ (3a) were synthesized in high yields by the reaction of (t-BuO)₂Si(OH)₂ and [(t-BuO)₂SiOH]₂O with R₂SiCl₂ and (R₂SiCl)₂O (R = Me, Ph). Compounds 1 - 6 were characterized by solution and solid-state ²⁹Si NMR spectroscopy, electrospray mass spectrometry and osmometric molecular weight determination. The molecular structure of 4 has been determined by single crystal X-ray diffraction and features a six-membered cyclo-siloxane ring that is essentially planar. The reduction of 1 - 6 with i-Bu₂AlH (DIBAL-H) led to the formation of the metastable aluminosiloxane (t-BuO)₂Si(OAli-Bu₂)₂ (7) along with Me₂SiH₂ and Ph₂SiH₂.

Secondary bonding in para-substituted diphenyltellurium dichlorides (p-XC6H4)2TeCl2 (X = H, Me, MeO) probed by 125Te MAS NMR spectroscopy. Crystal and molecular structure of (p-MeC6H4)2TeCl2

The solid-state structures of the previously known para-substituted diphenyltellurium dichlorides, (p-XC₆H₄)₂TeCl₂ (X=H (1), Me (2), MeO (3)) were investigated by ¹²⁵Te MAS NMR spectroscopy and in case of 2 by single crystal X-ray diffraction. The ¹²⁵Te-NMR shielding anisotropy (SA) was studied by tensor analyses based on relative intensities of the observed spinning sidebands. Solid-state NMR parameters, namely the isotropic chemical shift (δ_iso), anisotropy (ζ) and asymmetry (η), were discussed in relation to the molecular structures established by X-ray crystallography. The asymmetry (η) was found to be particularly sensitive to structural differences stemming mostly from the diverse secondary Te...Cl interactions, but no correlation with geometric parameters could be established.

A new class of eight-membered Sn2P2O4 heterocycles. Crystal structure and electrolytic dissociation in solution of cyclo-[R2Sn(OPPh2O)2SnR2](O3SCF3)2(R=Me, t-Bu)

The syntheses of cyclo-[R₂Sn(OPPh₂O)₂SnR₂](O₃SCF₃)₂ (R = Me (1), t-Bu (2)) by the consecutive reaction of R₂SnO (R = Me, t-Bu) with triflic acid and diphenylphosphinic acid are presented. In the solid state, 1 and 2 were investigated by ¹¹⁹Sn MAS and ³¹P MAS NMR spectroscopy as well as X-ray crystallography and appear to exist as ion pairs of cyclo-[R₂Sn(OPPh₂O)₂SnR₂]²⁺ dications and triflate anions. In solution, 1 and 2 are involved in extensive equilibria processes featuring cationic diorganotin(IV) species with Sn-O-P linkages, as evidenced by ¹¹⁹Sn and ³¹P NMR spectroscopy, electrospray mass spectrometry, and conductivity measurements.

New insights into the structures of diorganotellurium Oxides. The first polymeric diorganotelluroxane[(p-MeOC6H4)2TEO]n

The characterization of the previously reported diorganotellurium oxides R₂TeO (R = Ph (1) and p-MeOC₆H₄ (2)) was revisited by osmometric molecular weight determinations, ¹²⁵Te NMR spectroscopy, and electrospray spectrometry (ESMS) in solution and by 125Te MAS NMR spectroscopy in the solid state. The single-crystal X-ray structure of 2 revealed a polymeric arrangement that features a zigzag configured Te-O backbone without any secondary Te···O interactions. In solution 1 and 2 exist predominantly as monomers but appear to be in equilibrium with higher oligomers to a minor extent.

Synthesis and molecular structure of [n-Bu2(F)SnOSn(F)t-Bu2]2 - an unsymmetrically substituted tetraorganodistannoxane

The dimeric tetraorganodistannoxane [n-Bu₂(F)SnOSn(F)t-Bu₂]₂ (1) was prepared by the reaction of (t-Bu₂SnO)₃ with n-Bu₂SnF₂ and characterized in solution by multinuclear NMR spectroscopy and ESI MS spectrometry and in the solid state by ¹¹⁹Sn MAS NMR spectroscopy and single crystal X-ray diffraction.

Diorganotin dications stabilized by neutral ligands in the solid state: [R2Sn(H2O)2(OPPh3)2](O3SCF3)2 (R = Me, Bu)

The synthesis of [R₂Sn(H₂O)₂(OPPh₃)₂](O₃SCF₃)₂ (R = Me (1), Bu (2)) by the consecutive reaction of R₂SnO (R = Me, Bu) with triflic acid and Ph₃PO is described. Compounds 1 and 2 feature dialkyltin(IV) dications [R₂Sn(H₂O)₂(OPPh₃)₂]^₂+ apparently stabilized by the neutral ligands in the solid state. Compounds 1 and 2 readily dehydrate upon heating at 105 and 86 °C, respectively. The preparative dehydration of 1 afforded [Me₂Sn(OPPh₃)₂(O₃SCF₃)](O₃SCF₃) (1a), which features both bidentate and non-coordinating triflate anions. In compounds 1 and 2 the ligands Ph₃PO and H₂O are kinetically labile in solution and undergo reversible ligand exchange reactions. Compounds 1, 1a and 2 were characterized by multinuclear solution and solid-state NMR spectroscopy, IR spectroscopy, electrospray mass spectrometry, conductivity measurements, thermogravimetry and X-ray crystallography.