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D Lentz

Publications and source records attributed to D Lentz.

At least 19 recordsLinked to original sources

8,9-Didehydrofluoranthenes as building blocks for the synthesis of extended polycyclic aromatic hydrocarbons (PAHs).

[reaction: see text] The synthesis of phenyl-substituted 8,9-dibromofluoranthene and p-dodecylphenyl-substituted 8,9-fluoranthene anthranilic acid is presented. Their synthetic potential as 8,9-didehydrofluoranthene precursors is demonstrated in combination with a new biscyclopentadienone by the synthesis of novel phenyl-substituted PAHs with up to 14 annulated rings. The crystal structure of 7,16-diphenylfluorantheno[8,9-k]fluoranthene is given.

Journal Article↗

Syntheses of halogenated ethenyl isocyanide chromium complexes as organometallic precursor molecules for ethenyl and ethynyl isocyanides.

The radical alkylation of tetraethylammonium pentacarbonyl(cyano)chromate 1 yielded the halogenated ethyl isocyanide complexes [(CO)5Cr(CN-CClX-CClYF)] 3 (a, X= Cl, Y= F; b, X = F, Y= F and c, X=Y= Cl). Dehalogenation of 3 using zinc in diethyl ether gave [(CO)5Cr(CN-CX=CFY)] 4. The compounds 4a, b reacted with various nucleophiles exclusively at the difluoromethylene group. The unstable phosphorane 5, which is formed on reaction of 4b with trimethylphosphane, decomposed thermally and on hydrolysis yielding pentacarbonyl(1,2-difluoroethenyl isocyanide)chromium (6). The cyano substituent can be introduced in the beta position of the isocyanide function by reaction of 4a, b with potassium cyanide, leading to the formation of [(CO)5Cr(CN-CX=CF-CN)] (7). Reactions of 4a, b with organolithium or organomagnesium compounds yielded [(CO)5Cr(CN-CX=CF-R)] (8) and [(CO)5Cr(CN-CF=CF-C...C-CF=CF-NC)Cr(CO)5] (10). The trimethylsilyl group in 8a, b, d could be removed by a solution of potassium carbonate in methanol leading to [(CO)5Cr(CN-CX=CF-Cn-H)] (11) (n=2,4). Octacarbonyldicobalt reacted with 8e under coordination of the C-C triple bond to the hexacarbonyldicobalt fragment, resulting in the cluster compound 12. The crystal and molecular structure of 8i, 11 a, b, and 12 were elucidated by X-ray crystallography. The alkenyl and alkynyl isocyanides CN-CCl=CF2 (13a), CN-CF=CF2 (13b), CN-CCl=CClF (13c), CN-CF=CFH (14), CN-CC-H (15), CN-CC-CN (16), and CN-CCl=CF-CN (17) were obtained by flash vacuum pyrolysis of 4a, 4b, 4c, 6, and 7a, respectively.

Journal Article↗

Mesoderm-independent regulation of gastrulation movements by the src tyrosine kinase in Xenopus embryo.

In vitro studies have demonstrated the involvement of Src kinases in several aspects of cell scattering, including cell dissociation and motility. We have therefore sought to explore their functions in the context of the whole organism. Loss-of-function microinjection studies indicate that the ubiquitous Src, Fyn, and Yes tyrosine kinases are specifically implicated in Xenopus gastrulation movements. Injection of mRNAs coding for dominant negative forms of the ubiquitous members of the Src family, namely Fyn, Src, and Yes, perturbs gastrulation movements, resulting in the inability to close the blastopore. Injection of mRNA coding for Csk, a natural inhibitor of Src kinase activity, produces the same phenotypic alterations. The ubiquitous Src kinases have redundant functions in gastrulation movements since overexpression of one member of the family can compensate for the inhibition of another. Interfering mutants of the Src family also inhibit activin-induced morphogenetic movements of animal cap explants isolated from injected embryos. In contrast, these mutants do not interfere with mesoderm induction, as inferred from the presence of mesoderm derivatives and from the expression of early mesodermal markers in injected embryos. In addition, Src kinase activity measured by an in vitro kinase assay is elevated in gastrulating embryos and in FGF- and activin-treated animal caps, confirming the implication of Src enzymatic activity during gastrulation. Altogether, our results demonstrate that Src kinases are essential components of the machinery that drives gastrulation movements independent of mesoderm induction and suggest that Src activity is primarily implicated in cellular movements that take place during the process of cell intercalation.

Animals↗

Syntheses and 1H-, 13C- and 15N-NMR spectra of ethynyl isocyanide, H-C triple bond C-N triple bond C, D-C triple bond C-N triple bond C and prop-1-ynyl isocyanide, H3C-C triple bond C-N triple bond C, D3C-C triple bond C-N triple bond C: high resolution infrared specturm of prop-1-ynyl isocyanide

Ethynyl isocyanide, H-C triple bond C-N triple bond C (1a), deuteroethynyl isocyanide, D-C triple bond C-N triple bond C (1b), prop-1-ynyl isocyanide, H3C-C triple bond C-N triple bond C (1c), and trideuteroprop-1-ynyl isocyanide, D3C-C triple bond C-N triple bond C (1d) are synthesized by flash vacuum pyrolysis of suitable organometallic precursor molecules (CO)5Cr(CN-CCl triple bond CClH) (5a), (CO)5Cr(CN-CCI=CClD) (5b), (CO)5Cr(CN-CCl=CCl-CH3) (5c) and (CO)5Cr(CN-CCI=CCl-CD3) (5d), respectively. Compounds 5a-d are formed in two steps by radical alkylation of tetraethyl-ammonium pentacarbonyl(cyano)chromate, NEt4[Cr(CO)5(CN)] (2) by 1,1,2,2,-tetrachloroethane (3a), 1,1,2,2-tetrachloro-1,2-dideuteroethane (3b), 1,1,2,2,-tetrachloropropane (3c), and 1,1,2,2-tetrachloro- 1,3,3,3-tetradeutero-propane (3d) yielding [(CO)5Cr(CN-CCl2-CCl2-H)] (4a), [(CO)5Cr(CN-CCl2-CCl2D)] (4b), [(CO)5Cr(CN-CCl2-CCl2-CH3)] (4c), and [(CO)5Cr(CN-CCl2-CCl2-CD3)] (4d). Dehalogenation of 4a-d using zinc in diethylether/acetic acid gives 5a-d, respectively. A multinuclear NMR study revealed the 1H-, 13C- and 15N-NMR data of 1a and 1c. Molecular spectroscopic data of 1c were determined by high resolution infrared spectroscopy. The by-products of the pyrolysis are the E and Z isomers of the halogenated ethenyl isocyanides H(Cl)C=CCl-NC (6a) and H3C(Cl)C=CCl-NC (6c) which have been characterized by IR, MS and NMR spectroscopy.

Journal Article↗

Synthesis and an X-ray structure of soluble phenylacetylene macrocycles with two opposing bipyridine donor sites

The synthesis of the shape-persistent macrocycles 10a and 10b with two bipyridine units in opposing sides by Hagihara/Sonogashira cross-coupling chemistry of suitably functionalized building blocks is reported. X-ray analysis of single crystals of 10b shows a layered structure with channels filled with solvent molecules and parts of the flexible chains. with which the cycle is decorated for solubility reasons.

Journal Article↗

Crystal and molecular structures of trifluoroacrylonitrile, F2C=CF-CN, and trifluorovinyl isocyanide, F2C=CF-NC, by low-temperature X-ray crystallography and ab initio calculations.

The structures of trifluoroacrylonitrile, F2C=CF-CN, monoclinic, P2(1/n) (no. 14), a = 8.595(4), b = 8.748(1), c = 5.421(1) A, beta = 102.83(2) degrees, Z = 4, and its thermally unstable isomer trifluorovinyl isocyanide, F2C=CF-NC, monoclinic, P2(1/n), a = 8.501(2), b = 8.828(2), c = 5.599(2) A, beta = 101.11(2) degrees, Z = 4 were determined by X-ray crystal structure analysis at 113 and 128 K, respectively, from single crystals grown by partial melting and gradient cooling in small glass capillaries. Selected experimental bond lengths of F2C=CF-CN/F2C=CF-NC are as follows: C=C 1.326(1)/1.304(2), C...N 1.158(1)/1.167(2) A. The C-F bond lengths of the CF2 group are significantly shorter than those of the CF(NC) and CF(CN) units, respectively. The vibrational frequencies and molecular geometries of this cyanide/isocyanide pair were also calculated by ab initio methods for comparison with the experimental results, which were found to be in general agreement.

Journal Article↗

Phosphorylation of tyrosine residues 31 and 118 on paxillin regulates cell migration through an association with CRK in NBT-II cells.

Identification of signaling molecules that regulate cell migration is important for understanding fundamental processes in development and the origin of various pathological conditions. The migration of Nara Bladder Tumor II (NBT-II) cells was used to determine which signaling molecules are specifically involved in the collagen-mediated locomotion. We show here that paxillin is tyrosine phosphorylated after induction of motility on collagen. Overexpression of paxillin mutants in which tyrosine 31 and/or tyrosine 118 were replaced by phenylalanine effectively impaired cell motility. Moreover, stimulation of motility by collagen preferentially enhanced the association of paxillin with the SH2 domain of the adaptor protein CrkII. Mutations in both tyrosine 31 and 118 diminished the phosphotyrosine content of paxillin and prevented the formation of the paxillin-Crk complex, suggesting that this association is necessary for collagen-mediated NBT-II cell migration. Other responses to collagen, such as cell adhesion and spreading, were not affected by these mutations. Overexpression of wild-type paxillin or Crk could bypass the migration-deficient phenotype. Both the SH2 and the SH3 domains of CrkII are shown to play a critical role in this collagen-mediated migration. These results demonstrate the important role of the paxillin-Crk complex in the collagen-induced cell motility.

Amino Acid Substitution↗

Low-temperature crystallization and structure determination of N-(trifluoromethyl)formamide, N-(2,2,2-trifluoroethyl)formamide and 2,2,2-trifluoroethyl isocyanide.

Crystals of N-(trifluoromethyl)formamide, C(2)H(2)F(3)NO, (I), N-(2,2,2-trifluoroethyl)formamide, C(3)H(4)F(3)NO, (II), and 2,2,2-trifluoroethyl isocyanide, C(3)H(2)F(3)N, (III), were grown in situ on an X-ray diffractometer and analysed by single-crystal X-ray diffraction methods at low temperatures. Crystal data: (I) orthorhombic, P2(1)2(1)2(1), a = 4.547 (2) Å, b = 5.947 (3) Å, c = 14.731 (9) Å, V = 398.3 (4) Å(3), Z = 4, M(r) = 113.05, T = 143 K, D(x) = 1.885 Mg m(-3); (II) monoclinic, P2(1)/n, a = 4.807 (1) Å, b = 16.707 (3) Å, c = 6.708 (1) Å, beta = 109.90 (1) degrees, V = 506.6 (2) Å(3), Z = 4, M(r) = 127.07, T = 141 K, D(x) = 1.666 Mg m(-3); (III) orthorhombic, P2(1)2(1)2(1), a = 5.668 (2) Å, b = 9.266 (3) Å, c = 8.626 (2) Å, V = 453.0 (2) Å(3), Z = 4, M(r) = 109.06, T = 163 K, D(x) = 1.599 Mg m(-3). The results showed that in the crystal both formamides (I) and (II) are exclusively present in the form of the Z isomer, although measurements of solutions of (I) have shown that the E isomer prevails [Lentz et al. (1987). Angew. Chem. 99, 951-953]. In addition ab initio calculations for (I) predicted the E isomer to be the more stable one. In compound (III) the isocyanide group is staggered with respect to the trifluoroethyl group. In the crystal packing of (I) and (II) intermolecular N-H.O hydrogen bonds generate infinite chains. In (I), these chains are linked to form sheets by C-H.O contacts. In the crystal structure of (III) each isocyanide dipole is surrounded by four electronegative F atoms with intermolecular C.F contacts between 3.4 and 3.5 Å.

Journal Article↗

The Millimeter-Wave Spectrum of DCCNC

The millimeter-wave spectrum of deuteroethynylisocyanide has been observed and analyzed in the ground and in the first excited vibrational states (v4, v5, v6, v7) = (0100), (0010), and (0001). Rotational, centrifugal distortion, and l-type doubling constants are given. Copyright 1998 Academic Press.

Journal Article↗

Acute and chronic stroke: navigated spin-echo diffusion-weighted MR imaging.

PURPOSE: The authors evaluated a phase-navigated spin-echo (SE) motion-correction sequence for use at diffusion-weighted (DW) magnetic resonance (MR) imaging after cerebral infarction. MATERIALS AND METHODS: Twenty-nine patients underwent 32 conventional T2-weighted fast SE and SE DW imaging after stroke (n=25), transient ischemic attack (n=3), or reversible ischemic neurologic deficit (n=1). Imaging was performed in a standard head holder with standard padding. Apparent diffusion coefficient (ADC) maps were constructed. RESULTS: DW images depicted high signal intensity compatible with localization of the ischemic symptoms in all cases. Lesions were depicted more clearly on DW than on T2-weighted images. On DW images, acute infarct ADC values were uniformly low (mean, 0.401x10(-5) cm2/sec =+/- 0.143 [standard deviation]) compared with control ADC values (mean, 0.754x10(-5) cm2/sec +/- 0.201). ADC values of chronic infarcts were supranormal (mean, 1.591x10(-5) cm2/sec +/- 0.840) compared with control values (mean, 0.788x10(-5) cm2/sec +/- 0.166). DW imaging did not show a change after transient ischemic attack. with reversible ischemic neurologic deficit, however, hyperintensity on DW images and low ADC resolved after symptoms abated. CONCLUSION: Clinical phase-navigated SE DW imaging improved early diagnosis of stroke and helped differentiate acute from chronic stroke. Changes on DW images are reversed after symptoms resolve.

Acute Disease↗

Diagnosis of bronchiolitis obliterans in heart-lung transplantation patients: importance of bronchial dilatation on CT.

OBJECTIVE: The purpose of this study was to evaluate the significance of bronchial dilatation identified on high-resolution CT scans obtained after heart-lung transplantation. Bronchial dilatation has been identified on pathologic specimens and on high-resolution CT scans of patients with severe bronchiolitis obliterans after lung transplantation, but this finding has not previously been systematically studied as a manifestation of this complication. MATERIALS AND METHODS: We studied the high-resolution CT scans of 16 patients who had had heart and lung transplantation at least 1 year before, and compared the percentage of dilated bronchi with evidence of small airways disease shown on pulmonary function tests. RESULTS: We found a close correlation between the percentage of bronchi in the lower lobes that were dilated and the percent predicted forced expiratory volume in 1 sec, forced vital capacity, and forced expiratory flow between 25% and 75% of vital capacity. No other feature identified on high-resolution CT scans correlated with pulmonary function abnormalities. CONCLUSION: We conclude that dilatation of the lower lobe bronchi is a good indicator of bronchiolitis obliterans in this population, and that the percentage of dilated bronchi generally increases with increasing pulmonary dysfunction.

Biopsy↗

Glutaraldehyde-preserved venous valve transplantation in the dog.

Transplantation of femoral vein grafts was performed on 33 mongrel dogs to assess graft patency and valvular function after storage in glutaraldehyde. The grafts were removed from the donor, flushed with room temperature heparinized lactated Ringer's solution, and then stored in a 0.2% glutaraldehyde solution for 16 hr. At the time of grafting, the veins were again flushed with lactated Ringer's and anastomosed orthotopically to the recipient. An arteriovenous fistula was also created. Postoperatively the animals received daily doses of aspirin (2 mg/kg) and dipyridamol (50 mg). The following groups were studied: Group I (n = 10) served as controls and received fresh autografts. Group II (n = 13) received autografts stored for 16 hr in 0.2% glutaraldehyde. Group III (n = 10) received allografts stored similarly in glutaraldehyde for 16 hr. The grafts were monitored for evidence of patency. All grafts were removed for histological evaluation when patency was no longer detected or at the end of 7 weeks. Of the fresh and glutaraldehyde-preserved autografts (Group 1), 100% were patent at 7 weeks, and generally retained valve function. Patency of allografts was only slightly inferior but valve function was disappointingly poor at 7 weeks.

Animals↗