Parallel Spinors and Holonomy Groups on Pseudo-Riemannian Spin Manifolds

We describe the possible holonomy groups of simply connected irreducible non-locally symmetric pseudo-Riemannian spin manifolds which admit parallel spinors.     

A Palladium‐Catalyzed Carbonylation Approach to Eight‐Membered Lactam Derivatives with Antitumor Activity

The reactivity of 2‐(2‐alkynylphenoxy)anilines under PdI₂/KI‐catalyzed oxidative carbonylation conditions has been studied. Although a different reaction pathway could have been operating, N‐palladation followed by CO insertion was the favored pathway with all substrates tested, including those containing an internal or terminal triple bond. This led to the formation of a carbamoylpalladium species, the fate of which, as predicted by theoretical calculations, strongly depended on the nature of the substituent on the triple bond. In particular, 8‐endo‐dig cyclization preferentially occurred when the triple bond was terminal, leading to the formation of carbonylated ζ‐lactam derivatives, the structures of which have been confirmed by XRD analysis. These novel medium‐sized heterocyclic compounds showed antitumor activity against both estrogen receptor‐positive (MCF‐7) and triple negative (MDA‐MB‐231) breast cancer cell lines. In particular, ζ‐lactam 3 j′ may represent a novel and promising antitumor agent because biological tests clearly demonstrate that this compound significantly reduces cell viability and motility in both MCF‐7 and MDA‐MB‐231 breast cancer cell lines, without affecting normal breast epithelial cell viability.     

Instantaneous Fluorescence Quantum Yield—A New Quantity with Characteristic “Fingerprints” for Excited-State Processes

The instantaneous fluorescence quantum yield _ins—a new quantity for fluorescence studies defined as the ratio of the fluorescence intensity to the optical density, both measured at the moment of the maximum of the exciting pulse—proves to be a very sensitive function for excited-state processes. Dependent on the excitation intensity _ins exhibits characteristic features (maxima/minima) indicating, for example, excited-state absorptions and annihilation processes. _ins is therefore more informative as the intensity dependence of the usually utilized fluorescence yield, the information content of which is restricted because this function is hardly structured. In the paper the influences of specific molecular parameters (excited-state absorption cross section, annihilation constant) on _ins are given, problems of the experimental accessibility of _ins are discussed, and an experimental setup for determination of this new quantity is presented. The application of the method is demonstrated for identification of excited-state absorptions of organic molecules in solution.     

On the Absolute Configuration of Penlanfuran and Related Sesquiterpenoids of the Sponge Dysidea fragilis from the North-Brittany Sea

The 1,4-addition of vinylmagnesium bromide/CuBr-SMe₂ to (+)-(4s)-cryptone ((+)- 6 ) in THF in the presence of Me₃SiCI gives the silylenol ether 7 which partly undergoes hydrolysis to ketone 8 on aqueous workup; residual 7 is hydrolyzed with pyridinium p-toluenesulfonate (PyT_sOH) to give 8 which is protected in situ with ethylene glycol and then ozonolized to give aldehyde (? )- 10. The latter, on addition of 3-lithiofuran followed by dehydration and deprotection with Py T_sOH, gives the unnatural (4S)-enantiomer (+)- 2 of noroxopenlanfuran. All processes, except 11 → (+)- 2 , are of good yield. On the basis of previous chemical transformations, this also establishes the (4R)-configuration for penlanfuran ((?)- 1 ) and other sesquiterpenoids of the sponge Dysidea fragilis from the North-Brittany sea. Non viable routes to (±)-noroxoperlanfuran ((±)-2) are also discussed.     

Carbonyl derivatives of phthalocyaninatoiron(II), especially those containing group VI axial donor atoms. Crystal and molecular structure of carbonyl(N,N-dimethylformamide)phthalocyaninatoiron(II) and mössbauer studies of some of the products

The carbonyl adduct of phthalocyaninatoiron(II), FePc, with N,N-dimethylformamide (DMF) as axial ligand, FePc(CO)DMF, was prepared by the reaction of iron carbonyls, Fe(CO)₅ or Fe₂(CO)₉, with o-phthaalonitrile in DMF as solvent. Several carbonyl adducts of FePc of general formula FePc (CO)L are reported, with L being a ligand with oxygen, sulphur and nitrogen donor atoms (L = tetrahydrofuran, H₂O, CH₃OH, dimethylsulphoxide, tetrahydrothiophene, ammonia, n-propylamine, diethylamine, triethylamine). The crystal and molecular structure of FePc(CO)DMF·DMF was investigaed by X-ray diffraction methods. The compound has a monoclinic unit cell and space group P2₁/n, a 9.86(1), b 17.35(3), c 19.79(4) », β 87.9(2)°, Z = 4, U 3383 »³, D₃ 1.458 g cm^?3. The iron atom is hexacoordinated to the four inner nitrogen atoms of the macrocyle, to carbon monoxide (Fe—C distance 1.72(2) ») and to DMF (Fe—O distance 2.07(1) »). The extra DMF occupies lattice sites. All of the compounds reported in this paper are substantially diamagnetic. Mössbauer spectra show typical isomer shift parameters for the bis-adducts and for the carbonyl adduct, substantially independent of the nature of the axial ligand. The quadrupole splitting parameter of the carbonyl adducts is strongly affected by the nature of the axial ligand.     

Synthesis of some 2,3-Dihydro-11bH-thiazolo[3,2-d][1,4]benzoxazepin-5-(6H)one derivatives. A new heterocyclic ring system

Condensation of (S)-penicillamine methyl or ethyl ester hydrochloride with salicylaldehyde and its C-5 derivatives, provided the diastereomeric thiazolidine derivatives 1 and 2 . The resulting amino function was acylated to afford the amides 3 and 4. Cyclization of the latter led to the 2,3-dihydro-11bH-thiazolo[3,2-d]-[1,4]benzoxazepin-5-(6H)ones 5 and 6. Conformational data for these heterocyclic compounds are discussed.     

Water adducts of BX(3) and CX(3)(+): implications for structure, bonding, and reactivity

Good quality ab initio calculations (MP2) show that the water adducts of BX(3) and CX(3)(+) have totally different structures (X = F-I). While all H(2)O-BX(3) complexes have classical C(s) symmetric structures with strong B-O bonds and additional H-bonding, the heavier CX(3)(+) cations (X = Cl-I) form weakly bonded "non-classical" water adducts that maximize C-X pi-bonding rather than C-O sigma-bonding. The delocalization of the positive charge as the driving force for pi-bond formation is absent in BX(3), and therefore, pi-bonding is only weak and not structure determining in H(2)O-BX(3). Since the PES of all H(2)O --> EX(3)(0/+1) particles (E = B, C) is very flat, flexible basis sets (like TZVPP) are required to rigorously characterize the adducts. In earlier calculations (J. Am. Chem. Soc. 1997, 119, 6648), classical structures were reported for all H(2)O --> EX(3)(0/+1) (E = B, C) complexes, likely resulting from the insufficient quality of the basis sets employed. By introducing a positive charge to three coordinate boron-halogen cations Do --> BX(2)(+) (Do = NH(3), OH(2), X-H), also the B-X bonds shrink due to the stronger pi-bonding induced by the positive charge delocalization and if compared to the respective neutral compounds like H(2)N-BX(2) or BX(3). The "non-classical" water adducts also suggest that the mechanism of organic reactions involving carbenium ion intermediates with alpha-bromine or -iodine substituents and a nucleophile may proceed through halogen- rather than carbon coordination.     

Intein-mediated synthesis of geranylgeranylated Rab7 protein in vitro

Production of recombinant proteins is an important prerequisite for biotechnology and life sciences in general. However, there is a paucity of methods for production of posttranslationally modified recombinant proteins or proteins with non-native functional groups, such as fluorophores, spin labels, and so forth. In this work we have used a combination of organic synthesis and in vitro protein ligation to construct monoprenylated Rab7 GTPase. The protein was prepared from a recombinant N-terminal portion and a peptide mimicking the C terminus of Rab7. For construction of a synthetic six-amino-acid-long fluorescent monoprenylated peptide, we used a block condensation strategy. Ligation was achieved with a yield of >70%. The resulting protein was purified from the unligated peptide by a combination of organic extraction and phase partitioning and refolding. The refolded monoprenylated semisynthetic Rab7 protein (Rab7GG) formed a stable complex with its natural chaperone REP-1 (Rab escort protein 1) and could serve as an acceptor of the second prenyl group in the enzymatic prenylation reaction. Using fluorescence spectroscopy, we characterized the interaction of the Rab7GG:REP-1 complex with Rab geranylgeranyl transferase and came to the conclusion that it functioned as a genuine intermediate of the prenylation reaction. Thus, we present the first example of the in vitro generation of a semisynthetic lipidated protein using the native chemical ligation method.     

Conformational Analysis of Marine Polyhalogenated β-Chamigrenes Through Temperature-Dependent NMR Spectra

Temperature-dependent ¹H- and ¹³C-NMR spectra reveal that polyhalogenated marine β-chamigrenes or synthetic derivatives thereof which are trans-diequatorially, substituted at C(8) and C(9), such as rogiolol ((?)- 2 ), obtusol ((+)- 3 ), and their acetates (+)- 1 and (?)- 4 , undergo slow ring- A chair-chair inversion. Conformational equilibria and kinetics are investigated with the aid of synthetic model compounds and molecular-mechanics calculations. Thus, steric repulsions between Br_ax–C(2) and H_eq–C(7) are seen to disfavour thermodynamically conformers 1b , 2b , 3b , and 4b , which can only be detected through cross-saturation transfer, while additional steric repulsions between Me_ax–C(1) and OH_ax–C(3) make conformer 8b of obtusol epimer so scarcely populated that it can not be detected. In agreement, with (+)- 9 and (+)- 10 , which have a trigonal C(2), two conformers can be directly observed by NMR. The kinetic barriers, which are seen to arise mainly from steric repulsions between H_ax–C(14) and the axial H or halogen atoms at C(8) and C(10), are calculated and discussed with respect to well documented exocycliemethylidene-substituted cyclohexane(ene) systems. This helps to rationalize why in rogiolol acetate ((+)- 1 ) ring B is unusually inert towards Zn/Et₂O/AcOH which causes bromohydrine-group elimination from ring A.     

Reconstructing f(T) modified gravity from ECHDE and ECNADE models

We investigate alternative candidates to dark energy (DE) that can explain the current state of the Universe in the framework of the generalized teleparallel theory of gravity f(T), where T denotes the torsion scalar. To achieve this, we carry out a series of reconstructions taking into account the ordinary and entropy-corrected versions of the holographic and new agegraphic DE models. These models are used as alternatives to DE in the literature in order to describe the current state of our Universe. It is remarked that the proposed models indicate behavior akin to phantom or quintessence models. Furthermore, we also generate the parameters of the equation of state associated with entropy-corrected models and we observe a phase transition between the quintessence state and phantom state as it is shown by the recent observational data. We also investigate the stability of these models and we create the $\{r-s\}$ trajectories and compare with the ΛCDM limit. The behavior of certain physical parameters such as the speed of sound and the Statefinder diagnostic pair $\{r-s\}$ is compatible with the current observational data.