Selected Least Studied but not Forgotten Bioluminescent Systems

Bioluminescence is a form of chemiluminescence generated by luminous organisms. Luminous taxa have currently been reported from about 800 genera and probably over 10 000 species in the world. On the other hand, their bioluminescent systems, including chemical structures of luciferins/chromophores and the genes encoding luciferases/photoproteins, have been elucidated from only a few taxonomic groups, for example beetles, bacteria, dinoflagellates, ostracods and some cnidarians. Research efforts to understand unknown bioluminescence systems are being conducted around the world, and recently, for example, novel luciferin structures of luminous enchytraeid potworms and fungi were identified by the authors. In this study, we review the current status and perspectives, in the context of postgenomic era, of most likely novel but less‐revealed bioluminescence systems of ten selected organisms: earthworm, parchment tubeworm, fireworm, scaleworm, limpet, millipede, brittle star, acorn worms, tunicate and shark, which indeed are the next focus of our international collaboration.     

The use of mass spectrometry in obstetric and gynecology

The present review shows the utility of using mass spectrometry (MS) in obstetrics and gynecology. In this review different gas chromatography / mass spectrometry and liquid chromatography / mass spectrometry methods developed before to be used in obstetrics and gynecology are described. These methods are very useful to determine different hormones in pregnancy, fatty acids esters (related to the use of ethanol) in human meconium and toxic compounds in umbilical cord (as ethanol, steroids, morphine, cocaine, methadone and other drugs). It is also shown in this review the progress during last decades in the field of using mass spectrometry in obstetrics and gynecology (for screening in utero exposure of the child to alcohol, drugs and other toxic compounds). In the field of using mass spectrometry in obstetrics and gynecology are still many problems to solve. For example, the detection of fatty acids esters in meconium has several limitations, which affects the results. One limitation is multiple births. Also in fetal distress, meconium may be passed before birth, and in this case, the collection is impossible. Moreover the meconium is formed starting from the fourth month of pregnancy, so the fetal exposure at any toxic compounds during the first three months cannot be detected at all. To solve all of these, the best would be to combine the results obtained from meconium, with other results obtained from pregnancy serum, placenta or umbilical cord. The main reason for using MS in obstetrics and gynecology is that MS is a noninvasive and a complementary method. It offers the results at a very early point in time, even before the act of birth. Sometimes the use of mass spectrometry is the only alternative. This shows that these methods are of great interest for the future and need to be developed further.      

Divergent Reactivity of Rhodium(I) Carbenes Derived from Indole Annulations

Rhodium(I) carbenes were generated from propargylic alcohol derivatives as the result of a dehydrative indole annulation. Depending on the choice of the electron‐withdrawing group on the aniline nitrogen nucleophile, either a cyclopropanation product or dimerization product was obtained chemoselectively. Intramolecular hydroamidation occurred for the same type of propargylic alcohol derivatives when other transition‐metal catalysts were employed.     

Performance Analysis of Communication System with Nonlinear Power Amplifier

A communication system with nonlinear Power Amplifier (PA) is considered. The PA nonlinearity forces the designer of communication system to choose proper Back-Off, which influences three major parameters of the communication system: (i) power efficiency, (ii) Adjacent Channel Power Ratio (ACPR), and (iii) bit rate expressed by Mutual Information (MI). Having these three parameters, we propose to evaluate the performance of a communication system with nonlinear PA using the fact that ACPR is dictated by the regulator/communication standard. In what follows we propose to find power efficiency and MI as a function of ACPR. To illustrate the usefulness of the proposed method, the Solid State Power Amplifier (SSPA), and two linearized versions of SSPA are considered. The first version is a perfectly linearized PA using pre-distortion resulting with Soft Envelope Limiter (SEL), and the second is the Feed-Forward (FF) architecture based on SSPA. For each of the PAs ACPR, power efficiency and MI are found. While the analysis of SSPA and SEL is mainly based on the existing literature, the analysis of FF may be considered as a new contribution. From the results of the analysis it is concluded that linearization improves the overall performance of communication system. It is also shown that the pre-distortion method (SEL) shows better performance than FF.     

Inverse seesaw in NMSSM and 126 GeV Higgs boson

We consider extensions of the next-to-minimal supersymmetric model (NMSSM) in which the observed neutrino masses are generated through a TeV scale inverse seesaw mechanism. The new particles associated with this mechanism can have sizable couplings to the Higgs field which can yield a large contribution to the mass of the lightest CP-even Higgs boson. With this new contribution, a 126 GeV Higgs is possible along with order of 200 GeV masses for the stop quarks for a broad range of tan β. The Higgs production and decay in the diphoton channel can be enhanced due to this new contribution. It is also possible to solve the little hierarchy problem in this model without invoking a maximal value for the NMSSM trilinear coupling and without severe restrictions on the value of tan β.     

An example of the refinement of positional disorder modeled as compositional disorder in [5‐(2‐formylphenyl)‐10,15,20‐triphenylporphyrinato]nickel(II)

The title compound, [Ni(C₄₅H₂₈N₄O)], crystallizes in the space group I2d and resides on a crystallographic fourfold rotoinversion axis with only a quarter of the complex in the asymmetric unit. The complex displays positional disorder as the one aldehyde group on the ligand can be located at four different positions. It was necessary to model this as compositional disorder to obtain a correct model and refinement. The practical approach to the refinement is explained.     

Ethylene polymerization catalyzed by substituted pyrazole nickel complexes

(Pyrazole)nickel dibromide complexes, (3,5-Me₂pz)₂NiBr₂ (1), (3-Mepz)₄NiBr₂ (2), (pz)₄NiBr₂ (3) and (3,5-^tBu₂pz)₂NiBr₂ (4), were prepared by the reaction of the appropriate pyrazole with (DME)NiBr₂. Solid-state structures of these complexes show a direct relation between the steric bulk of the pyrazole ligand and structure, with more bulky ligands forming four-coordinate complexes (1 and 4) whereas the less bulky ligands formed six-coordinate complexes (2 and 3). Activation of selected complexes (1 and 3) with methylaluminoxane (MAO) produced species that catalyzed the polymerization of ethylene to form high density polyethylene.     

Structural isomers of aryl-substituted eta(3)-propargyl complexes: eta(2)-1-Metalla(methylene)cyclopropene and eta(3)-benzyl complexes

Hydride abstraction from C(5)Me(5)(CO)(2)Re(eta(2)-PhC triple bond CCH(2)Ph) (1) gave a 3:1 mixture of eta(3)-propargyl complex [C(5)Me(5)(CO)(2)Re(eta(3)-PhCH-C triple bond CPh)][BF(4)] (5) and eta(2)-1-metalla(methylene)cyclopropene complex [C(5)Me(5)(CO)(2)Re(eta(2)-PhC-C=CHPh)][BF(4)] (6). Observation of the eta(2)-isomer requires 1,3-diaryl substitution and is favored by electron-donating substituents on the C(3)-aryl ring. Interconversion of eta(3)-propargyl and eta(2)-1-metalla(methylene)cyclopropene complexes is very rapid and results in coalescence of Cp (1)H NMR resonances at about -50 degrees C. Protonation of the alkynyl carbene complex C(5)Me(5)(CO)(2)Re=C(Ph)C triple bond CPh (22) gave a third isomer, the eta(3)-benzyl complex [C(5)Me(5)(CO)(2)Re[eta(3)(alpha,1,2)-endo,syn-C(6)H(5)CH(C triple bond CC(6)H(5))]][BF(4)] (23) along with small amounts of the isomeric complexes 5 and 6. While 5 and 6 are in rapid equilibrium, there is no equilibration of the eta(3)-benzyl isomer 23 with 5 and 6.     

Zirconium, hafnium, and tantalum amide silyl complexes: their preparation and conversion to metallaheterocyclic complexes via gamma-hydrogen abstraction by silyl ligands

New transition metal silyl amide complexes (Me(2)N)(3)Ta[N(SiMe(3))(2)](SiPh(2)Bu(t)) (1) and (Me(2)N)M[N(SiMe(3))(2)](2)(SiPh(2)Bu(t)) (M = Zr, 2a, and Hf, 2b) were found to undergo gamma-H abstraction by the silyl ligands to give metallaheterocyclic complexes (3) and (M = Zr, 4a, and Hf, 4b), respectively. The conversion of 1 to 3 follows first-order kinetics with DeltaH() = 23.6(1.6) kcal/mol and DeltaS() = 3(5) eu between 288 and 313 K. The formation of 4a from (Me(2)N)Zr[N(SiMe(3))(2)](2)Cl (5a) and Li(THF)(2)SiPh(2)Bu(t) (6) involves the formation of the intermediate 2a, followed by gamma-H abstraction. Kinetic studies of these consecutive reactions, a second-order reaction to give 2a and then a first-order gamma-H abstraction to give 4a, were conducted by an analytical method and a numerical method. At 278 K, the rate constants k(1) and k(2) for the two consecutive reactions are 2.17(0.03) x 10(-)(3) M(-)(1) s(-)(1) and 5.80(0.15) x 10(-)(5) s(-)(1) by the analytical method. The current work is a rare kinetic study of the A + B --> C --> D (+ E) consecutive reactions. Kinetic studies of the formation of a metallaheterocyclic moiety have, to our knowledge, not been reported. In addition, gamma-H abstraction by a silyl ligand to give such a metallaheterocyclic moiety is new. Theoretical investigations of the gamma-H abstraction by silyl ligands have been conducted by density functional theory calculations at the Becke3LYP (B3LYP) level, and they revealed that the formation of the metallacyclic complexes through gamma-H abstraction is entropically driven. X-ray crystal structures of (Me(2)N)(3)Ta[N(SiMe(3))(2)](SiPh(2)Bu(t)) (1), (Me(2)N)Zr[N(SiMe(3))(2)](2)Cl (5a), and (M = Zr, 4a, and Hf, 4b) are also reported.