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Energy transfer as parametric excitation: an examination of nonlinearity in enzymatic reaction, nerve conduction, muscle contraction, electron tunneling, and electron transfer.

Chemical parametric excitation is presented as the fundamental mechanism of energy transfer. Together with the Franck-Condon principle, it provides a mechanically sound explanation for enzymatic reaction, nerve excitation, muscle contraction, and electron transfer at a basic level. Intermediate between macroscopic models of membrane asymmetry and molecular models, the new model rests on a systematic approach, proposed here, to organizational aspects of the energy transfer processes. In support, a derivation is given of the chemical analog of the Manley-Rowe power conservation relations for parametrically excited electrical networks. This extension to chemical systems indicates for the first time an explanation of power flow directionality and delegates a pumping role to the enzyme. The generalized Manley-Rowe relations are suggested to be a universal law of nature. In such case, nonlinearity could be attributable to the coupling of three systems by these generalized Manley-Rowe conditions relating flows/reactions/oscillations--even though separately each system might be described by linear (Onsager) relations.

Animals↗

[Enzyme histochemical and electron microscopic studies on the problem of infiltrating (invasive) tumor growth. 2. Electron microscopic studies].

Tumour cells of 12 mammary carcinomas, 14 ovarian carcinomas, 10 malignant melanomas of the man and 24 transplantation tumours of rats were studied by the electron microscope in their relation to the surrounding tissue. On the contact surface between tumour cells (mammary carcinomas) and surrounding tissue a focal or extensive loss of the cell membranes in seen. This causes a release of cytoplasmic parts, especially of ribosome-like material. The adjacent connective tissue shows a splitting of the collagenous bundles and a fibrilloysis. In the infiltrated skeletal muscle (ransplantation tumours of rats) the tumour cells connect directly to the muscle cells. These are eroded showing ruptured fibres and loosened filaments and mitochondria, giving a moth eaten appearance. As a result of these findings we presume that the destruction of the tissue surrounding the tumour is mainly initiated by the tumour cells. For ovarian carcinomas and malignant melanomas (with few exceptions) there is no morphological sign for a specific enzymatic-lytic effect of the living tumour cells to the surrounding tissue. The findings are discussed in the aspect of the invasive tumour growth.

Cell Nucleus↗

DFT description of the electronic structure and spectromagnetic properties of strongly correlated electronic systems: NiII, CuII and ZnII o-dioxolene complexes.

The spectroscopic and magnetic properties of dioxolene complexes of zinc, copper and nickel were studied by DFT calculations on model complexes of formulas [(NH(3))(4)M(II)(SQ)](+) (M=Zn, Ni; SQ=semiquinonato) and [(NH(3))(2)Cu(II)(SQ)](+). Standard approaches such as time-dependent DFT (TDDFT), the Slater transition state (STS), and broken symmetry (BS) were found to be unable to completely account for the physical properties of the systems, and complete active space-configuration interaction (CAS-CI) calculations based on the Kohn-Sham (KS) orbitals was applied. The CAS-CI energies, properly corrected with multireference perturbation theory (MR-PT), were found to be in good agreement with experimental data. We present here a calculation protocol that has a low CPU cost/accuracy ratio and seems to be very promising for interpreting the properties of strongly correlated electronic systems in complexes of real chemical size.

Journal Article↗

Light and electron microscopy study of carbohydrate antigens found in the electron-lucent layer of Pneumocystis carinii cysts.

The localization and biochemical nature of antigens found in the electron-lucent layer (ELL) of Pneumocystis carinii cysts using polyclonal rabbit antibodies are described. These antigens, specific for the cystic stages of the parasite, were shared by organisms from different hosts, suggesting that they represent functionally important components of the cyst cell wall. The binding sites were situated on an interwoven net of fibrils in the ELL produced by mild to strong proteolysis. Degradation of this residue by glucanase and chitinase confirms that this layer contains branched glucan and chitin. In contrast, the prompt susceptibility of the polysaccharide-rich ELL to proteolysis reveals that proteins are also relevant in building up the cyst-wall glucan skeleton. It is therefore concluded that the formation of the Pneumocystis cyst wall shows differences to the typical fungal cell-wall architecture. The taxonomical debate regarding this unique protist is ongoing, and consideration of these immunological and morphological findings may be useful for the study of the biology and phylogeny of Pneumocystis.

AIDS-Related Opportunistic Infections↗

Development of a System to Provide Full, Real-time Remote Control of a Scanning Electron Microscope across the Second Generation Internet: The Teaching SEM.

The development and makeup of a real-time full remote control system for the University of Michigan, Department of Materials Science and Engineering Teaching SEM is described. The instrument was initially controlled via the campus local area Ethernet network and cable TV network. The latest implementation employs Fast Ethernet, Asynchronous Transfer Mode (ATM) networks, and moving picture experts group (MPEG) video encoding to effect the remote control via the computer network alone. Remote control demonstrations from Washington, DC, Dearborn, MI, and Emerson School, Ann Arbor, MI are described.

Journal Article↗

Total skin electron therapy: a technique which can be implemented on a conventional electron linear accelerator.

PURPOSE: A technique for treating whole-body skin with an electron linear accelerator with nominal energies in the range 4-8 MeV is presented. Stationary fields at an extended source-skin distance are used with the patient treated in a reclined position. METHODS AND MATERIALS: The relative beam data, absolute dosimetry measurements and the patient setup parameters are presented. The calculations required to correct for patient size are discussed. RESULTS: The technique described uses a six field circumferential cycle, with longitudinally matched fields along the length of the patient. Treatment times are reasonable using the standard dose rate of the machine. The uniformity of the skin dose measured on three patients was found to be comparable to that of other total skin treatment techniques. CONCLUSION: A technique for treating conditions like mycosis fungoides is presented requiring relatively simple supporting dosimetry. No modifications to the unit are required and no sophisticated treatment apparatus is necessary, which makes the technique attractive to smaller Institutions, especially in developing countries, where technical support may be limited.

Calibration↗

Identification of drugs using a gas chromatography-mass spectrometry system equipped with electron impact-chemical ionization and electron impact-field ionizationfield desorption combination sources.

In a case of toxicological analysis by gas chromatography (GC)-mass spectrometry-data system, chemical ionization (CI), field ionization (FI) and electron impact data are shown to lead rapidly to assignments for all significant GC peaks. Valuable data include not only full spectra in the three ionization modes, but also exact mass measurements in the FI or CI mode. Such measurements, obtained by a dynamic peak-matching technique, lead to the elemental composition of the compounds of interest. This knowledge makes the assignment of key GC peaks unequivocal and provides an extremely high level of confidence regarding the identity of whole metabolite series. It is also shown that the nature of the FI information is very similar to that obtained from CI data.

Aminopyrine↗

Azido derivatives of low-valent group 14 elements: synthesis, characterization, and electronic structure of [(n-Pr)2ATI]GeN3 and [(n-Pr)2ATI]SnN3 featuring heterobicyclic 10-pi-electron ring systems.

Treatment of THF solutions of [(n-Pr)2ATI]MCl (where [(n-Pr)2ATI]- = N-(n-propyl)-2-(n-propylamino)troponiminate; M = Ge and Sn) with sodium azide affords the compounds [(n-Pr)2ATI]MN3 in excellent yield. X-ray analyses revealed that these Ge(II) and Sn(II) compounds feature linear azide moieties and planar heterobicyclic C7N2M ring systems. Germanium and tin atoms adopt a pyramidal geometry. IR spectra of [(n-Pr)2ATI]GeN3 and [(n-Pr)2ATI]SnN3 display a nu asym(N3) band at 2048 and 2039 cm-1, respectively. DFT calculations on the corresponding methyl-substituted species demonstrate that the geometrical and electronic structure of these two species are very similar, and the dominant canonical form of the metal-azide moiety is M-N-N identical to N. The tin system is, as expected, slightly more ionic. A comparative CASSCF/DFT study on the model system H-Sn-N3 illustrates that the DFT approach is viable for the calculation of the structures of these species.

Journal Article↗

Metallonitrosyl fragment as electron acceptor: intramolecular charge transfer, long range electronic coupling, and electrophilic reactivity in the trans-[NCRu(py)(4)(CN)Ru(py)(4)NO](3+) ion.

The new complex trans-[NCRu(py)(4)(CN)Ru(py)(4)NO](PF(6))(3) (I) was synthesized. In acetonitrile solution, I shows an intense visible band (555 nm, epsilon = 5800 M(-1) cm(-1)) and other absorptions below 350 nm, associated with d(pi) --> pi(py) and pi(py) --> pi(py) transitions. The visible band is presently assigned as a donor-acceptor charge transfer (DACT) transition from the remote Ru(II) to the delocalized [Ru(II)-NO(+)] moiety. Photoinduced release of NO is observed upon irradiation at the DACT band. Application of the Hush model reveals strong electronic coupling, with H(DA) = approximately 2000 cm(-1). The difference between the optical absorption energy and redox potentials for the donor and acceptor sites (Ru(III,II), 1.40 V, and NO(+)/NO, 0.50 V, vs Ag/AgCl, 3 M KCl, respectively) (hnu - DeltaE(red)) is 1.33 eV, a large value which probably relates to the significant changes in distances and angles for the Ru-N-O moiety upon reduction. UV-vis absorptions, IR frequencies, and redox potentials are solvent-dependent. Controlled potential reduction (of NO(+)) and oxidation (of Ru(II) associated with the dicyano-chromophore) of I afford stable species, [NCRu(II)(py)(4)(CN)Ru(py)(4)NO](2+) (I(red)) and [NCRu(III)(py)(4)(CN)Ru(py)(4)NO](4+) (I(ox)), respectively, which are characterized by UV-vis and IR spectroscopies. I(red) shows an EPR spectrum characteristic of [Ru(II)-NO(*)] complexes. Compound I is electrophilically reactive in aqueous solution above pH 5: values of the equilibrium constant for the reaction [NCRu(py)(4)(CN)Ru(py)(4)NO](3+)+ 2 OH(-) <--> [NCRu(py)(4)(CN)Ru(py)(4)NO(2)](+) + H(2)O, K = 3.2 +/- 1.4 x 10(15) M(-2), and of the rate constant for the nucleophilic addition of OH(-), k = 9.2 +/- 0.2 x 10(3) M(-1) s(-1)(25 degrees C, I = 1 M), are obtained, with DeltaH = 90.7 +/- 3.8 kJ mol(-1) and DeltaS = 135 +/- 13 J K(-1) mol(-1). The oxidized complex, I(ox), shows an enhanced electrophilic reactivity toward OH(-). This addition reaction is followed by irreversible processes, which most probably lead to disproportionation of bound nitrite and other products.

Journal Article↗

Reduction pathway of end-on terminally coordinated dinitrogen. IV. Geometric, electronic, and vibrational structure of a W(IV) dialkylhydrazido complex and its two-electron-reduced derivative undergoing N-N cleavage upon protonation.

The molybdenum and tungsten dialkylhydrazido complexes [M(dppe)2 (NNC5H10)]2+ (M = Mo, W; compounds A(Mo) and A(W)) and their two-electron-reduced counterparts [M(dppe)2 (NNC5H10)] (compounds B(Mo) and B(W)) are characterized structurally and spectroscopically. The crystal structure of B(W) indicates a geometry between square pyramidal and trigonal bipyramidal with the NNC5H10 group in the apical position and in the trigonal plane of the complex, respectively. Temperature-dependent 31P NMR spectra of B(Mo) show that this geometry is present in solution as well. At room temperature, rapid Berry pseudorotation between the "axial" and "equatorial" ligand positions gives rise to a singlet in the 31P NMR spectrum. This exchange process is slowed at low temperature, leading to a doublet. The N-N distance of B(W) is 1.388 A, and the W-N distance is 1.781 A. Infrared and Raman spectroscopy applied to A(W), B(W), and their 15N isotopomers reveals extensive mixing between the N-N and W-N vibrations of the metal-N-N core with the modes of the piperidine ring. The N-N force constant of A(W) is determined to be 6.95 mdyn/A, which is close to the values of the Mo and W NNH2 complexes. In B(W), the N-N force constant decreases to 6.4 mdyn/A, which is between the values found for the Mo/W NNH3 and NNH2 complexes. This allows us to attribute N-N double bond character to A(W) and intermediate character between the double and single bonds for the N-N bond of B(W). These findings are supported by DFT calculations. More importantly, the HOMO of B(W) corresponds to a linear combination of the metal d(sigma) orbital with a ligand orbital having N-N sigma* character, inducing a weakening of the N-N bond. This contributes to the cleavage of the N-N bond taking place upon protonation of B(W) at the Nbeta atom of the NNC5H10 group.

Journal Article↗

Terpyridine Zn(II), Ru(III), and Ir(III) complexes: the relevant role of the nature of the metal ion and of the ancillary ligands on the second-order nonlinear response of terpyridines carrying electron donor or electron acceptor groups.

Coordination of 4'-(C6H4-p-X)-2,2':6',2''-terpyridines [X = NO2, NBu2, (E)-CH=CH-C6H4-p-NBu2, (E,E)-(CH=CH)2-C6H4-p-NMe2] to Zn(II), Ru(III), and Ir(III) metal centers induces a significant enhancement of the absolute value of the second-order nonlinear optical (NLO) response of the terpyridine, measured by means of both electric field induced second harmonic generation and solvatochromic methods. By varying the nature of the metal center, the enhanced second-order NLO response shifts from positive to negative. Such a shift is controlled by electronic charge-transfer transitions, such as metal-to-ligand or ligand-to-metal transitions, in addition to the intraligand charge transfer. The enhancement generated by coordination is also controlled by the chelation effect and by fine-tuning of the ancillary ligands.

Journal Article↗