Shift Of Nu Research Articles

The Role of Women's Leadership in the Traditional Muslim Religious Movement (New Paradigm in PBNU Leadership 2022-2027)

<em>Seeing the structure of PBNU for the 2022-2027 Period, Gus Yahya (Top Leader of PBNU) gave an important role for women to join the structure of PBNU's daily management, after approximately 96 years PBNU did not involve women in its staff structure. This certainly affects the direction of PBNU organizational policies in the future. This study intends to analyze the shift in NU's religious paradigm related to the role of women in collective leadership at PBNU and its implications in responding to changing times as well as welcoming a new civilization within NU which is entering the second century. This research includes library research with a socio-phenomenological approach. This study resulted in the finding that the paradigm shift in NU leadership was based on changes in religious understanding and empirical experiences of NU clerics (Kiai and Nyai) in various aspects of life, religious, social, political, and cultural. In addition, many NU programs related to women such as reproductive health, sexual violence, migrant women workers, reproductive health, and women's radicalism are considerations for the importance of women's involvement in the development and implementation of these programs. Strategic roles in PBNU given to women such as Nyai Dr. (H.C) Sinta Nuriyah Abdurrahman at Musytasyar, Nyai Nafisah Ali Maksum at A'wan, Alissa Wahid and Khafifah Indar Parawansa at Tanfidziyah.</em>

Islamic Politics Configuration after New Order: PKB practice in Probolinggo, Indonesia

After the 1998 reformation era, PKB becomes one of the parties that gained a good reputation. Interestingly, unlike NU in the 1940s to 1970s, when it actively took a part in electoral politics by carrying out the agenda of formalizing Islam, PKB sought to synthesize the value of Islam and Indonesia in the context of a pluralistic state and pay attention to secular issues such as political education. In Probolinggo, the issue of political education became one of the post-reform political issues. This paper aims to formulate political education as designed in PKB's political program, as well as the changing of the political Islam articulation after the reformation. To get accurate data and results, a political sociology approach was used to understand political education within the PKB platform, and to measure the extent to which the ideational formulation is capable of being implemented at the practical and local levels in Probolinggo. The data obtained were analyzed in three contexts; the context of social and political configuration in Probolinggo, the context of political transformation in NU, and the context of the articulation change of post-reform political Islam. The results concluded that PKB political education in Probolinggo faced several constraints, both structural and non-structural, while the relevance was to provide contextualization of the reformation at the national level, marking a shift in NU's political paradigm, as well as the transformation of post-New Order political Islam.

HIGH SPECTRAL RESOLUTION MEASUREMENT OF THE SUNYAEV–ZEL'DOVICH EFFECT NULL WITH Z-Spec

The Sunyaev-Zel'dovich (SZ) effect spectrum crosses through a null where dT_CMB = 0 near nu_0 = 217 GHz. In a cluster of galaxies, nu_0 can be shifted from the canonical thermal SZ effect value by corrections to the SZ effect scattering due to the properties of the inter-cluster medium. We have measured the SZ effect in the hot galaxy cluster RX J1347.5-1145 with Z-Spec, an R ~ 300 grating spectrometer sensitive between 185 and 305 GHz. These data comprise a high spectral resolution measurement around the null of the SZ effect and clearly exhibit the transition from negative to positive dT_CMB over the Z-Spec band. The SZ null position is measured to be nu_0 = 225.8 \pm 2.5 (stat.) \pm 1.2 (sys.) GHz, which differs from the canonical null frequency by 3.0 sigma and is evidence for modifications to the canonical thermal SZ effect shape. Assuming the measured shift in nu_0 is due only to relativistic corrections to the SZ spectrum, we place the limit T_e = 17.1 \pm 5.3 keV from the zero-point measurement alone. By simulating the response of the instrument to the sky, we are able to generate likelihood functions in {y_0, T_e, v_pec} space. For v_pec = 0 km/s, we measure the best fitting SZ model to be y_0 = 4.6 (+0.6, -0.9) x 10^-4, T_e,0 = 15.2 (+12,-7.4) keV. When v_pec is allowed to vary, a most probable value of v_pec = +450 \pm 810 km/s is found.

Surface Raman Spectroscopy of the Interface of Tris-(8-hydroxyquinoline) Aluminum with Mg

Surface Raman spectroscopy in ultrahigh vacuum is used to interrogate interfaces formed between tris-(8-hydroxyquinoline) aluminum (Alq(3)) and vapor-deposited Mg. The Raman spectral results for deposition of Mg mass thicknesses between 5 and 20 A indicate formation of a complex interfacial region composed primarily of Mg-Alq(3) adducts and small-grained amorphous or nanocrystalline graphite, the presence of which may have a significant effect on the electronic properties of this metal-organic interface. The observed shifts in nu(ring), nu(C-N), nu(Al-N), and nu(Al-O) modes along with the appearance of nu(Mg-C) and nu(Mg-O) modes suggest a structure for the Mg-Alq(3) adduct in which Mg is bound to the O and C atoms of Alq(3). In addition, several intense, broad modes are observed that are consistent with partial graphitization of the Alq(3) film.

Improper Hydrogen-Bonding CH·Y Interactions in Binary Methanol Systems As Studied by FTIR and Raman Spectroscopy

Fourier Transform infrared spectroscopy and Raman spectroscopy have been used to investigate hydrogen bonding of methanol in different solvents with an aim to explore potential experimental evidence for improper hydrogen bonding involving the methyl group of methanol as suggested by various computational studies. Pure methanol and solutions of methanol in water, acetonitrile, carbon tetrachloride, deuterium oxide, and deuterated acetonitrile have been studied over a range of concentrations. Wavenumber shifts of the CH stretching vibrations were examined to determine if the CH from methanol participates in hydrogen bonding. New concepts of the vibrational wavenumber and integrated intensity at infinite dilution are proposed and given the respective symbols nu(CH(o)) and C(j,CH)*(o). Using the results obtained for methanol in carbon tetrachloride as a reference, shifts in nu(CH(o)) of methanol to higher wavenumbers (blue shifts) were observed in each of the other solvents studied, with the shifts being greatest for the methanol-water interactions. The shifts in vibrational wavenumber suggest possible improper hydrogen bonding, although at this stage a definitive conclusion is not possible. The C(j,CH)*(o) results show that there is no distinguishable change in the methanol CH stretch integrated intensity in carbon tetrachloride and acetonitrile, while there is a significant decrease in the methanol CH stretch integrated intensity in the water solutions.

Peptide CαDα Stretch Frequencies in a Hydrated Conformation Are Perturbed Mainly by Cα−Dα···O Hydrogen Bonding

We have shown (J. Phys. Chem. A 2004, 108, 10923; 2007, 111, 5300) that the C(alpha)D(alpha) stretch frequency, nu(CD), can discriminate between uniform alpha(R), beta, and polyproline II conformations of isolated peptides. Similar results for such peptides to which explicit waters are hydrogen bonded exhibit shifts in nu(CD) from those of the isolated structures. We demonstrate that the main source of these frequency shifts is the formation of C(alpha)-D(alpha)...O hydrogen bonds to water. Taking into account C-H...O(water) hydrogen bonding, together with the traditional bonding of peptide groups to water, can be expected to increase our understanding of the interaction of proteins with their aqueous environment.

Formation, Reactivity, and Photorelease of Metal Bound Nitrosyl in [Ru(trpy)(L)(NO)]n+(trpy = 2,2′:6′,2′′-Terpyridine, L = 2-Phenylimidazo[4,5-f]1,10-phenanthroline)

Nitrosyl complexes with {Ru-NO} (6) and {Ru-NO} (7) configurations have been isolated in the framework of [Ru(trpy)(L)(NO)] ( n+ ) [trpy = 2,2':6',2''-terpyridine, L = 2-phenylimidazo[4,5- f]1,10-phenanthroline] as the perchlorate salts [ 4](ClO 4) 3 and [ 4](ClO 4) 2, respectively. Single crystals of protonated material [ 4-H (+)](ClO 4) 4.2H 2O reveal a Ru-N-O bond angle of 176.1(7) degrees and triply bonded N-O with a 1.127(9) A bond length. Structures were also determined for precursor compounds of [ 4] (3+) in the form of [Ru(trpy)(L)(Cl)](ClO 4).4.5H 2O and [Ru(trpy)(L-H)(CH 3CN)](ClO 4) 3.H 2O. In agreement with largely NO centered reduction, a sizable shift in nu(NO) frequency was observed on moving from [ 4] (3+) (1953 cm (-1)) to [ 4] (2+) (1654 cm (-1)). The Ru (II)-NO* in isolated or electrogenerated [ 4] (2+) exhibits an EPR spectrum with g 1 = 2.020, g 2 = 1.995, and g 3 = 1.884 in CH 3CN at 110 K, reflecting partial metal contribution to the singly occupied molecular orbital (SOMO); (14)N (NO) hyperfine splitting ( A 2 = 30 G) was also observed. The plot of nu(NO) versus E degrees ({RuNO} (6) --> {RuNO} (7)) for 12 analogous complexes [Ru(trpy)(L')(NO)] ( n+ ) exhibits a linear trend. The electrophilic Ru-NO (+) species [ 4] (3+) is transformed to the corresponding Ru-NO 2 (-) system in the presence of OH (-) with k = 2.02 x 10 (-4) s (-1) at 303 K. In the presence of a steady flow of dioxygen gas, the Ru (II)-NO* state in [ 4] (2+) oxidizes to [ 4] (3+) through an associatively activated pathway (Delta S++ = -190.4 J K (-1) M (-1)) with a rate constant ( k [s (-1)]) of 5.33 x 10 (-3). On irradiation with light (Xe lamp), the acetonitrile solution of paramagnetic [Ru(trpy)(L)(NO)] (2+) ([ 4] (2+)) undergoes facile photorelease of NO ( k NO = 2.0 x 10 (-1) min (-1) and t 1/2 approximately 3.5 min) with the concomitant formation of the solvate [Ru (II)(trpy)(L)(CH 3CN)] (2+) [ 2'] (2+). The photoreleased NO can be trapped as an Mb-NO adduct.

Interaction of acetonitrile with Na-zeolites: adsorption modes and vibrational dynamics in the zeolite channels and cavities

The interaction of acetonitrile with the extra-framework Na(+) cations in zeolites, namely Na-LTA and Na-FER, was investigated. The relative stabilities of possible types of adsorption complexes were calculated at the periodic DFT level. Individual effects on the complex stability and on the vibrational dynamics of adsorbed acetonitrile were qualitatively analysed on various cluster models. The acetonitrile primarily interacts with the Na(+) cation (via the N end), and the complex stability is modulated by the interaction of the methyl group with the framework oxygen atoms, which has a partial hydrogen-bond character. In line with the results of recent analyses of CO interactions with metal-exchanged zeolites [D. Nachtigallová, O. Bludský, C. O. Areán, R. Bulanek and P. Nachtigall, Phys. Chem. Chem. Phys., 2006, 8, 4849], two types of effects should be taken into consideration for acetonitrile complexes in Na-zeolites: (i) the effects from the bottom, reflecting the accessibility and coordination of the primary metal cation, to which the acetonitrile molecule is bonded via the N atom; and (ii) the effects from the top, including H-bond formation (stabilising effect) or repulsion due to the secondary metal cation. The effect from the bottom results in a blue shift of nu(CN) while the effect from the top (H-bond formation) results in a red shift in both nu(CN) and nu(CH).

Spectroelectrochemistry and DFT Analysis of a New {RuNO}n Redox System with Multifrequency EPR Suggesting Conformational Isomerism in the {RuNO}7 State

The compound [Ru(NO)(bpym)(terpy)](PF6)3, bpym = 2,2'-bipyrimidine and terpy = 2,2':6',2"-terpyridine, with a {RuNO}6 configuration (angle Ru-N-O 175.2(4) degrees ) was obtained from the structurally characterized precursor [Ru(NO2)(bpym)(terpy)](PF6), which shows bpym-centered reduction and metal-centered oxidation, as evident from EPR spectroscopy. The relatively labile [Ru(NO)(bpym)(terpy)](3+), which forms a structurally characterized acetonitrile substitution product [Ru(CH3CN)(bpym)(terpy)](PF6)2 upon treatment with CH3OH/CH3CN, is electrochemically reduced in three one-electron steps of which the third, leading to neutral [Ru(NO)(bpym)(terpy)], involves electrode adsorption. The first-two reduction processes cause shifts of nu(NO) from 1957 via 1665 to 1388 cm(-1), implying a predominantly NO-centered electron addition. UV-vis-NIR Spectroscopy shows long-wavelength ligand-to-ligand charge transfer absorptions for [Ru(II)(NO(-I))(bpym)(terpy)]+ in the visible region, whereas the paramagnetic intermediate [Ru(NO)(bpym)(terpy)](2+) exhibits no distinct absorption maximum above 309 nm. EPR spectroscopy of the latter at 9.5, 95, and 190 GHz shows the typical invariant pattern of the {RuNO}7 configuration; however, the high-frequency measurements at 4 and 10 K reveal a splitting of the g1 and g2 components, which is tentatively attributed to conformers resulting from the bending of RuNO. DFT calculations support the assignments of oxidation states and the general interpretation of the electronic structure.

Vibrational Spectroscopy of CO in Gas-Phase Rhodium Cluster−CO Complexes

Infrared spectra of isolated unsaturated rhodium cluster-CO complexes in the region of the CO stretching vibration, nu(CO), are measured using a molecular beam depletion technique. These spectra provide benchmarks for interpreting values of nu(CO) that are found when CO is used to probe Rh surfaces and supported Rh nanoparticles. Supported nanoparticles have shifts of nu(CO) of as much as +100 cm-1 compared to the free clusters measured here, indicative of significant charge transfer to the support.

Tris(trifluoromethyl)borane carbonyl, (CF3)3BCO-synthesis, physical, chemical and spectroscopic properties, gas phase, and solid state structure.

Tris(trifluoromethyl)borane carbonyl, (CF(3))(3)BCO, is obtained in high yield by the solvolysis of K[B(CF(3))(4)] in concentrated sulfuric acid. The in situ hydrolysis of a single bonded CF(3) group is found to be a simple, unprecedented route to a new borane carbonyl. The related, thermally unstable borane carbonyl, (C(6)F(5))(3)BCO, is synthesized for comparison purposes by the isolation of (C(6)F(5))(3)B in a matrix of solid CO at 16 K and subsequent evaporation of excess CO at 40 K. The colorless liquid and vapor of (CF(3))(3)BCO decomposes slowly at room temperature. In the gas phase t(1/2) is found to be 45 min. In the presence of a large excess of (13)CO, the carbonyl substituent at boron undergoes exchange, which follows a first-order rate law. Its temperature dependence yields an activation energy (E(A)) of 112 kJ mol(-)(1). Low-pressure flash thermolysis of (CF(3))(3)BCO with subsequent isolation of the products in low-temperature matrixes, indicates a lower thermal stability of the (CF(3))(3)B fragment, than is found for (CF(3))(3)BCO. Toward nucleophiles (CF(3))(3)BCO reacts in two different ways: Depending on the nucleophilicity of the reagent and the stability of the adducts formed, nucleophilic substitution of CO or nucleophilic addition to the C atom of the carbonyl group are observed. A number of examples for both reaction types are presented in an overview. The molecular structure of (CF(3))(3)BCO in the gas phase is obtained by a combined microwave-electron diffraction analysis and in the solid state by single-crystal X-ray diffraction. The molecule possesses C(3) symmetry, since the three CF(3) groups are rotated off the two possible positions required for C(3)(v)() symmetry. All bond parameters, determined in the gas phase or in the solid state, are within their standard deviations in fair agreement, except for internuclear distances most noticeably the B-CO bond lengths, which is 1.69(2) A in the solid state and 1.617(12) A in the gas phase. A corresponding shift of nu(CO) from 2267 cm(-)(1) in the solid state to 2251 cm(-)(1) in the gas phase is noted in the vibrational spectra. The structural and vibrational study is supported by DFT calculations, which provide, in addition to the equilibrium structure, confirmation of experimental vibrational wavenumbers, IR-band intensities, atomic charge distribution, the dipole moment, the B-CO bond energy, and energies for the elimination of CF(2) from (CF(3))(x)()BF(3)(-)(x)(), x = 1-3. In the vibrational analysis 21 of the expected 26 fundamentals are observed experimentally. The (11)B-, (13)C-, and (19)F-NMR data, as well as the structural parameters of (CF(3))(3)BCO, are compared with those of related compounds.

Resonance Raman studies of the stoichiometric catalytic turnover of a substrate-stearoyl-acyl carrier protein delta(9) desaturase complex.

Resonance Raman spectroscopy has been used to study the effects of substrate binding (stearoyl-acyl carrier protein, 18:0-ACP) on the diferric centers of Ricinus communis 18:0-ACP Delta(9) desaturase. These studies show that complex formation produces changes in the frequencies of nu(s)(Fe-O-Fe) and nu(as)(Fe-O-Fe) consistent with a decrease in the Fe-O-Fe angle from approximately 123 degrees in the oxo-bridged diferric centers of the as-isolated enzyme to approximately 120 degrees in oxo-bridged diferric centers of the complex. Analysis of the shifts in nu(s)(Fe-O-Fe) and nu(as)(Fe-O-Fe) as a function of 18:0-ACP concentration also suggests that 4e(-)-reduced Delta9D containing two diferrous centers has a higher affinity for 18:0-ACP than resting Delta9D containing two diferric centers. Catalytic turnover of a stoichiometric complex of 18:0-ACP and Delta9D was used to investigate whether an O-atom from O(2) would be incorporated into a bridging position of the resultant mu-oxo-bridged diferric centers during the desaturation reaction. Upon formation of approximately 70% yield of 18:1-ACP product in the presence of (18)O(2), no incorporation of an (18)O atom into the mu-oxo bridge position was detected. The result with 18:0-ACP Delta(9) desaturase differs from that obtained during the tyrosyl radical formation reaction of the diiron enzyme ribonucleotide reductase R2 component, which proceeds with incorporation of an O-atom from O(2) into the mu-oxo bridge of the resting diferric site. The possible implications of these results for the O-O bond cleavage reaction and the nature of intermediates formed during Delta9D catalysis are discussed.

Ground-State, Mode-Dependent Vibronic Coupling in Some Simple, Cyanide-Bridged Transition-Metal Donor-Acceptor Complexes.

Patterns of the shifts in bridging cyanide-stretching frequencies have been examined in several fully saturated, &mgr;-cyano, bi- or trimetallic transition-metal donor-acceptor (D/A) complexes. An earlier (Watzky, M. A.; et al.Inorg. Chem. 1996, 35, 3463) inference that the bridging ligand nuclear and the D/A electronic coordinates are entangled is unequivocally demonstrated by the 32 cm(-)(l) lower frequency of nu(CN) for (NH(3))(5)Cr(CNRu(NH(3))(5))(4+) than for the cyanopentaamminechromium(III) parent. This contrasts to the 41 cm(-)(1) increase in nu(CN) upon ruthenation of (NH(3))(5)RhCN(2+). More complex behavior has been found for cis and trans trimetallic, donor-acceptor complexes. The symmetric combination of CN(-) stretching frequencies in trans-Cr(III)(MCL)(CNRu(II)(NH(3))(5))(2)(5+) complexes (MCL = a tetraazamacrocyclic ligand) shifts 100-140 cm(-)(1) to lower frequency, and the antisymmetric combination shifts less than about 30 cm(-)(1). This contrast in the shifts of the symmetric and the antisymmetric combinations of the CN stretches persists even in a trans complex with no center of symmetry. Two CN stretches have also been resolved in an analogous cis complex, and both shift to lower frequency by about 60 cm(-)(1). The net shift, summed over all the CN-stretching frequencies, is about the same for the bis-ruthenates of related dicyano complexes. A simple, symmetry-adapted perturbation theory treatment of the coupled vibrations is employed to deal with the opposing effects of the "kinematic" shifts (delta) of nu(CN) to higher frequency, expected in the absence of D/A coupling, and shifts ( f ) of nu(CN) to lower frequency that occur when D/A coupling is large. The Rh(III)- and Cr(III)-centered complexes correspond to different limits of this model: delta > f and delta < f, respectively. When referenced by means of this model to complexes with Rh(III) acceptors, the shifts in trimetallic complexes, summed over the symmetric and antisymmetric combinations of CN stretches, are about twice those of bimetallic complexes. Similarly referenced and summed over all bridging CN frequencies, the shifts of nu(CN) to lower energies are proportional to the oscillator strength of the electronic, donor-acceptor charge-transfer transition. The simplest interpretation of this correlation is that the donor-acceptor coupling in these systems is a function of the nuclear coordinates of the bridging ligand. This behavior of these complexes is semiquantitatively consistent with expectation for CN(-)-mediated vibronic (pseudo-Jahn-Teller) coupling of neighboring donors and acceptors, and the observed Ru(II)/CN(-) CT absorption parameters can be used in a simple, semiclassical vibronic model to predict shifts in nu(CN) that are in reasonable agreement with those observed.

Nu Shifts in Betatron Oscillations from Uniform Perturbations in the Presence of Non-Linear Magnetic Guide Fields

Uniform magnetic field perturbations cause a closed orbit distortion in a circular accelerator. If the magnetic guide field is non-linear these perturbations can also cause a Nu shift in the betatron oscillations. Such a shift in radial Nu values has been observed in the Bevalac while studying the low energy resonant extraction system. In the Bevalac, the radial perturbation comes from the quadrants being magnetically about 0.8% longer than 900. The normal effect of this type of perturbation is a radial closed orbit shift and orbit distortion. The nu shift, associated with this type of perturbation in the presence of a non-linear guide field, is discussed in this paper. A method of handling the non-linear n values is discussed as well as the mechanism for the associated Nu shift. Computer calculations are compared to measurements.