Determinan Kualitas Reviu Laporan Keuangan Pemerintah Daerah

This study aims to examine the effect of accounting competence, independence and time pressure on the quality of the review of local government financial statements (LKPD). This research uses quantitative methods conducted at the Inspectorate of Regencies / Cities in Kediri Exclamation with a total population of 285 employees. While the sample of respondents totaling 132 employees was taken by using purposive sampling technique. The data used is primary data collected through questionnaires. While data analysis in this study is using the SEM-PLS approach with the SmartPLS 3.0 program. The results showed that accounting competence, independence and time pressure had a positive effect on the quality of LKPD review. These results indicate that more better accounting competence and the reviewer independence, it will make the better quality of the LKPD review. While the presence of time pressure will not make the quality of the review decreases.Abstrak. Penelitian ini bertujuan untuk menguji pengaruh kompetensi akuntansi, independensi dan tekanan waktu terhadap kualitas reviu laporan keuangan pemerintah daerah (LKPD). Penelitian ini menggunakan metode kuantitatif yang dilakukan di Inspektorat Kabupaten/Kota se-Eks Karesidenan Kediri dengan total populasi berjumlah 285 pegawai. Sedangkan sampel sebagai responden berjumlah 132 pegawai diambil dengan menggunakan teknik purposive sampling. Data yang digunakan merupakan data primer yang dikumpulkan melalui penyebaran kueisoner. Sedangkan analisis data menggunakan pendekatan SEM-PLS melalui program SmartPLS 3.0. Hasil penelitian menunjukkan bahwa kompetensi akuntansi, independensi, dan tekanan waktu berpengaruh positif terhadap kualitas reviu LKPD. Hasil tersebut menunjukkan bahwa semakin baik kompetensi akuntansi dan independensi pereviu, maka akan semakin baik kualitas reviu LKPD. Sedangkan adanya tekanan waktu tidak akan membuat kualitas reviu menurun.

Modeling the interactions between peptide functions and Sr2+ : Formamide-Sr2+ reactions in the Gas Phase

International audienc

The heparin-Ca2+ interaction: metal influence characterized by MS/MS and UVPD experiments

Communication par afficheInternational audienc

Modelling peptide-metal dication interactions : Formamide-Ca2+ reactions in the Gas Phase.

International audienc

Unimolecular reactivity upon collision of uracil-Ca2+ complexes in the gas phase: Comparison with uracil-M+ (M = H, alkali metals) and uracil-M2+ (M = Cu, Pb) systems

International audienc

Direct Evidence for Tautomerization of the Uracil Moiety within the Pb2+/Uridine-5′-monophosphate Complex: A Combined Tandem Mass Spectrometry and IRMPD study

International audienc

Interaction of Cisplatin with Adenine and Guanine: A Combined IRMPD, MS/MS, and Theoretical Study

International audienceInfrared multiple photon dissociation (IRMPD) spectroscopy of cis-[Pt(NH3)2(G)Cl]+ and cis-[Pt(NH3)2(A)Cl]+ ions (where A is adenine and G is guanine) has been performed in two spectral regions, 950-1900 and 2900-3700 cm-1. Quantum chemical calculations at the B3LYP/LACV3P/6-311G** level yield the optimized geometries and IR spectra for the conceivable isomers of cis-[Pt(NH3)2(G)Cl]+ and cis-[Pt(NH3)2(A)Cl]+, whereby the cisplatin residue is attached to the N7, N3, or carbonyl oxygen atom, (O6), of guanine and to the N7, N3, or N1 position of adenine, respectively. In addition to the conventional binding sites of native adenine, complexes with N7-H tautomers have also been considered. In agreement with computational results, the IR characterization of cis-[Pt(NH3)2(G)Cl]+ points to a covalent structure where Pt is bound to the N7 atom of guanine. The characterized conformer has a hydrogen-bonding interaction between a hydrogen atom of one NH3 ligand and the carbonyl group of guanine. The experimental C═O stretching feature of cis-[Pt(NH3)2(G)Cl]+ at 1718 cm-1, remarkably red-shifted with respect to an unperturbed C═O stretching mode, is indicative of a lengthened CO bond in guanine, a signature that this group is involved in hydrogen bonding. The IRMPD spectra of cis-[Pt(NH3)2(A)Cl]+ are consistent with the presence of two major isomers, PtAN3 and PtAN1, where Pt is bound to the N3 and N1 positions of native adenine, respectively

Heparin-like disaccharides: effect of metallic complexation in fragmentation pathways as characterized by MS/MS and UVPD experiments

Communication par afficheNational audienc

Gas-Phase Collision Induced Dissociation Mechanisms of Peptides : Theoretical and Experimental study of N-Formylalanylamide Fragmentation

International audienceIn order to shed light on the fragmentation mechanisms occurring during the collision induced dissociation (CID) of peptides in the gas phase, we have studied a model system, the N-formylalanylamide (HCO-Ala-NH2), by coupling experimental and theoretical methods. In particular, we have addressed two different questions arising in such experiments: (i) what is (are) the structure(s) of the ion before collision, and (ii) what are the fragmentation mechanisms occurring after collision with the target gas. For the first question, we coupled the potential energy surface (PES) study done by means of density functional theory (DFT), with Infra Red Multiple Photon Dissociation (IRMPD) spectroscopy. For the second problem, which is actually the main topic of the present work, we coupled quantum mechanics plus molecular mechanics (QM + MM) direct chemical dynamics simulations with tandem mass spectrometry (MS/MS). In addition, in order to better delineate the fragmentation mechanisms and validate those proposed by simulations, isotopic labeling experiments using 2H and 13C were performed. Thanks to the interplay between simulations and experiments, it was possible to successfully identify the fragmentation pathways leading to b1, y1, a1 and immonium ions. Our mechanisms support the "mobile proton" picture that is supposed to trigger the peptide fragmentation in the gas phase, confirming, from a chemical dynamics point of view, previous theoretical and experimental studies on similar systems

A COMBINED EXPERIMENTAL AND DFT INVESTIGATION OF ISOMERIC HEPARIN DISACCHARIDES METAL COMPLEXES

Communication par afficheHeparin (HP) glycosaminoglycans (GAGs) 1 , an anticoagulant drug, are recognized to be a biologically important polysaccharide, and have been involved in many biological processes such as blood coagulation, cell-cell and cell-matrix interaction inflammatory processes, cell growth, lipid transport and metabolism.  Why is it important to study the interaction between HP and metal cations? The effect of metal ions on protein-carbohydrate complexes is largely unknown. Heparin-biomolecule interaction can be influenced by the binding of metal ions to these complexes 2. For example, it has been reported that physiological Ca 2+ induces conformational changes in heparin that are necessary for the interaction between the anticoagulant Heparin and Annexin V, a protein proposed to play an important role in the inhibition of blood coagulation 3. It is therefore a Calcium-dependant interaction.  What is our strategy? Experimentally our aim was to study (Ca(II-H)) + and (Ca(II-A)) + complexes by tandem ESI/MS. Once generated in the gas phase, ions then undergo a fragmentation process by Collision Induced Dissociation (CID). The Ca 2+ cation induces different conformational changes in both isomers, resulting in completely different fragmentation pathways. Theoretically our aim is to explain this Metal-HP interaction by DFT calculations and delineate mechanisms of dissociation accounting for the experimental data.  Why II-A and II-H isomers? Without metal there is no difference in the MS/MS spectra of these two isomers. Only 0,2 A 2 fragmentation is observed. With Ca 2+ dissociation pattern changes drastically. Interaction between Acetyl/Ca 2+ must be important in the dissociation process. O O COOH HO OH O OH OH NH 2 OSO 3 O O COOH HO OH O OH OH NHAc OSO 3 0,2 A 2 * 0,2 X 1 * II-H II-A MS/MS results: Experiments were carried out on a LTQ Orbitrap XL mass spectrometer coupled to an ESI source. Nitrogen gas was used as collision gas. Computational results: The geometries were optimized using the density functional theory (DFT) with the B3LYP hybrid functional and 6-311G** basis set. Refined relative energies were obtained at the 6-311++G(3df,2p) level. Without Ca 2+ all the calculated 50 conformers, for each disaccharide, are very close in energy (50KJ/mol). High Binding Energy (BE) values (~1400 KJ/mol) are obtained. As deduced from the conformers calculation and the BE values, the metal complex stabilizes strongly one structure. It seems safe to deduce that both sugars lose partially their possibilities to change structurally. Biologically, this consideration could be critical in order to explain the strong interactions aforementioned. Analytically, when (Ca(HP)) + is formed, the molecule loses it flexibility due to the fixation structure effect and therefore it is noticed a decrease in the number of fragments. Leary et al. 4 delineates mechanisms of dissociation for isomeric HP without metal based upon CID experiments and H/D exchange. Another mechanism has been tested in this work but those pathways remain the most favorable ones.  0,2 A 2 Dissociation The acetyl group in II-A blocks the R1 (Rearrangement) step. Nevertheless, it is still possible to transfer the proton through the acetyl carbonyl group. The energy associated (PT2 barrier) is however bigger (163 KJ/mol) than for II-H (-55 KJ/mol).  0,2 X 1 Dissociation Starting from the initial structures, and using the dissociation mechanism given by Leary et al. shown below, the same methodology will be employed in order to unravel the 0,2 X 1 fragmentation pattern. , Ca 2