Synthesis, Structural Variations and Trends In the Properties of Unique Dinuclear and Polynuclear Complexes of Bis(Pyrazolyl)Methane Ligands In Solid State and Solution

The semi-rigid ligands, p-[CH(pz)2]2C6H4, Lp, m-[CH(pz)2]2C6H2, Lm, and m-[CH(3,5-Me2pz)2]2C6H4, Lm* (pz = pyrazolyl ring), link two bis(pyrazolyl)methane units into a single molecule by a rigid phenylene spacer and are used to study the structural variations and magnetic interactions in self-assembled first row, divalent transition metal complexes in polymeric, dinuclear and dinuclear metallacyclic settings. The formation of these architectures highly depend on the geometry of these ligands: anti, the two -CH(pz)2 units are on the opposite side of the plane defined by the phenylene spacer, or syn, both -CH(pz)2 units are on the same side of the phenylene spacer. The first chapter focuses on structural modifications in dinuclear or polymeric copper(II) complexes of Lp, in anti conformation, induced by slight changes in the solvent of crystallization, and the effect of these changes on the supramolecular organization and weak hydrogen bonding patterns in these complexes. Opposite to the structural diversity generated with Lp in anti conformation, Lm and Lm* prefer to self-assemble into dinuclear metallacycles, by adopting syn conformation. In these units the divalent metal centers are also linked by a small anionic bridge, X = F-, Cl-, Br-, OH-, CN-, N3-, to generate [M2(μ-X)(μ-L)2]3+, where L = Lm or Lm*. The tendency of these ligands to form a single structural type prompted us to tackle a fundamental problem in magnetism: carefully designed systems that control the geometry around the metal centers are lacking, therefore magneto-structural correlations are based on compounds where several structural parameters vary simultaneously. As demonstrated in chapters II-V, this [M2(μ-X)(μ-L)2]3+ metallacyclic system, for the first time, uniquely allows the overall structure to be maintained constant while a single structural feature, directly affecting the antiferromagnetic superexchange interactions, is selectively altered. The copper(II) series, [Cu2(μ-X)(μ-Lm*)2](ClO4)3, represents the first series of dinuclear complexes with a strict linear Cu-X-Cu bridging arrangement, enabling extremely strong antiferromagnetic superexchange pathways. The magnetic susceptibilities of the copper(II) complexes are close to 0, even at room temperature, allowing the study of these compounds in solution by different NMR techniques. In chapter VI, I show that the structure, geometry and magnetic interactions in solution and solid state are similar. Chapter VII is centered around the dynamic behavior of [Zn2(μ-OH)(μ-Lm)2](ClO4)3 in solution. The VT-NMR and spin saturation transfer experiments reveal an unprecedented example of concerted Berry pseudorotation at two metal sites accompanied by the simultaneous 180° ring flip of the phenylene spacer - termed the Carolina Twist and Flip mechanism. This process is hindered by the methyl groups on the pyrazolyl rings for [M2(μ-OH)(μ-Lm*)2](ClO4)3, M = Zn(II), Cd(II). Chapter VIII discusses the synthesis and characterization of an unusual cubane type structure, [M4(μ-OH)4(μ-Lm)2(Solvent)4](ClO4)4 where M = Ni(II) or Cd(II). The nickel(II) centers are ferromagnetically coupled and the cadmium(II) compound undergoes a similar rearrangement to [Zn2(μ-OH)(μ-Lm)2](ClO4)3

Kinerja Rumah Sakit Darurat Wisma Atlet Kemayoran dalam Penanggulangan Bencana Covid-19

Penelitian ini berjudul Kinerja Rumah Sakit Darurat Wisma Atlet Kemayoran dalam Penanggulangan Bencana Covid-19. Metode penelitian yang digunakan adalah deskripsif dengan pendekatan kualitatif. Adapun narasumber penelitian ini diantaranya adalah pasien dan atau mantan pasien Rumah Sakit Darurat Wisma Atlet Kemayoran dan Satuan Tugas Kesehatan Rumah Sakit Darurat Wisma Atlet Kemayoran. Teknik pengumpulan data yang digunakan berupa wawancara, observasi serta dokumentasi. Analisis data dilakukan dengan pengumpulan data, kondensasi data, penyajian data, dan penarikan kesimpulan. Tujuan dari penelitian ini yaitu untuk mengetahui bagaimana kinerja Rumah Sakit Darurat Wisma Atlet Kemayoran dalam penanggulangan bencana Covid-19. Penelitian ini mengguanakan teori kinerja dengan indikator yang dikemukakan oleh Bastian dan Dwiyanto dimana terdapat tiga indikator untuk mengukur kinerja diantaranya akuntabilitas, efektifitas, dan efisiensi. Hasil penelitian menunjukan bahwa kinerja Rumah Sakit Darurat Wisma Atlet Kemayoran sudah berjalan dengan baik. Dilihat dari indikator akuntabilitas dimana informasi yang dibutuhkan dapat diakses melalui media yang telah disediakan seperti instagram, call center, dan whatsapp group pasien. Pelayanan kesehatan yang diberikan telah dilaksanakan secara ketat dan sesuai prosedur kesehatan mulai dari pelayanan teknis hingga peralatan sesuai dengan standar WHO. Kemudian pada indikator efektifitas, kinerja yang dilaksanakan telah berjalan efektif dilihat dari tercapainya visi dan misi, kepuasan pasien, dan dampak yang dirasakan dari adanya Rumah Sakit Darurat Wisma Atlet Kemayoran. Selanjutnya pada indikator efisiensi, Rumah Sakit Darurat Wisma Atlet Kemayoran telah secara efisien menggunakan fasilitas kesehatan yang ada untuk membantu proses kesembuhan pasien

ANÁLISE DOS IMPACTOS SOCIAIS GERADOS EM UM NEGÓCIO: um estudo em uma Associação de Produtores de um Assentamento

O objetivo desta proposta de pesquisa é analisar o modelo de negócio do Assentamento Serra de Paranaíba-MS e os impactos sociais aos produtores assentados associados. O associativismo é uma forma de organizar os assentamentos - e uma forma de negócio de impacto social. Um modelo de negócios deve ter: 1) proposição de valor; 2) clientes-alvo; 3) canais de distribuição; 4) relacionamento; 5) configuração de valor; 6) competências; 7) parcerias; 8) estrutura de custos; 9) modelo de receita. E por se tratar de um negócio de impacto social, deve-se considerar: equação lucro social: o lucro social e o lucro ambiental; proposta de valor: stakeholders e produto/serviço; constelação de valor: cadeia de valor interna e cadeia de valor externa; e equação lucro econômico: as receitas de vendas, estrutura de custos e capital empregado sem perda econômica. A pesquisa se caracteriza como qualitativa e exploratória. Os dados serão coletados por meio de entrevistas com os assentados vinculados a Associação de Produtores do Assentamento Serra. Os dados serão tratados conforme a análise de conteúdo

Effect of slight crosslinking on the mechanical relaxation behavior of poly(2-ethoxyethyl methacrylate) chains

The synthesis, thermal and mechanical characterizations of uncrosslinked and lightly crosslinked poly(2-ethoxyethyl methacrylate) are reported. The uncrosslinked poly(2-ethoxyethyl methacrylate) exhibits in the glassy state two relaxations called in increasing order of temperature, the gamma and beta processes respectively. These are followed by a prominent glass rubber or alpha relaxation. By decreasing the chains mobility by a small amount of crosslinking, the beta relaxation disappears and the peak maximum associated with the alpha relaxation is shifted from 268 K to 278 K, at 1 Hz. An investigation of the storage relaxation modulus of the crosslinked polymer indicates two inflexion points that presumably are related to segmental motions of dangling chains of the crosslinked networks and to cooperative motions of the chains between crosslinking points. Nanodomains formed by side-groups flanked by the backbone give rise to a Maxwell Wagner Sillars relaxation in the dielectric spectra that have no incidence in the mechanical relaxation spectra.We thank Dr. J. Guzman (Madrid) for providing us with the CEOEMA sample. This work was financially supported by the DGCYT and CAM through the Grant MAT2008-06725-C03 and MAT2012-33483. In memoriam of Professor Emeritus Evaristo Riande in recognition of his contribution to Polymer Science.Carsí Rosique, M.; Sanchis Sánchez, MJ.; Díaz Calleja, R.; Riande, E.; Nugent, MJD. (2013). Effect of slight crosslinking on the mechanical relaxation behavior of poly(2-ethoxyethyl methacrylate) chains. European Polymer Journal. 49(6):1495-1502. doi:10.1016/j.eurpolymj.2012.12.012S1495150249

Rapid precipitation : an alternative to solvent casting for organic solar cells

Rapid precipitation, immersion of a liquid formulation into a nonsolvent, is compared with drop casting for fabricating organic solar cells. Blends comprising poly‐3‐hexylthiophene (P3HT), phenyl‐C61‐butyric acid methyl ester (PCBM), and chlorobenzene were processed into bulk samples by using two distinct routes: rapid precipitation and drop casting. The resulting structure, phases, and crystallinity were analyzed by using small‐angle neutron scattering, X‐ray diffraction, differential scanning calorimetry, and muon spin resonance. Rapid precipitation was found to induce a finely structured phase separation between PCBM and P3HT, with 65 wt % crystallinity in the P3HT phase. In contrast, solvent casting resulted in a mixed PCBM/P3HT phase with only 43 wt % P3HT crystallinity. The structural advantages conferred by rapid precipitation were shown to persist following intense thermal treatments

P3HT-Based Solar Cells: Structural Properties and Photovoltaic Performance

Each year we are bombarded with B.Sc. and Ph.D. applications from students that want to improve the world. They have learned that their future depends on changing the type of fuel we use and that solar energy is our future. The hope and energy of these young people will transform future energy technologies, but it will not happen quickly. Organic photovoltaic devices are easy to sketch, but the materials, processing steps, and ways of measuring the properties of the materials are very complicated. It is not trivial to make a systematic measurement that will change the way other research groups think or practice. In approaching this chapter, we thought about what a new researcher would need to know about organic photovoltaic devices and materials in order to have a good start in the subject. Then, we simplified that to focus on what a new researcher would need to know about poly-3-hexylthiophene:phenyl-C61-butyric acid methyl ester blends (P3HT: PCBM) to make research progress with these materials. This chapter is by no means authoritative or a compendium of all things on P3HT:PCBM. We have selected to explain how the sample fabrication techniques lead to control of morphology and structural features and how these morphological features have specific optical and electronic consequences for organic photovoltaic device applications

Investigation of slow dynamic processes in amorphous and crystalline polymers by 1D-MAS NMR spectroscopy

The investigation of slow molecular dynamics in several polymers (amorphous and semicrystalline) by 1D-MAS exchange NMR methods, was the aim of this work. In this work, new 1D-MAS exchange experiments are described together with the results obtained, for polymers, ranging from amorphous to semicrystalline polymers. For the relevance of the results obtained with these methods, the experimental data were always correlated with those obtained from other experimental techniques like dielectric spectroscopy, mechanical relaxation, DSC, HCS, etc. (orig.)SIGLEAvailable from: http://sundoc.bibliothek.uni-halle.de/diss-online/03/03H063/prom.pdf / FIZ - Fachinformationszzentrum Karlsruhe / TIB - Technische InformationsbibliothekDEGerman