Pelaksanaan Perlindungan Hukum Bagi Awak Kapal pada PT Pelayaran Nasional Indonesia (Pelni) Semarang

Penelitian dari pelaksanaan perlindungan hukum bagi awak kapal pada PT.Pelayaran Nasional Indonesia (Pelni) Semarang ini bertujuan untuk mengetahui pelaksanaan perlindungan hukum bagi awak kapal serta mengetahui dan menganalisis hambatan-hambatan apa saja yang muncul serta upaya apa yang dilakukan PT Pelayaran Nasional Indonesia (Pelni) Semarang dalam menanggulangi hambatan pelaksanaan perlindungan hukum terhadap pekerja atau anak buah kapal. Hasil penelitian ini adalah jika dilihat dari segi perjanjian kerja laut maka tidak mencerminkan kepastian hukum yang pasti. Segi hak waktu kerja, istirahat, dan cuti, PT.Pelni Semarang telah dapat melaksanakan ketentuan dalam Pasal 79 ayat (2) UU Nomor 13 Tahun 2003 tentang Ketenagakerjaan. Segi kesehatan dan keselamatan kerja, PT.Pelni telah sesuai dengan ketentuan dari UU No.1 Tahun 1970 tentang keselamatan kapal dan telah sesuai dengan ketentuan Peraturan Pelaksanaan tentang Kecelakaan Pelaut. Hambatan dalam pelaksanaan perlindungan hukum ini kurangnya kesadaran hukum para pekerja di kapal atau anak buah kapal (ABK), dan Serikat pekerja (SP) dikuasai oleh Perusahaan dan sikap pemerintah pusat yang pasif dalam merespon permasalahan yang berkaitan dengan transportasi laut. Sehingga kesimpulan penulisan ini yaitu dari segi perjanjian kerja laut tidak mencerminkan kepastian hukum yang pasti, hak waktu kerja, istirahat dan cuti, serta segi kesehatan dan keselamatan kerja sudah sesuai dengan ketentuan pelaksanaan perlindungan hukum

Stepwise Construction of Heterobimetallic Cages by an Extended Molecular Library Approach

Two novel heterobimetallic complexes, a trigonal-bipyramidal and a cubic one, have been synthesized and characterized using the same <i>C</i>₃-symmetric metalloligand, prepared by a simple subcomponent self-assembly strategy. Adopting the molecular library approach, we chose a mononuclear, preorganized iron­(II) complex as the metallo­ligand capable of self-assembly into a trigonal-bipyramidal or a cubic aggregate upon coordination to cis-protected <i>C</i>₂-symmetric palladium­(II) or unprotected tetravalent palladium­(II) ions, respectively. The trigonal-bipyramidal complex was characterized by NMR and UV–vis spectroscopy, electrospray ionization mass spectrometry (ESI-MS), and single-crystal X-ray diffraction. The cubic structure was characterized by NMR and UV–vis spectroscopy and ESI-MS

New Chiral Cyclohexylhemicucurbit[6]uril

The first enantiomerically pure members of the cucurbituril family, (<i>all-S</i>)- and (<i>all-R</i>)-cyclohexylhemicucurbit[6]urils (cycHC), were synthesized in good yield (up to 85%). The crystal structure of this new macrocycle clearly shows its ball-like shape. CycHC monomers adopt a “zigzag” conformation, having apolar cyclohexyls around the openings and polar ureas in the middle. Cyclohexylhemicucurbit[6]urils formed complexes with halides, carboxylic acids and amines and diastereomeric complexes with methoxyphenylacetic acid in organic media. The association constants of cycHC with small organic compounds were evaluated by diffusion NMR in chloroform

DOSY NMR, X‑ray Structural and Ion-Mobility Mass Spectrometric Studies on Electron-Deficient and Electron-Rich M₆L₄ Coordination Cages

A novel modular approach to electron-deficient and electron-rich M₆L₄ cages is presented. From the same starting compound, via a minor modulation of the synthesis route, two <i>C</i>₃-symmetric ligands <b>L1</b> and <b>L2</b> with different electronic properties are obtained in good yield. The trifluoro-triethynylbenzene-based ligand <b>L1</b> is more electron-deficient than the well-known 2,4,6-tri­(4-pyridyl)-1,3,5-triazine, while the trimethoxy-triethynylbenzene-based ligand <b>L2</b> is more electron-rich than the corresponding benzene analogue. Complexation of the ligands with cis-protected square-planar [(dppp)­Pt­(OTf)₂] or [(dppp)­Pd­(OTf)₂] corner-complexes yields two electron-deficient (<b>1a</b> and <b>1b</b>) and two electron-rich (<b>2a</b> and <b>2b</b>) M₆L₄ cages. The single crystal X-ray diffraction study of <b>1a</b> and <b>2a</b> confirms the expected octahedral shape with a ca. 2000 ų cavity and ca. 11 Å wide apertures. The crystallographically determined diameters of <b>1a</b> and <b>2a</b> are 3.7 and 3.6 nm, respectively. The hydrodynamic diameters obtained from the DOSY NMR in CDCl₃:CD₃OD (4:1), and diameters calculated from collision cross sections (CCS) acquired by ion-mobility mass spectrometry (IM-MS) were for all four cages similar. In solution, the cage structures have diameters between 3.3 to 3.6 nm, while in the gas phase the corresponding diameters varied between 3.4 to 3.6 nm. In addition to the structural information the relative stabilities of the Pt₆L₄ and Pd₆L₄ cages were studied in the gas phase by collision-induced dissociation (CID) experiments, and the photophysical properties of the ligands <b>L1</b> and <b>L2</b> and cages <b>1a</b>, <b>1b</b>, <b>2a</b>, and <b>2b</b> were studied by UV–vis and fluorescence spectroscopy

DOSY NMR, X‑ray Structural and Ion-Mobility Mass Spectrometric Studies on Electron-Deficient and Electron-Rich M₆L₄ Coordination Cages

A novel modular approach to electron-deficient and electron-rich M₆L₄ cages is presented. From the same starting compound, via a minor modulation of the synthesis route, two <i>C</i>₃-symmetric ligands <b>L1</b> and <b>L2</b> with different electronic properties are obtained in good yield. The trifluoro-triethynylbenzene-based ligand <b>L1</b> is more electron-deficient than the well-known 2,4,6-tri­(4-pyridyl)-1,3,5-triazine, while the trimethoxy-triethynylbenzene-based ligand <b>L2</b> is more electron-rich than the corresponding benzene analogue. Complexation of the ligands with cis-protected square-planar [(dppp)­Pt­(OTf)₂] or [(dppp)­Pd­(OTf)₂] corner-complexes yields two electron-deficient (<b>1a</b> and <b>1b</b>) and two electron-rich (<b>2a</b> and <b>2b</b>) M₆L₄ cages. The single crystal X-ray diffraction study of <b>1a</b> and <b>2a</b> confirms the expected octahedral shape with a ca. 2000 ų cavity and ca. 11 Å wide apertures. The crystallographically determined diameters of <b>1a</b> and <b>2a</b> are 3.7 and 3.6 nm, respectively. The hydrodynamic diameters obtained from the DOSY NMR in CDCl₃:CD₃OD (4:1), and diameters calculated from collision cross sections (CCS) acquired by ion-mobility mass spectrometry (IM-MS) were for all four cages similar. In solution, the cage structures have diameters between 3.3 to 3.6 nm, while in the gas phase the corresponding diameters varied between 3.4 to 3.6 nm. In addition to the structural information the relative stabilities of the Pt₆L₄ and Pd₆L₄ cages were studied in the gas phase by collision-induced dissociation (CID) experiments, and the photophysical properties of the ligands <b>L1</b> and <b>L2</b> and cages <b>1a</b>, <b>1b</b>, <b>2a</b>, and <b>2b</b> were studied by UV–vis and fluorescence spectroscopy

DOSY NMR, X‑ray Structural and Ion-Mobility Mass Spectrometric Studies on Electron-Deficient and Electron-Rich M₆L₄ Coordination Cages

A novel modular approach to electron-deficient and electron-rich M₆L₄ cages is presented. From the same starting compound, via a minor modulation of the synthesis route, two <i>C</i>₃-symmetric ligands <b>L1</b> and <b>L2</b> with different electronic properties are obtained in good yield. The trifluoro-triethynylbenzene-based ligand <b>L1</b> is more electron-deficient than the well-known 2,4,6-tri­(4-pyridyl)-1,3,5-triazine, while the trimethoxy-triethynylbenzene-based ligand <b>L2</b> is more electron-rich than the corresponding benzene analogue. Complexation of the ligands with cis-protected square-planar [(dppp)­Pt­(OTf)₂] or [(dppp)­Pd­(OTf)₂] corner-complexes yields two electron-deficient (<b>1a</b> and <b>1b</b>) and two electron-rich (<b>2a</b> and <b>2b</b>) M₆L₄ cages. The single crystal X-ray diffraction study of <b>1a</b> and <b>2a</b> confirms the expected octahedral shape with a ca. 2000 ų cavity and ca. 11 Å wide apertures. The crystallographically determined diameters of <b>1a</b> and <b>2a</b> are 3.7 and 3.6 nm, respectively. The hydrodynamic diameters obtained from the DOSY NMR in CDCl₃:CD₃OD (4:1), and diameters calculated from collision cross sections (CCS) acquired by ion-mobility mass spectrometry (IM-MS) were for all four cages similar. In solution, the cage structures have diameters between 3.3 to 3.6 nm, while in the gas phase the corresponding diameters varied between 3.4 to 3.6 nm. In addition to the structural information the relative stabilities of the Pt₆L₄ and Pd₆L₄ cages were studied in the gas phase by collision-induced dissociation (CID) experiments, and the photophysical properties of the ligands <b>L1</b> and <b>L2</b> and cages <b>1a</b>, <b>1b</b>, <b>2a</b>, and <b>2b</b> were studied by UV–vis and fluorescence spectroscopy

DOSY NMR, X‑ray Structural and Ion-Mobility Mass Spectrometric Studies on Electron-Deficient and Electron-Rich M₆L₄ Coordination Cages

A novel modular approach to electron-deficient and electron-rich M₆L₄ cages is presented. From the same starting compound, via a minor modulation of the synthesis route, two <i>C</i>₃-symmetric ligands <b>L1</b> and <b>L2</b> with different electronic properties are obtained in good yield. The trifluoro-triethynylbenzene-based ligand <b>L1</b> is more electron-deficient than the well-known 2,4,6-tri­(4-pyridyl)-1,3,5-triazine, while the trimethoxy-triethynylbenzene-based ligand <b>L2</b> is more electron-rich than the corresponding benzene analogue. Complexation of the ligands with cis-protected square-planar [(dppp)­Pt­(OTf)₂] or [(dppp)­Pd­(OTf)₂] corner-complexes yields two electron-deficient (<b>1a</b> and <b>1b</b>) and two electron-rich (<b>2a</b> and <b>2b</b>) M₆L₄ cages. The single crystal X-ray diffraction study of <b>1a</b> and <b>2a</b> confirms the expected octahedral shape with a ca. 2000 ų cavity and ca. 11 Å wide apertures. The crystallographically determined diameters of <b>1a</b> and <b>2a</b> are 3.7 and 3.6 nm, respectively. The hydrodynamic diameters obtained from the DOSY NMR in CDCl₃:CD₃OD (4:1), and diameters calculated from collision cross sections (CCS) acquired by ion-mobility mass spectrometry (IM-MS) were for all four cages similar. In solution, the cage structures have diameters between 3.3 to 3.6 nm, while in the gas phase the corresponding diameters varied between 3.4 to 3.6 nm. In addition to the structural information the relative stabilities of the Pt₆L₄ and Pd₆L₄ cages were studied in the gas phase by collision-induced dissociation (CID) experiments, and the photophysical properties of the ligands <b>L1</b> and <b>L2</b> and cages <b>1a</b>, <b>1b</b>, <b>2a</b>, and <b>2b</b> were studied by UV–vis and fluorescence spectroscopy

Experimental and Theoretical Investigation of Structures, Stoichiometric Diversity, and Bench Stability of Cocrystals with a Volatile Halogen Bond Donor

We present a combined experimental and theoretical study of the structures and bench stability of halogen-bonded cocrystals involving the volatile halogen bond donor octafluoro-1,4-diiodobutane, with phenazine and acridine as acceptors. Cocrystallization experiments using mechanochemistry and solution crystallization revealed three chemically and structurally distinct cocrystals. Whereas only one cocrystal form has been observed with acridine, cocrystallization with phenazine led to two stoichiometrically different cocrystals, in which phenazine employs either one or two nitrogen atoms per molecule as halogen bond acceptor sites. Cocrystal stability was evaluated experimentally by simultaneous thermogravimetric analysis and differential thermal analysis or differential scanning calorimetry, real-time powder X-ray diffraction monitoring of cocrystals upon storage in open air, and theoretically by using dispersion-corrected periodic density functional theory. The use of real-time powder X-ray diffraction enabled the comparison of rates of cocrystal decomposition, and the observed trends in cocrystal stability were reproduced by the ranking of theoretically calculated cocrystal decomposition enthalpies. Whereas all cocrystals eventually lose the volatile halogen bond donor upon storage in open air or by heating, these experimental and theoretical studies show that the cocrystal of acridine is the most stable, in agreement with its more basic properties. The stoichiometric variations of the phenazine cocrystal also exhibit a notable difference in stability, with the cocrystal containing the halogen bond acceptor and donor in a 1:1 stoichiometric ratio being of particularly low stability, decomposing in open air within minutes

Enantiomerically Pure Trinuclear Helicates via Diastereoselective Self-Assembly and Characterization of Their Redox Chemistry

A tris­(bipyridine) ligand <b>1</b> with two BINOL (BINOL = 2,2′-di­hydroxy-1,1′-binaphthyl) groups has been prepared in two enantiomerically pure forms. This ligand undergoes completely diastereo­selective self-assembly into <i>D</i>₂-symmeteric double-stranded trinuclear helicates upon coordination to copper­(I) and silver­(I) ions and to <i>D</i>₃-symmetric triple-stranded trinuclear helicates upon coordination to copper­(II), zinc­(II), and iron­(II) ions as demonstrated by mass spectrometry, NMR and CD spectroscopy in combination with quantum chemical calculations and X-ray diffraction analysis. According to the calculations, the single diastereomers that are formed during the self-assembly process are strongly preferred compared to the next stable diastereomers. Due to this strong preference, the self-assembly of the helicates from racemic <b>1</b> proceeds in a completely narcissistic self-sorting manner with an extraordinary high degree of self-sorting that proves the power and reliability of this approach to achieve high-fidelity diastereo­selective self-assembly via chiral self-sorting to get access to stereo­chemically well-defined nanoscaled objects. Furthermore, mass spectrometric methods including electron capture dissociation MS^<i>n</i> experiments could be used to elucidate the redox behavior of the copper helicates

“Two-Story” Calix[6]arene-Based Zinc and Copper Complexes: Structure, Properties, and O₂ Binding

A new “two-story” calix[6]­arene-based ligand was synthesized, and its coordination chemistry was explored. It presents a tren cap connected to the calixarene small rim through three amido spacers. X-ray diffraction studies of its metal complexes revealed a six-coordinate Zn^II complex with all of the carbonyl groups of the amido arms bound and a five-coordinate Cu^II complex with only one amido arm bound. These dicationic complexes were poorly responsive toward exogenous neutral donors, but the amido arms were readily displaced by small anions or deprotonated with a base to give the corresponding monocationic complexes. Cyclic voltammetry in various solvents showed a reversible wave for the Cu^II/Cu^I couple at very negative potentials, denoting an electron-rich environment. The reversibility of the system was attributed to the amido arms, which can coordinate the metal center in both its +II and +I redox states. The reversibility was lost upon anion binding to Cu. Upon exposure of the Cu^I complex to O₂ at low temperature, a green species was obtained with a UV–vis signature typical of an <i>end-on</i> superoxide Cu^II complex. Such a species was proposed to be responsible for oxygen insertion reactions onto the ligand according to the unusual and selective four-electron oxidative pathway previously described with a “one-story” calix[6]­tren ligand