Industry 4.0 and its impact on employment

Tato bakalářská práce zpracovává téma Průmyslu 4.0 a zkoumá, jaký má vliv na zaměstnanost v konkrétním podniku. V teoretické části jsou vymezeny základní pojmy týkající se Průmyslu 4.0, popsány průmyslové revoluce a popsány dopady konceptu Průmyslu 4.0 na společnost a trh práce. V praktické části proběhla podrobná analýza podniku, jeho produktu a výrobních procesů. Následně je za pomoci polostrukturovaného dotazníku s odborníkem z vedení společnosti zjištěno, jak společnost Průmysl 4.0 vnímá, jaké kroky zavedla, jakým směrem se chce v budoucnosti orientovat a jaký má Průmysl 4.0 vliv na zaměstnanost. Na závěr jsou zodpovězeny výzkumné otázky a vyhodnoceno splnění cíle této bakalářské práce.ObhájenoThis bachelor thesis deals with the topic of Industry 4.0 and examines how it affects employment in a particular company. The theoretical part defines the basic concepts related to Industry 4.0, describes the industrial revolutions, and describes the impacts of the concept of Industry 4.0 on society and the labor market. In the practical part there was a detailed analysis of the company, its product and production processes. Subsequently, with the help of a semi-structured questionnaire with an expert from the company's management, it is found out how Industry 4.0 perceives, what steps it has taken, what direction it wants to take in the future and how Industry 4.0 has an impact on employment. Finally, the research questions are answered and the fulfillment of the goal of the bachelor thesis is evaluated

Electronic Structures of Reduced and Superreduced Ir_2(1,8-diisocyanomenthane)_4^(n+) Complexes

Molecular and electronic structures of Ir_2(1,8-diisocyanomenthane)_4^(n+) (Ir(dimen)^(n+)) complexes have been investigated by DFT for n = 2, 1, 0 (abbreviated 2+, 1+, 0). Calculations reproduced the experimental structure of 2+, ν(C≡N) IR, and visible absorption spectra of all three oxidation states, as well as the EPR spectrum of 1+. We have shown that the two reduction steps correspond to successive filling of the Ir–Ir pσ orbital. Complexes 2+ and 1+ have very similar structures with 1+ having a shorter Ir–Ir distance. The unpaired electron density in 1+ is delocalized along the Ir–Ir axis and over N atoms of the eight C≡N– ligands. The second reduction step 1+ → 0 changes the Ir(CN−)_4 coordination geometry at each Ir site from approximately planar to seesaw whereby one −N≡C–Ir–C≡N– moiety is linear and the other bent at the Ir (137°) as well as N (146°) atoms. Although complex 0 is another example of a rare (pσ)2 dimetallic species (after [Pt_2(μ-P_2O_5(BF_2)_2)_4]^(6–), J. Am. Chem. Soc. 2016, 138, 5699), the redistribution of lower lying occupied molecular orbitals increases electron density predominantly at the bent C≡N– ligands whose N atoms are predicted to be nucleophilic reaction centers

Thermally Tunable Dual Emission of the d^8–d^8 Dimer [Pt_2(μ-P_2O_5(BF_2)_2)_4]^(4–)

High-resolution fluorescence, phosphorescence, as well as related excitation spectra, and, in particular, the emission decay behavior of solid [Bu_4N]_4[Pt_2(μ-P_2O_5(BF_2)_2)_4], abbreviated Pt(pop-BF_2), have been investigated over a wide temperature range, 1.3–310 K. We focus on the lowest excited states that result from dσ^*pσ (5d_z2–6p_z) excitations, i.e., the singlet state S_1 (of ^1A_2u symmetry in D_(4h)) and the lowest triplet T_1, which splits into spin–orbit substates A_(1u)(^3A_(2u)) and E_u(^3A_(2u)). After optical excitation, an unusually slow intersystem crossing (ISC) is observed. As a consequence, the compound shows efficient dual emission, consisting of blue fluorescence and green phosphorescence with an overall emission quantum yield of ∼100% over the investigated temperature range. Our investigation sheds light on this extraordinary dual emission behavior, which is unique for a heavy-atom transition metal compound. Direct ISC processes in Pt(pop-BF_2) are largely forbidden due to spin-, symmetry-, and Franck–Condon overlap-restrictions and, therefore, the ISC time is as long as 29 ns for T < 100 K. With temperature increase, two different thermally activated pathways, albeit still relatively slow, are promoted by spin-vibronic and vibronic mechanisms, respectively. Thus, distinct temperature dependence of the ISC processes results and, as a consequence, also of the fluorescence/phosphorescence intensity ratio. The phosphorescence lifetime also is temperature-dependent, reflecting the relative population of the triplet T_1 substates E_u and A_(1u). The highly resolved phosphorescence shows a ∼220 cm^(–1) red shift below 10 K, attributable to zero-field splitting of 40 cm^(–1) plus a promoting vibration of 180 cm^(–1)

Electron hopping through proteins

Biological redox machines require efficient transfer of electrons and holes for function. Reactions involving multiple tunneling steps, termed “hopping,” often promote charge separation within and between proteins that is essential for energy storage and conversion. Here we show how semiclassical electron transfer theory can be extended to include hopping reactions: graphical representations (called hopping maps) of the dependence of calculated two-step reaction rate constants on driving force are employed to account for flow in a rhenium-labeled azurin mutant as well as in two structurally characterized redox enzymes, DNA photolyase and MauG. Analysis of the 35 Å radical propagation in ribonucleotide reductases using hopping maps shows that all tyrosines and tryptophans on the radical pathway likely are involved in function. We suggest that hopping maps can facilitate the design and construction of artificial photosynthetic systems for the production of fuels and other chemicals

Ultrafast Wiggling and Jiggling: Ir_2(1,8-diisocyanomenthane)_4^(2+)

Binuclear complexes of d^8 metals (Pt^(II), Ir^I, Rh^I,) exhibit diverse photonic behavior, including dual emission from relatively long-lived singlet and triplet excited states, as well as photochemical energy, electron, and atom transfer. Time-resolved optical spectroscopic and X-ray studies have revealed the behavior of the dimetallic core, confirming that M–M bonding is strengthened upon dσ* → pσ excitation. We report the bridging ligand dynamics of Ir2(1,8-diisocyanomenthane)_4^(2+)(Ir(dimen)), investigated by fs–ns time-resolved IR spectroscopy (TRIR) in the region of C≡N stretching vibrations, ν(C≡N), 2000–2300 cm^(–1). The ν(C≡N) IR band of the singlet and triplet dσ*pσ excited states is shifted by −22 and −16 cm^(–1) relative to the ground state due to delocalization of the pσ LUMO over the bridging ligands. Ultrafast relaxation dynamics of the ^1dσ*pσ state depend on the initially excited Franck–Condon molecular geometry, whereby the same relaxed singlet excited state is populated by two different pathways depending on the starting point at the excited-state potential energy surface. Exciting the long/eclipsed isomer triggers two-stage structural relaxation: 0.5 ps large-scale Ir–Ir contraction and 5 ps Ir–Ir contraction/intramolecular rotation. Exciting the short/twisted isomer induces a ∼5 ps bond shortening combined with vibrational cooling. Intersystem crossing (70 ps) follows, populating a ^3dσ*pσ state that lives for hundreds of nanoseconds. During the first 2 ps, the ν(C≡N) IR bandwidth oscillates with the frequency of the ν(Ir–Ir) wave packet, ca. 80 cm^(–1), indicating that the dephasing time of the high-frequency (16 fs)^(−1) C≡N stretch responds to much slower (∼400 fs)^(−1)Ir–Ir coherent oscillations. We conclude that the bonding and dynamics of bridging di-isocyanide ligands are coupled to the dynamics of the metal–metal unit and that the coherent Ir–Ir motion induced by ultrafast excitation drives vibrational dephasing processes over the entire binuclear cation

Relaxation Dynamics of Pseudomonas aeruginosa Re^I(C)O_3(α-diimine)(HisX)^+ (X=83, 107, 109, 124, 126)Cu-^(II) Azurins

Photoinduced relaxation processes of five structurally characterized Pseudomonas aeruginosa Re^I(CO)_3(α-diimine)(HisX) (X = 83, 107, 109, 124, 126)Cu^(II) azurins have been investigated by time-resolved (ps−ns) IR spectroscopy and emission spectroscopy. Crystal structures reveal the presence of Re-azurin dimers and trimers that in two cases (X = 107, 124) involve van der Waals interactions between interdigitated diimine aromatic rings. Time-dependent emission anisotropy measurements confirm that the proteins aggregate in mM solutions (D2O, KPi buffer, pD = 7.1). Excited-state DFT calculations show that extensive charge redistribution in the ReI(CO)_3 → diimine ^3MLCT state occurs: excitation of this ^3MLCT state triggers several relaxation processes in Re-azurins whose kinetics strongly depend on the location of the metallolabel on the protein surface. Relaxation is manifested by dynamic blue shifts of excited-state ν(CO) IR bands that occur with triexponential kinetics: intramolecular vibrational redistribution together with vibrational and solvent relaxation give rise to subps, 2, and 8−20 ps components, while the ~10^2 ps kinetics are attributed to displacement (reorientation) of the Re^I(CO)_3(phen)(im) unit relative to the peptide chain, which optimizes Coulombic interactions of the Re^I excited-state electron density with solvated peptide groups. Evidence also suggests that additional segmental movements of Re-bearing β-strands occur without perturbing the reaction field or interactions with the peptide. Our work demonstrates that time-resolved IR spectroscopy and emission anisotropy of Re^I carbonyl−diimine complexes are powerful probes of molecular dynamics at or around the surfaces of proteins and protein−protein interfacial regions

Electronic Structures of Reduced and Superreduced Ir-2(1,8-diisocyanomenthane)(4)(n+) Complexes

This work was supported by the NSF CCI Solar Fuels Program (CHE-1305124). Additional support was provided by the Arnold and Mabel Beckman Foundation, the Ministry of Education of the Czech Republic (grant LD14129), and COST Actions CM1202 and CM1405

Ultrafast Wiggling and Jiggling: Ir_2(1,8-diisocyanomenthane)_4^(2+)

Binuclear complexes of d^8 metals (Pt^(II), Ir^I, Rh^I,) exhibit diverse photonic behavior, including dual emission from relatively long-lived singlet and triplet excited states, as well as photochemical energy, electron, and atom transfer. Time-resolved optical spectroscopic and X-ray studies have revealed the behavior of the dimetallic core, confirming that M–M bonding is strengthened upon dσ* → pσ excitation. We report the bridging ligand dynamics of Ir2(1,8-diisocyanomenthane)_4^(2+)(Ir(dimen)), investigated by fs–ns time-resolved IR spectroscopy (TRIR) in the region of C≡N stretching vibrations, ν(C≡N), 2000–2300 cm^(–1). The ν(C≡N) IR band of the singlet and triplet dσ*pσ excited states is shifted by −22 and −16 cm^(–1) relative to the ground state due to delocalization of the pσ LUMO over the bridging ligands. Ultrafast relaxation dynamics of the ^1dσ*pσ state depend on the initially excited Franck–Condon molecular geometry, whereby the same relaxed singlet excited state is populated by two different pathways depending on the starting point at the excited-state potential energy surface. Exciting the long/eclipsed isomer triggers two-stage structural relaxation: 0.5 ps large-scale Ir–Ir contraction and 5 ps Ir–Ir contraction/intramolecular rotation. Exciting the short/twisted isomer induces a ∼5 ps bond shortening combined with vibrational cooling. Intersystem crossing (70 ps) follows, populating a ^3dσ*pσ state that lives for hundreds of nanoseconds. During the first 2 ps, the ν(C≡N) IR bandwidth oscillates with the frequency of the ν(Ir–Ir) wave packet, ca. 80 cm^(–1), indicating that the dephasing time of the high-frequency (16 fs)^(−1) C≡N stretch responds to much slower (∼400 fs)^(−1)Ir–Ir coherent oscillations. We conclude that the bonding and dynamics of bridging di-isocyanide ligands are coupled to the dynamics of the metal–metal unit and that the coherent Ir–Ir motion induced by ultrafast excitation drives vibrational dephasing processes over the entire binuclear cation

Reduced and Superreduced Diplatinum Complexes

A d^8–d^8 complex [Pt_2(μ-P_2O_5(BF_2)_4]^(4–) (abbreviated Pt(pop-BF_2)^(4–)) undergoes two 1e– reductions at E_(1/2) = −1.68 and E_p = −2.46 V (vs Fc+/Fc) producing reduced Pt(pop-BF_2)^(5–) and superreduced Pt(pop-BF_2)^(6–) species, respectively. The EPR spectrum of Pt(pop-BF_2)^(5–) and UV–vis spectra of both the reduced and the superreduced complexes, together with TD-DFT calculations, reveal successive filling of the 6pσ orbital accompanied by gradual strengthening of Pt–Pt bonding interactions and, because of 6pσ delocalization, of Pt–P bonds in the course of the two reductions. Mayer–Millikan Pt–Pt bond orders of 0.173, 0.268, and 0.340 were calculated for the parent, reduced, and superreduced complexes, respectively. The second (5–/6−) reduction is accompanied by a structural distortion that is experimentally manifested by electrochemical irreversibility. Both reduction steps proceed without changing either d^8 Pt electronic configuration, making the superreduced Pt(pop-BF_2)^(6–) a very rare 6p^2 σ-bonded binuclear complex. However, the Pt–Pt σ bonding interaction is limited by the relatively long bridging-ligand-imposed Pt–Pt distance accompanied by repulsive electronic congestion. Pt(pop-BF_2)^(4–) is predicted to be a very strong photooxidant (potentials of +1.57 and +0.86 V are estimated for the singlet and triplet dσ*pσ excited states, respectively)