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Sintetizovali smo seriju Ni kompleksa koristeći različite donorske ligande na bazi NNO hidrazona i azidne anjone. Tri kompleksa su kristalizovala kao dvonuklearna, Ni(II) jona su koordinovani sa NNO ligandom i tri azidna liganda (dva mostna). U četvrtom kompleksu, Ni (II) je koordinovan sa dva NNO liganda. Da bismo razumeli ove različite ishode, izračunali smo ∆G energije za dimerizaciju i formiranje kompleksa sa dva NNO liganda, iz mononuklearnih kompleksa. Energije su izračunate koristeći M06-2X metodu sa Grimeovom D3 disperzionom korekcijom i def2-TZVP bazisom. Iako je dimerizacija povoljnija u svim slučajevima, ∆G energetska razlika je samo 1,7 kcal/mol za četvrti kompleks. Ova mala razlika se može prevazići energijama interakcije sa rastvorom ili u kristalnim strukturama. ∆G energetske razlike u drugim kompleksima su od 5 kcal/mol do 15 kcal/mol., We have synthesized a series of a Ni complex using different NNO hydrazone-based donor ligands and azide anions. Three complexes crystallized as dinuclear, Ni(II) ions are coordinated with NNO ligand and three azide ligands (two bridging). In the fourth complex, Ni(II) is coordinated with two NNO ligands. To understand these different outcomes, we calculated the ∆G energies for dimerization and formation of complexes with two NNO ligands, from mononuclear complexes. The energies are calculated using the M06-2X method with Grimmes D3 dispersion correction and def2-TZVP basis. Aldo the dimerization is more favorable in all cases, the ∆G energy difference is only 1.7 kcal/mole for the fourth complex. This small difference could be overcome by the interaction energies with the solution or in the crystal structures. The ∆G energy differences in other complexes are from 5 kcal/mol to 15 kcal/mol.

Algal biomass is a viable source of chemicals andmetabolites for various energy, nutritional, medicinal and agricultural uses. While stresses have commonly been used to induce metabolite accumulation in microalgae in attempts to enhance high-value product yields, this is often very detrimental to growth. Therefore, understanding how to modify metabolism without deleterious consequences is highly beneficial. We demonstrate that low-doses (1–5 Gy) of ionizing radiation in the X-ray range induces a non-toxic, hormetic response in microalgae to promote metabolic activation. We identify specific radiation exposure parameters that give reproducible metabolic responses in Chlorella sorokiniana caused by transcriptional changes. This includes up-regulation of >30 lipid metabolismgenes, such as genes encoding an acetyl-CoA carboxylase subunit, phosphatidic acid phosphatase, lysophosphatidic acid acyltransferase, and diacylglycerol acyltransferase. The outcome is an increased lipid yield in stationary phase cultures by 25% in just 24 hours, without any negative effects on cell viability or biomass.

Companies can help their employees better manage their finances through employee benefits programs such as financial counseling and retirement planning assistance. These programs provide employees with the necessary knowledge and tools to make wise financial decisions, thereby improving their financial management capabilities and positively impacting their long-term financial well-being. A good and stable working relationship provides many financial benefits, such as income stability, additional benefits, and company support in professional development and financial management. This research uses a qualitative method with data collection based on a thorough literature search and literature sources. In addition, the psychological and emotional impact of layoffs also needs to be considered as it can threaten employees' quality of life and mental health. Therefore, it is important for companies and governments to provide support and assistance programs for employees affected by layoffs to help them recover and achieve financial stability and well-being in the future. Layoffs can have serious consequences including loss of income, cash flow disruption, debt, loss of social security and health insurance, and psychological distress. The negative impact of layoffs is not only limited to finances, but also includes stress, anxiety, depression and disruption of personal relationships. Therefore, it is important for companies and governments to work together to provide support and assistance programs to employees affected by layoffs.

Companies can help their employees better manage their finances through employee benefits programs such as financial counseling and retirement planning assistance. These programs provide employees with the necessary knowledge and tools to make wise financial decisions, thereby improving their financial management capabilities and positively impacting their long-term financial well-being. A good and stable working relationship provides many financial benefits, such as income stability, additional benefits, and company support in professional development and financial management. This research uses a qualitative method with data collection based on a thorough literature search and literature sources. In addition, the psychological and emotional impact of layoffs also needs to be considered as it can threaten employees' quality of life and mental health. Therefore, it is important for companies and governments to provide support and assistance programs for employees affected by layoffs to help them recover and achieve financial stability and well-being in the future. Layoffs can have serious consequences including loss of income, cash flow disruption, debt, loss of social security and health insurance, and psychological distress. The negative impact of layoffs is not only limited to finances, but also includes stress, anxiety, depression and disruption of personal relationships. Therefore, it is important for companies and governments to work together to provide support and assistance programs to employees affected by layoffs.

The Next Generation Science Standards (NGSS) have high requirements regarding science knowledge and academic vocabulary that need to be taught to students using research-based curriculum and teaching techniques. Students who receive Special Education services or who are ELL are known to encounter difficulties learning new and complex scientific concepts but, according to NGSS, they need to be held accountable to the same standards as their typical peers. Numerous studies show that Project-Based Learning (P-BL) together with scaffolding and group learning have been used successfully in science classrooms at different grade levels. Since school districts started to implement NGSS, there has not been enough research conducted to indicate how the new requirements address the various needs of a diverse student body, and there is still need of more studies that are assessing different ways in which the new science standards are being applied in classrooms. This study searches for evidence of whether a science curriculum that is currently used in a school district in Southern California and which was designed as a P-BL, integrated science curriculum for General Education classes, is also effective for students who receive Special Education services or who are ELL.

The Next Generation Science Standards (NGSS) have high requirements regarding science knowledge and academic vocabulary that need to be taught to students using research-based curriculum and teaching techniques. Students who receive Special Education services or who are ELL are known to encounter difficulties learning new and complex scientific concepts but, according to NGSS, they need to be held accountable to the same standards as their typical peers. Numerous studies show that Project-Based Learning (P-BL) together with scaffolding and group learning have been used successfully in science classrooms at different grade levels. Since school districts started to implement NGSS, there has not been enough research conducted to indicate how the new requirements address the various needs of a diverse student body, and there is still need of more studies that are assessing different ways in which the new science standards are being applied in classrooms. This study searches for evidence of whether a science curriculum that is currently used in a school district in Southern California and which was designed as a P-BL, integrated science curriculum for General Education classes, is also effective for students who receive Special Education services or who are ELL.

[Objective] Gait disturbance lowers activities of daily living in patients with Parkinson’s disease (PD) and related disorders. However, the effectiveness of pharmacological, surgical and rehabilitative treatments is limited. We recently developed a novel neuromodulation approach using gait-combined closed-loop transcranial electrical stimulation (tES) for healthy volunteers and patients who are post-stroke, and achieved significant entrainment of gait rhythm and an increase in gait speed. Here, we tested the efficacy of this intervention in patients with Parkinsonian gait disturbances. [Methods] Twenty-three patients were randomly assigned to a real intervention group using gait-combined closed-loop oscillatory tES over the cerebellum at the frequency of individualised comfortable gait rhythm, and to a sham control group. [Results] Ten intervention sessions were completed for all patients and showed that the gait speed (F(1, 21)=13.0, p=0.002) and stride length (F(1, 21)=8.9, p=0.007) were significantly increased after tES, but not after sham stimulation. Moreover, gait symmetry measured by swing phase time (F(1, 21)=11.9, p=0.002) and subjective feelings about freezing (F(1, 21)=14.9, p=0.001) were significantly improved during gait. [Conclusions] These findings showed that gait-combined closed-loop tES over the cerebellum improved Parkinsonian gait disturbances, possibly through the modulation of brain networks generating gait rhythms. This new non-pharmacological and non-invasive intervention could be a breakthrough in restoring gait function in patients with PD and related disorders.

For pluripotent stem cell (PSC)-based regenerative therapy against diabetes, the differentiation efficiency to pancreatic lineage cells needs to be improved based on the mechanistic understanding of pancreatic differentiation. Here, we aimed to elucidate the molecular mechanisms underlying pancreatic endoderm differentiation by searching for factors that regulate a crucial pancreatic endoderm marker gene, NKX6.1. Unbiasedly screening an siRNA knockdown library, we identified a candidate transcription factor, HHEX. HHEX knockdown suppressed the expression of another pancreatic endoderm marker gene, PTF1A, as well as NKX6.1, independently of PDX1, a known regulator of NKX6.1 expression. In contrast, the overexpression of HHEX upregulated the expressions of NKX6.1 and PTF1A. RNA-seq analysis showed decreased expressions of several genes related to pancreatic development, such as NKX6.1, PTF1A, ONECUT1 and ONECUT3, in HHEX knockdown pancreatic endoderm. These results suggest that HHEX plays a key role in pancreatic endoderm differentiation.

The plasma shutter is a thin solid foil (or series of them) placed in front of the main target irradiated by high intense laser. It can mitigate the prepulse and also shape the main pulse, resulting in the generation of a steep-rising front and local intensity increase of the pulse. We study the application of the shutter for ion acceleration via 3D PIC simulations assuming Si₃N₄ plasma shutter, ultrathin silver target and a PW-class laser. The application of shutter results in increase of maximal ion energy for both linear and circular polarizations. It also significantly reduces the beam divergence for the linear polarization. In the case of circular polarization, the transmitted laser pulse obtains a spiral-like intensity profile. The structure is transferred into the electron density profile of the shutter and the main target behind it. The use of a double-shutter is studied via a combination of 2D PIC and hydrodynamic simulations assuming the laser pulse accompanied by a sub-ns prepulse. We present a prototype of the double-shutter and the design of the whole shutter-target setup. The generated steep-front has also positive effect on different scenario with low-Z double-layer targets. The 3D shutter simulation is also represented via an interactive Virtual Reality visualization.

Objectives: The CD274 (programmed cell death 1 ligand 1, PD-L1)/PDCD1 (programmed cell death 1, PD-1) immune checkpoint axis is known to regulate the antitumor immune response. Evidence also supports an immunosuppressive effect of Fusobacterium nucleatum. We hypothesised that tumor CD274 overexpression might be inversely associated with abundance of F. nucleatum in colorectal carcinoma. Methods: We assessed tumor CD274 expression by immunohistochemistry and F. nucleatum DNA within tumor tissue by quantitative PCR in 812 cases among 4465 incident rectal and colon cancer cases that had occurred in two prospective cohort studies. Multivariable logistic regression analyses with inverse probability weighting were used to adjust for selection bias because of tissue data availability and potential confounders including microsatellite instability status, CpG island methylator phenotype, LINE-1 methylation level and KRAS, BRAF and PIK3CA mutations. Results: Fusobacterium nucleatum DNA was detected in tumor tissue in 109 (13%) cases. Tumor CD274 expression level was inversely associated with the amount of F. nucleatum in colorectal cancer tissue (P = 0.0077). For one category-unit increase in three ordinal F. nucleatum categories (negative vs. low vs. high), multivariable-adjusted odds ratios (with 95% confidence interval) of the low, intermediate and high CD274 categories (vs. negative) were 0.78 (0.41–1.51), 0.64 (0.32–1.28) and 0.50 (0.25–0.99), respectively (Ptrend = 0.032). Conclusions: Tumor CD274 expression level was inversely associated with the amount of F. nucleatum in colorectal cancer tissue, suggesting that different immunosuppressive mechanisms (i.e. PDCD1 immune checkpoint activation and tumor F. nucleatum enrichment) tend to be used by different tumor subgroups.

In this paper, we report the synthesis, characterization, and X-ray structure analysis of one octahedral Ni(II) complex, [Ni(HL1 )2](BF4)2*H2O, formed by coordination of two ligands with NNS donor atom sets (HL1 ligand, (E)-2-(1-(thiazol-2-yl)ethylidene)hydrazine-1-carbothioamide), and Ni(III) complex, [Ni(L2 )(N3)3], formed by coordination of one hydrazone ligand coordinated through NNO donor set and three azide anions (HL2Cl ligand, (E)−1-(2-oxo-2-(2-(1-(pyridin-2- yl)ethylidene)hydrazinyl)ethyl)pyridin-1-ium chloride), complemented by DFT calculations. To the best of our knowledge this is the first Ni(III) complex obtained under ambient conditions.

In this paper, we report the synthesis, characterization, and X-ray structure analysis of one octahedral Ni(II) complex, [Ni(HL1 )2](BF4)2*H2O, formed by coordination of two ligands with NNS donor atom sets (HL1 ligand, (E)-2-(1-(thiazol-2-yl)ethylidene)hydrazine-1-carbothioamide), and Ni(III) complex, [Ni(L2 )(N3)3], formed by coordination of one hydrazone ligand coordinated through NNO donor set and three azide anions (HL2Cl ligand, (E)−1-(2-oxo-2-(2-(1-(pyridin-2- yl)ethylidene)hydrazinyl)ethyl)pyridin-1-ium chloride), complemented by DFT calculations. To the best of our knowledge this is the first Ni(III) complex obtained under ambient conditions.

The HL ligand, (E)-2-(1-(thiazol-2-yl)ethylidene)hydrazine-1-carbothioamide, was obtained from the condensation reaction of thiosemicarbazide and 2-acetylthiazole in water. The reaction of the HL ligand with the metal salt MnCl2·4H2O in a molar ratio 1:1 in methanol/water mixture results in the formation of bis Mn(II) complex with composition [MnL2]. Complex 1 crystallizes in the triclinic crystal system with space group P−1. The Mn(II) ion is hexacoordinated with two tridentate ligands L through NNS sets of donor atoms. The geometry around the Mn is described as a distorted trigonal prism (Fig. 1). The reaction of the ligand HL with Fe(BF4)2·6H2O in a molar ratio 1:1 in methanol results in the formation of bis Fe(III) complex with composition [Fe(L)2]BF4·H2O. The Fe(III) ion with L form six-coordinate complex in which two deprotonated ligand molecules coordinate in a mer arrangement, forming a distorted octahedral complex by chelation through NNS sets of donor atoms (Fig. 1). Complex 2 crystallizes in the orthorhombic crystal system with space group Pbca.

Poster presented at The Training School of COST action CA21101 COSY ,,Multiscale modeling of the properties of compounds: From isolated molecules to 3D materials relevant for industrial and astrophysical application", Belgrade, Serbia, 19th – 22nd September 2023.

The plasma shutter is a thin solid foil (or series of them) placed in front of the main target irradiated by high intense laser. It can mitigate the prepulse and also shape the main pulse, resulting in the generation of a steep-rising front and local intensity increase of the pulse. We study the application of the shutter for ion acceleration via 3D PIC simulations assuming Si₃N₄ plasma shutter, ultrathin silver target and a PW-class laser. The application of shutter results in increase of maximal ion energy for both linear and circular polarizations. It also significantly reduces the beam divergence for the linear polarization. In the case of circular polarization, the transmitted laser pulse obtains a spiral-like intensity profile. The structure is transferred into the electron density profile of the shutter and the main target behind it. The use of a double-shutter is studied via a combination of 2D PIC and hydrodynamic simulations assuming the laser pulse accompanied by a sub-ns prepulse. We present a prototype of the double-shutter and the design of the whole shutter-target setup. The generated steep-front has also positive effect on different scenario with low-Z double-layer targets. The 3D shutter simulation is also represented via an interactive Virtual Reality visualization.

The condensation product of 7-acetyl-6-azaindole and Girard’s T reagent ((E)-2-(2-(1-(1H-pyrrolo[2,3-c]pyridin-7-yl)ethylidene)hydrazineyl)-N,N,N-trimethyl-2-oxoethan-1-aminium, HL ligand) was used as a ligand in the reaction with Cu(BF4)2·6H2O and NaN3. The reaction led to the formation of a binuclear Cu(II) complex containing two end-to-end (di-µ-1,3-N3) azide bridges, as well as two NNO-donor hydrazone ligands, forming an axially elongated square pyramidal geometry around each Cu(II) center.

The condensation product of 7-acetyl-6-azaindole and Girard’s T reagent ((E)-2-(2-(1- (1H-pyrrolo[2,3-c]pyridin-7-yl)ethylidene)hydrazineyl)-N,N,N-trimethyl-2-oxoethan-1-aminium, HL ligand) was used as a ligand in the reaction with Cu(BF4)2·6H2O and NaN3. The reaction led to the formation of a binuclear Cu(II) complex containing two end-to-end (di-µ-1,3-N3) azide bridges, as well as two NNO-donor hydrazone ligands, forming an axially elongated square pyramidal geometry around each Cu(II) center.

Fe(III) and Mn(II) complexes with condensation product of thiosemicarbazide and 2-acetylthiazole (HL1, (E)-2-(1-(thiazol-2-yl)ethylidene)hydrazine-1-carbothioamide) have been synthesized and characterized by single-crystal X-ray diffraction, IR spectroscopy, and elemental analysis. In both complexes, the thiosemicarbazone ligand is coordinated in deprotonated form through the NNS donor set of atoms. However, while Fe(III) complex is in the doublet ground state with distorted octahedral geometry, the coordination environment around Mn(II) is distorted trigonal-prismatic, and the sextet state is found to be the ground state. DFT calculations were performed to rationalize spin state preferences, and continuous shape measure describes the deviation from ideal six-coordinated polyhedral geometries in the ground and excited states. Antimicrobial activity (against a panel of Gram-negative and Gram-positive bacteria, two yeast, and one fungal strain), brine shrimp assay, and DPPH radical scavenging activity of both complexes were evaluated, and these results relate to the electronic structure of the complexes.

In this paper, we report the synthesis, characterization, and X-ray structure analysis of one octahedral Ni(II) complex, [Ni(HL1 )2](BF4)2*H2O, formed by coordination of two ligands with NNS donor atom sets (HL1 ligand, (E)-2-(1-(thiazol-2-yl)ethylidene)hydrazine-1-carbothioamide), and Ni(III) complex, [Ni(L2 )(N3)3], formed by coordination of one hydrazone ligand coordinated through NNO donor set and three azide anions (HL2Cl ligand, (E)−1-(2-oxo-2-(2-(1-(pyridin-2- yl)ethylidene)hydrazinyl)ethyl)pyridin-1-ium chloride), complemented by DFT calculations. To the best of our knowledge this is the first Ni(III) complex obtained under ambient conditions.

In this paper, we report the synthesis, characterization, and X-ray structure analysis of one octahedral Ni(II) complex, [Ni(HL1 )2](BF4)2*H2O, formed by coordination of two ligands with NNS donor atom sets (HL1 ligand, (E)-2-(1-(thiazol-2-yl)ethylidene)hydrazine-1-carbothioamide), and Ni(III) complex, [Ni(L2 )(N3)3], formed by coordination of one hydrazone ligand coordinated through NNO donor set and three azide anions (HL2Cl ligand, (E)−1-(2-oxo-2-(2-(1-(pyridin-2- yl)ethylidene)hydrazinyl)ethyl)pyridin-1-ium chloride), complemented by DFT calculations. To the best of our knowledge this is the first Ni(III) complex obtained under ambient conditions.

Mn(II) and Fe(III) complexes with condensation product of thiosemicarbazide and 2-acetylthiazole have been synthesized and characterized by single-crystal X-ray diffraction. Two complexes have the same ligand system – bis tridentate coordination of the thiosemicarbazone ligand through the NNS donor set of atoms. Furthermore, the central metal ions in both cases have the same d5 electronic configuration. However, measured magnetism and analysis of the crystal geometries show that these two complexes have a different number of unpaired electrons. We rationalized the results by electronic structure calculations based on density functional theory. High-spin Mn(II) complex has trigonal-prismatic geometry with ionic metal-ligand bonding. Hund's rule of maximum multiplicity is responsible for its sextet spin-ground state. On the other hand, low-spin Fe(III) complex has octahedral coordination and strong metal-ligand covalency with delocalization of spin density toward ligands. Low-spin, doublet state is favored because of the nephelauxetic effect, i.e., smaller pairing energy in Fe(III) complex. Our results show that the difference in the electronic structure of the two complexes, i.e., different spin-ground states, directly affects these molecules' structure, magnetism, reactivity, and biological activities.

The ligand (HLCl) was synthetized by the reaction of 2-acetylpyridine and Girard’s P reagent in molar ratio 1 : 1 in ethanol (1–2 drops of cc. HCl were added). The reaction of hydrazone ligand with the metal salt Ni(BF4)2·6H2O and NaN3 in a molar ratio 1:1:4 in methanol/acetonitrile/water mixture results in the formation of Ni(III) complex with composition [NiL(N3)3]. The tridentate ligand (HLCl) is coordinated in deprotonated, formally neutral, form to the nickel ion through NNO set of donor atoms forming two five-membered chelate rings and the other three coordination sites are occupied by meridionally coordinated azide anions. The ligand (HLCl) was characterized by elemental analysis, IR and NMR spectroscopy and structure of the complex was defined by X-ray analysis, IR and EPR spectroscopy, molar conductivity and elemental analysis. DFT calculations were performed to determine stability and rationalise formation of Ni(III) complex.

The ligand (HLCl) was synthetized by the reaction of 2-acetylpyridine and Girard’s P reagent in molar ratio 1 : 1 in ethanol (1–2 drops of cc. HCl were added). The reaction of hydrazone ligand with the metal salt Ni(BF4)2·6H2O and NaN3 in a molar ratio 1:1:4 in methanol/acetonitrile/water mixture results in the formation of Ni(III) complex with composition [NiL(N3)3]. The tridentate ligand (HLCl) is coordinated in deprotonated, formally neutral, form to the nickel ion through NNO set of donor atoms forming two five-membered chelate rings and the other three coordination sites are occupied by meridionally coordinated azide anions. The ligand (HLCl) was characterized by elemental analysis, IR and NMR spectroscopy and structure of the complex was defined by X-ray analysis, IR and EPR spectroscopy, molar conductivity and elemental analysis. DFT calculations were performed to determine stability and rationalise formation of Ni(III) complex.

Mn(II) and Fe(III) complexes with condensation product of thiosemicarbazide and 2-acetylthiazole have been synthesized and characterized by single-crystal X-ray diffraction. Two complexes have the same ligand system – bis tridentate coordination of the thiosemicarbazone ligand through the NNS donor set of atoms. Furthermore, the central metal ions in both cases have the same d5 electronic configuration. However, measured magnetism and analysis of the crystal geometries show that these two complexes have a different number of unpaired electrons. We rationalized the results by electronic structure calculations based on density functional theory. High-spin Mn(II) complex has trigonal-prismatic geometry with ionic metal-ligand bonding. Hund's rule of maximum multiplicity is responsible for its sextet spin-ground state. On the other hand, low-spin Fe(III) complex has octahedral coordination and strong metal-ligand covalency with delocalization of spin density toward ligands. Low-spin, doublet state is favored because of the nephelauxetic effect, i.e., smaller pairing energy in Fe(III) complex. Our results show that the difference in the electronic structure of the two complexes, i.e., different spin-ground states, directly affects these molecules' structure, magnetism, reactivity, and biological activities.

In [15], Leonardi and Ruiz-Lopez propose an additively homomorphic public key encryption scheme whose security is expected to depend on the hardness of the learning homomorphism with noise problem (LHN). Choosing parameters for their primitive requires choosing three groups $G$, $H$, and $K$. In their paper, Leonardi and Ruiz-Lopez claim that, when $G$, $H$, and $K$ are abelian, then their public key cryptosystem is not quantum secure. In this paper, we study security for finite abelian groups $G$, $H$, and $K$ in the classical case. Moreover, we study quantum attacks on instantiations with solvable groups., Comment: 20 pages, changes in compliance with the referees' suggestions, to appear in the Springer AWM volume "Women in Numbers Europe 4 - Research Directions in Number Theory"

Fe(III) and Mn(II) complexes with condensation product of thiosemicarbazide and 2-acetylthiazole (HL1, (E)-2-(1-(thiazol-2-yl)ethylidene)hydrazine-1-carbothioamide) have been synthesized and characterized by single-crystal X-ray diffraction, IR spectroscopy, and elemental analysis. In both complexes, the thiosemicarbazone ligand is coordinated in deprotonated form through the NNS donor set of atoms. However, while Fe(III) complex is in the doublet ground state with distorted octahedral geometry, the coordination environment around Mn(II) is distorted trigonal-prismatic, and the sextet state is found to be the ground state. DFT calculations were performed to rationalize spin state preferences, and continuous shape measure describes the deviation from ideal six-coordinated polyhedral geometries in the ground and excited states. Antimicrobial activity (against a panel of Gram-negative and Gram-positive bacteria, two yeast, and one fungal strain), brine shrimp assay, and DPPH radical scavenging activity of both complexes were evaluated, and these results relate to the electronic structure of the complexes., Additional crystallographic and computational results, and the Cartesian coordinates of all DFT optimized structures

Fe(III) and Mn(II) complexes with condensation product of thiosemicarbazide and 2-acetylthiazole (HL1, (E)-2-(1-(thiazol-2-yl)ethylidene)hydrazine-1-carbothioamide) have been synthesized and characterized by single-crystal X-ray diffraction, IR spectroscopy, and elemental analysis. In both complexes, the thiosemicarbazone ligand is coordinated in deprotonated form through the NNS donor set of atoms. However, while Fe(III) complex is in the doublet ground state with distorted octahedral geometry, the coordination environment around Mn(II) is distorted trigonal-prismatic, and the sextet state is found to be the ground state. DFT calculations were performed to rationalize spin state preferences, and continuous shape measure describes the deviation from ideal six-coordinated polyhedral geometries in the ground and excited states. Antimicrobial activity (against a panel of Gram-negative and Gram-positive bacteria, two yeast, and one fungal strain), brine shrimp assay, and DPPH radical scavenging activity of both complexes were evaluated, and these results relate to the electronic structure of the complexes.

Fe(III) and Mn(II) complexes with condensation product of thiosemicarbazide and 2-acetylthiazole (HL1, (E)-2-(1-(thiazol-2-yl)ethylidene)hydrazine-1-carbothioamide) have been synthesized and characterized by single-crystal X-ray diffraction, IR spectroscopy, and elemental analysis. In both complexes, the thiosemicarbazone ligand is coordinated in deprotonated form through the NNS donor set of atoms. However, while Fe(III) complex is in the doublet ground state with distorted octahedral geometry, the coordination environment around Mn(II) is distorted trigonal-prismatic, and the sextet state is found to be the ground state. DFT calculations were performed to rationalize spin state preferences, and continuous shape measure describes the deviation from ideal six-coordinated polyhedral geometries in the ground and excited states. Antimicrobial activity (against a panel of Gram-negative and Gram-positive bacteria, two yeast, and one fungal strain), brine shrimp assay, and DPPH radical scavenging activity of both complexes were evaluated, and these results relate to the electronic structure of the complexes.

In this paper, we report the synthesis, characterization, and X-ray structure analysis of one octahedral Ni(II) complex, [Ni(HL1 )2](BF4)2*H2O, formed by coordination of two ligands with NNS donor atom sets (HL1 ligand, (E)-2-(1-(thiazol-2-yl)ethylidene)hydrazine-1-carbothioamide), and Ni(III) complex, [Ni(L2 )(N3)3], formed by coordination of one hydrazone ligand coordinated through NNO donor set and three azide anions (HL2Cl ligand, (E)−1-(2-oxo-2-(2-(1-(pyridin-2- yl)ethylidene)hydrazinyl)ethyl)pyridin-1-ium chloride), complemented by DFT calculations. To the best of our knowledge this is the first Ni(III) complex obtained under ambient conditions., 1. Experimental section. 2. Single crystal X-ray diffraction study. 3. Computational details. 4. Additional details

Crystal data for complex 2.

Crystal data for complex 1.

Ferrers diagram rank-metric codes were introduced by Etzion and Silberstein in 2009. In their work, they proposed a conjecture on the largest dimension of a space of matrices over a finite field whose nonzero elements are supported on a given Ferrers diagram and all have rank lower bounded by a fixed positive integer $d$. Since stated, the Etzion-Silberstein conjecture has been verified in a number of cases, often requiring additional constraints on the field size or on the minimum rank $d$ in dependence of the corresponding Ferrers diagram. As of today, this conjecture still remains widely open. Using modular methods, we give a constructive proof of the Etzion-Silberstein conjecture for the class of strictly monotone Ferrers diagrams, which does not depend on the minimum rank $d$ and holds over every finite field. In addition, we leverage on the last result to also prove the conjecture for the class of MDS-constructible Ferrers diagrams, without requiring any restriction on the field size., Comment: 21 pages

The expected growth in the demand for passenger and freight services exacerbates the challenges of reducing transport GHG emissions, especially as commercial low-carbon alternatives to petroleum fuels are limited for shipping, air and long-distance road travel. Biofuels can offer a pathway to significantly reduce emissions from these sectors, as they can easily substitute for conventional liquid fuels in internal combustion engines. In this paper, we assess the potential of bioenergy to reduce transport GHG emissions through an analysis leveraging various integrated assessment models and scenarios, as part of the 33rd Energy Modeling Forum study (EMF-33). We find that bioenergy can contribute a significant, albeit not dominant, proportion of energy supply to the future transport sector: in scenarios aiming to keep the temperature increase below 2 °C by the end of the twenty-first century, models project that in 2100 bioenergy can provide on average 42 EJ/yr (ranging from 5 to 85 EJ/yr) for transport (compared to 3.7 EJ in 2018), mainly through lignocellulosic fuels. This makes up 9–62% of final transport energy use. Only a small amount of bioenergy is projected to be used in transport through electricity and hydrogen pathways, with a larger role for biofuels in road passenger transport than in freight. The association of carbon capture and storage (CCS) with bioenergy technologies (BECCS) is a key determinant in the role of biofuels in transport, because of the competition for biomass feedstock to provide other final energy carriers along with carbon removal. Among models that consider CCS in the biofuel conversion process the average market share of biofuels is 21% in 2100 (ranging from 2 to 44%), compared to 10% (0–30%) for models that do not. Cumulative direct emissions from the transport sector account for half of the emission budget (from 306 to 776 out of 1,000 GtCO2). However, the carbon intensity of transport decreases as much as other energy sectors in 2100

Dysphagia is a severe disability affecting daily life in patients with amyotrophic lateral sclerosis (ALS). It is caused by degeneration of both the bulbar motor neurons and cortical motoneurons projecting to the oropharyngeal areas. A previous report showed decreased event-related desynchronization (ERD) in the medial sensorimotor areas in ALS dysphagic patients. In the process of degeneration, brain reorganization may also be induced in other areas than the sensorimotor cortices. Furthermore, ALS patients with dysphagia often show a longer duration of swallowing. However, there have been no reports on brain activity in other cortical areas and the time course of brain activity during prolonged swallowing in these patients. In this case report, we investigated the distribution and the time course of ERD and corticomuscular coherence (CMC) in the beta (15-25 Hz) frequency band during volitional swallow using electroencephalography (EEG) in two patients with ALS. Case 1 (a 71-year-old man) was diagnosed 2 years before the evaluation. His first symptom was muscle weakness in the right hand; 5 months later, dysphagia developed and exacerbated. Since his dietary intake decreased, he was given an implantable venous access port. Case 2 (a 64-year-old woman) was diagnosed 1 year before the evaluation. Her first symptom was open-nasal voice and dysarthria; 3 months later, dysphagia developed and exacerbated. She was given a percutaneous endoscopic gastrostomy. EEG recordings were performed during volitional swallowing, and the ERD was calculated. The average swallow durations were 7.6 ± 3.0 s in Case 1 and 8.3 ± 2.9 s in Case 2. The significant ERD was localized in the prefrontal and premotor areas and lasted from a few seconds after the initiation of swallowing to the end in Case 1. The ERD was localized in the lateral sensorimotor areas only at the initiation of swallowing in Case 2. CMC was not observed in either case. These results suggest that compensatory processes fo

Cell therapies using human induced pluripotent stem cell (hiPSC)-derived nephron progenitor cells (NPCs) are expected to ameliorate acute kidney injury (AKI). However, using hiPSC-derived NPCs clinically is a challenge because hiPSCs themselves are tumorigenic. LIN28A, ESRG, CNMD and SFRP2 transcripts have been used as a marker of residual hiPSCs for a variety of cell types undergoing clinical trials. In this study, by reanalyzing public databases, we found a baseline expression of LIN28A, ESRG, CNMD and SFRP2 in hiPSC-derived NPCs and several other cell types, suggesting LIN28A, ESRG, CNMD and SFRP2 are not always reliable markers for iPSC detection. As an alternative, we discovered a lncRNA marker gene, MIR302CHG, among many known and unknown iPSC markers, as highly differentially expressed between hiPSCs and NPCs, by RNA sequencing and quantitative RT-PCR (qRT-PCR) analyses. Using MIR302CHG as an hiPSC marker, we constructed two assay methods, a combination of magnetic bead-based enrichment and qRT-PCR and digital droplet PCR alone, to detect a small number of residual hiPSCs in NPC populations. The use of these in vitro assays could contribute to patient safety in treatments using hiPSC-derived cells.

We report on the cryogenic properties of a low-contraction silicon-aluminum composite, namely Japan Fine Ceramics SA001, to use as a packaging structure for cryogenic silicon devices. SA001 is a silicon--aluminum composite material (75% silicon by volume) and has a low thermal expansion coefficient ($\sim$1/3 that of aluminum). The superconducting transition temperature of SA001 is measured to be 1.18 K, which is in agreement with that of pure aluminum, and is thus available as a superconducting magnetic shield material. The residual resistivity of SA001 is 0.065 $\mathrm{\mu \Omega m}$, which is considerably lower than an equivalent silicon--aluminum composite material. The measured thermal contraction of SA001 immersed in liquid nitrogen is $\frac{L_{293\mathrm{K}}-L_{77\mathrm{K}}}{L_{293\mathrm{K}}}=0.12$%, which is consistent with the expected rate obtained from the volume-weighted mean of the contractions of silicon and aluminum. The machinability of SA001 is also confirmed with a demonstrated fabrication of a conical feedhorn array, with a wall thickness of 100 $\mathrm{\mu m}$. These properties are suitable for packaging applications for large-format superconducting detector devices., Comment: 8 pages, 4 figures, 1 table, accepted for the Journal of Low Temperature Physics for the LTD19 special issue

In this paper, the previously synthesized Cu(II) complex ([CuL1(N3) (CH3OH)]BF4) with N,N,N-trimethyl-2-oxo-2-(2-(1-(thiazol-2-yl)ethylidene)hydrazinyl)ethan-1-aminium chloride, has been characterized and its biological activity has been studied in detail. The Cu(II) complex consists of ligand coordinated in a deprotonated, formally neutral zwitter-ionic form, via NNO atoms, one azido ligand and one methanol molecule. The Cu(II) complex was selected due to results of the cytotoxic activity, the brine shrimp test and DPPH radical scavenging activity, which were previously performed. The effects of Cu(II) complex on cell cycle phase distribution of cervical adenocarcinoma HeLa cells were investigated in order to examine the mechanisms of its anticancer activity. The measurement of intracellular ROS levels in HeLa and HaCaT cell lines were evaluated in order to explore their possible generation and the role in cytotoxic activity. The possible anti-invasive and anti-angiogenic properties of Cu(II) complex were evaluated. DNA binding experiments, including fluorescence displacement study and DNA cleavage experiments, were performed in order to obtain information on the type of DNA-metal complex interactions. © 2022 Serbian Chemical Society. All rights reserved.

Selected bond lengths (Å) and angles (°) of complexes 1 and 2. Comparison of Co-Nthiazole, Co-Nimine and Co-Sthiolate bond lengths (Å) in octahedral Co(III)-N4S2 complexes with thiosemicarbazone based ligands. Comparison of Co-Npy, Co-Nimine, Co-Nazide and Co-Oenolate bond lengths (Å) in octahedral Co(III)N4O2–Co(III)N2O(N3)3 complexes with hydrazone and azide ligands.Hydrogen-bond parameters for complex 1.Intermolecular p×××p interaction parameters for complex 2. Hydrogen-bond parameters for complex 2.Crystal packing of 1 showing self-assembled complex cations within a layer parallel with the (001) lattice plane by means of intermolecular N–H×××N and N–H×××S hydrogen bonds and (b) Intermolecular p×××p interactions between thiazole rings.Crystal packing of 2 showing 2D assembly parallel with the (10-1) lattice plane generated by intermolecular p×××p interactions and C–H×××N hydrogen bonds.Cartesian coordinates of all DFT optimized structures

Two Co(III) complexes with condensation product of thiosemicarbazide and 2-acetylthiazole (HL1 ligand, (E)-2-(1-(thiazol-2-yl)ethylidene)hydrazine-1-carbothioamide) and the condensation product of 2-acetylpyridine and Girard's P reagent (HL2Cl ligand, (E)-1-(2-oxo-2-(2-(1-(pyridin-2-yl)ethylidene)hydrazinyl)ethyl)pyridin-1-ium chloride) have been synthesized and characterized based on the results of single-crystal X-ray diffraction, NMR and IR spectroscopy and elemental analysis. Cobalt(III) complex with HL1 ligand, [Co(L1)2]BF4⋅H2O (1), is bis octahedral complex in which two deprotonated ligand molecules coordinate in a mer arrangement through two NNS sets of donor atoms. In cobalt(III) complex with HL2Cl, [Co(L2)(N3)3] (2), the ligand is coordinated in deprotonated, formally neutral, form to Co(III) ion in tridentate fashion through NNO set of donor atoms, and the other three coordination sites of a monokis octahedron are occupied by meridionally coordinated azide anions. DFT calculations were performed to elucidate coordination preferences of these ligands toward Co(III) ion.

Two Co(III) complexes [Co(L1)2]BF4·H2O (1) and [Co(L2)(N3)3] (2) with condensation product of thiosemicarbazide and 2-acetylthiazole (HL1) and the condensation product of 2-acetylpyridine and Girard’s P reagent (HL2Cl) and Co(BF4)2·6H2O have been synthesized. Complexes were characterized by elemental analysis, IR and NMR spectroscopy and X-ray crystallographic analysis. DFT calculations revealed the thermodynamical stability of obtained complexes., Kompleks [Co(L1)2]BF4·H2O (1) dobijen je u reakciji Co(BF4)2·6H2O sa kondenzacionim proizvodom tiosemikarbazida i 2-acetiltiazola (HL1), dok je kompleks [Co(L2)(N3)3] (2) dobijen u reakciji iste soli sa kondenzacionim proizvodom 2-acetilpiridina i Žirarovog P reagensa (HL2Cl). Oba kompleksa su okarakterisana elementalnom analizom, IC i NMR spektroskopijom i rendgenskom strukturnom analizom. DFT proračunima određena je termodinamička stabilnost kompleksa.

The HL ligand was synthesized in the reaction of thiosemicarbazide and 2-acetylthiazole in molar ratio 1:1 in water, with 3 drops of 2M HCl. Complex [Fe(L)2]BF4·H2O (1) was synthesized in the reaction of ligand and Fe(BF4)6·6H2O in MeOH, after complete dissolution of Fe(BF4)2·6H2O in the reaction mixture, NaN3 was added. In the reaction of ligand (HL), MnCl2·4H2O and NaN3, in molar rotio 1 : 1 : 4, Mn(II) complex (2) was obtained. Complexes 1 and 2 were characterized by elemental analysis, IR and UV/Vis spectroscopy and X-ray crystallographic analysis. Both complexes 1 and 2 with HL ligand are bis octahedral complexes in which two deprotonated ligand molecules coordinate in a mer arrangement through two NNS sets of donor atoms, through thiazole and imine nitrogens and thioenolate sulfur., Ligand (HL) sintetisan je u reakciji tiosemikarbazida i 2-acetiltiazola u molarnom odnosu 1 : 1 u vodi, u kiseloj sredini. Kompleks [Fe(L)2]BF4·H2O (1) dobijen je u reakciji liganda i Fe(BF4)2·6H2O u metanolu i nakon potpunog rastvaranja Fe(II) soli dodat je NaN3 u višku (1 : 1 : 4). U reakciji liganda (HL), MnCl2·4H2O i NaN3 u molarnom odnosu 1 : 1 : 4, dobijen je kompleks Mn(II), [Mn(L)2] (2). Kompleksi 1 i 2 okarakterisani su elementalnom analizom, IC spektroskopijom, UV/Vis spektroskopijom i rendgenskom strukturnom analizom. Kod oba kompleksa 1 i 2 dolazi do forimiranja bis oktaedarske geometrije tako što se za centralni metalni jon koordinuju dva deprotonovana liganda preko dva NNS donorska seta atoma u mer okruženju. Do koordinacije liganda za centralni metalni jon, kako Fe(III), tako i Mn(II), dolazi preko dva azota, od kojih jedan potiče iz tiazola, a drugi iz iminske grupe, kao i preko sumpora iz tioenolatne grupe.

Poster presented at: 58th Meeting of the Serbian Chemical Society, Belgrade, Serbia, June 9-10, 2022.

The HLCl ligand with metal salts Cu(BF4)2‧6H2O / MnCl2‧4H2O / Zn(BF4)2‧6H2O and NaN3, in methanol form mononuclear penta-coordinated complexes [CuL(N3)(CH3OH)]BF4 (1) and [ZnL(N3)2] (2) and binuclear [Mn2L2(µ-1,1-N3)2(N3)2]⋅2CH3OH (3) complex. Complexes 1, 2 and 3 were characterized by elemental analysis, IR spectroscopy, single-crystal X-ray diffraction, and DFT calculations., U reakciji liganda HLCl sa solima metala Cu(BF4)2‧6H2O / MnCl2‧4H2O / Zn(BF4)2‧6H2O i NaN3 u metanolu, dobijeni su mononuklearni kompleksi koordinacionog broja pet: [CuL(N3)(CH3OH)]BF4 (1) i [ZnL(N3)2] (2) i dinuklearni kompleks [Mn2L2(µ-1,1-N3)2(N3)2]⋅2CH3OH (3). Kompleksi 1, 2 i 3 okarakterisani su elementalnom analizom, IC spektroskopijom, rendgenskom stukturnom analizom i DFT proračunima.

Poster presented at: 58th Meeting of the Serbian Chemical Society, Belgrade, Serbia, June 9-10, 2022.

Poster presented at: 58th Meeting of the Serbian Chemical Society, Belgrade, Serbia, June 9-10, 2022.

Two Co(III) complexes with condensation product of thiosemicarbazide and 2-acetylthiazole (HL1 ligand, (E)-2-(1-(thiazol-2-yl)ethylidene)hydrazine-1-carbothioamide) and the condensation product of 2-acetylpyridine and Girard's P reagent (HL2Cl ligand, (E)-1-(2-oxo-2-(2-(1-(pyridin-2-yl)ethylidene)hydrazinyl)ethyl)pyridin-1-ium chloride) have been synthesized and characterized based on the results of single-crystal X-ray diffraction, NMR and IR spectroscopy and elemental analysis. Cobalt(III) complex with HL1 ligand, [Co(L1)2]BF4⋅H2O (1), is bis octahedral complex in which two deprotonated ligand molecules coordinate in a mer arrangement through two NNS sets of donor atoms. In cobalt(III) complex with HL2Cl, [Co(L2)(N3)3] (2), the ligand is coordinated in deprotonated, formally neutral, form to Co(III) ion in tridentate fashion through NNO set of donor atoms, and the other three coordination sites of a monokis octahedron are occupied by meridionally coordinated azide anions. DFT calculations were performed to elucidate coordination preferences of these ligands toward Co(III) ion.

In this paper, the previously synthesized Cu(II) complex ([CuL1(N3) (CH3OH)]BF4) with N,N,N-trimethyl-2-oxo-2-(2-(1-(thiazol-2-yl)ethylidene)hydrazinyl)ethan-1-aminium chloride, has been characterized and its biological activity has been studied in detail. The Cu(II) complex consists of ligand coordinated in a deprotonated, formally neutral zwitter-ionic form, via NNO atoms, one azido ligand and one methanol molecule. The Cu(II) complex was selected due to results of the cytotoxic activity, the brine shrimp test and DPPH radical scavenging activity, which were previously performed. The effects of Cu(II) complex on cell cycle phase distribution of cervical adenocarcinoma HeLa cells were investigated in order to examine the mechanisms of its anticancer activity. The measurement of intracellular ROS levels in HeLa and HaCaT cell lines were evaluated in order to explore their possible generation and the role in cytotoxic activity. The possible anti-invasive and anti-angiogenic properties of Cu(II) complex were evaluated. DNA binding experiments, including fluorescence displacement study and DNA cleavage experiments, were performed in order to obtain information on the type of DNA-metal complex interactions. © 2022 Serbian Chemical Society. All rights reserved.