Publications

Herein, we report a straightforward, scalable synthetic route towards poly(ionic liquid) (PIL) homopolymer nanovesicles (NVs) with a tunable particle size of 50 to 120 nm and a shell thickness of 15 to 60 nm via one-step free radical polymerization induced self-assembly. By increasing monomer concentration for polymerization, their nanoscopic morphology can evolve from hollow NVs to dense spheres, and finally to directional worms, in which a multilamellar packing of PIL chains occurred in all samples. The transformation mechanism of NVs’ internal morphology is studied in detail by coarse-grained simulations, revealing a correlation between the PIL chain length and the shell thickness of NVs. To explore their potential applications, PIL NVs with varied shell thickness are in situ functionalized with ultra-small (1 ∼ 3 nm in size) copper nanoparticles (CuNPs) and employed as electrocatalysts for CO2 electroreduction. The composite electrocatalysts exhibit a 2.5-fold enhancement in selectivity towards C1products (e.g., CH4), compared to the pristine CuNPs. This enhancement is attributed to the strong electronic interactions between the CuNPs and the surface functionalities of PIL NVs. This study casts new aspects on using nanostructured PILs as new electrocatalyst supports in CO2 conversion to C1 products.

Membrane electrode assemblies in gas diffusion cells enable CO2 reduction at industrially relevant rates, yet their long-term operational stability is often limited by the formation of solid precipitates (e.g. K2CO3) in the cathode pores. This is a consequence of a combination of 1) local alkalization due to the electrochemical reaction, 2) generation of (bi)carbonate by chemical reaction of CO2 with the alkaline electrolyte, and 3) the presence of alkali metal cations. In catholyte-free, zero-gap cells using anion exchange membranes, the presence of electrolyte cations at the cathode is the result of unintended crossover from the anolyte, and a detailed understanding of the factors enabling this crossover is lacking. Here we show that the anolyte concentration governs the flux of cation migration through the membrane, and this substantially influences the behaviors of copper catalysts in catholyte-free CO2 electrolysers. Systematic variation of the anolyte ionic strength (using aqueous KOH or KHCO3) correlated with drastic changes in the observed product selectivity – most notably, at low ionic strength, Cu catalysts produced predominantly CO, in contrast to the mixture of C2+ products typically observed on Cu. In this talk, we examine the factors influencing ion crossover and the resulting effects on catalyst structure and activity, under conditions of both CO2 and CO reduction. Operando X-ray absorption spectroscopy and quasi in situ X-ray photoelectron spectroscopy were used to study how the catalyst is affected by operation conditions. Our results show that even in catholyte-free cells, cation effects (including unintended ones) can significantly influence reaction pathways, and this must be considered in future development of catalysts and devices.

Membrane electrode assemblies enable CO2 electrolysis at industrially relevant rates, yet their operational stability is often limited by formation of solid precipitates in the cathode pores, triggered by cation crossover from the anolyte due to imperfect ion exclusion by anion exchange membranes. Here we show that anolyte concentration affects the degree of cation movement through the membranes, and this substantially influences the behaviors of copper catalysts in catholyte-free CO2 electrolysers. Systematic variation of the anolyte (KOH or KHCO3) ionic strength produced a distinct switch in selectivity between either predominantly CO or C2+ products (mainly C2H4) which closely correlated with the quantity of alkali metal cation (K+) crossover, suggesting cations play a key role in C-C coupling reaction pathways even in cells without discrete liquid catholytes. Operando X-ray absorption and quasi in situ X-ray photoelectron spectroscopy revealed that the Cu surface speciation showed a strong dependence on the anolyte concentration, wherein dilute anolytes resulted in a mixture of Cu+ and Cu0 surface species, while concentrated anolytes led to exclusively Cu0 under similar testing conditions. These results show that even in catholyte-free cells, cation effects (including unintentional ones) significantly influence reaction pathways, important to consider in future development of catalysts and devices.

Dealing with climate change and environmental issues must begin with the acceptance of the position that the environmental crisis is equivalent to the economic, political, or health crisis, which is typically the focus of our political and legal apparatus. It has such a broad scope that it exceeds the level of the individual right to a healthy environment and cannot be measured solely through the lens of concretely determined cases of violation. Its visible consequences cannot be justified by achieving some higher economic, social, or other goals, such as, first and foremost, economic benefits from accelerated economic development at the expense of reckless environmental destruction. Numerous laws and regulations in the Republic of North Macedonia cover almost every aspect of the environment. However, some of them are considered outdated and unsuitable for the country’s current situation. Another perceived weakness of the environmental legal framework is the lack of implementation as a result of the institutional division of state authorities responsible for enforcement and insufficient personnel and technical resources in local administration and inspection services. It is encouraging that the entire environmental legislation is being revised and perceived flaws are being addressed. Despite the beginning of the process of enacting new or amending existing laws for specific areas of environmental protection, many open questions remain in key areas as well as strategic goals and policies. 

To address the challenge of selectivity toward single products in Cu-catalyzed electrochemical CO2 reduction, one strategy is to incorporate a second metal with the goal of tuning catalytic activity via synergy effects. In particular, catalysts based on Cu modified with post-transition metals (Sn or In) are known to reduce CO2 selectively to either CO or HCOO– depending on their composition. However, it remains unclear exactly which factors induce this switch in reaction pathways and whether these two related bimetal combinations follow similar general structure–activity trends. To investigate these questions systematically, Cu–In and Cu–Sn bimetallic catalysts were synthesized across a range of composition ratios and studied in detail. Compositional and morphological control was achieved via a simple electrochemical synthesis approach. A combination of operando and quasi-in situ spectroscopic techniques, including X-ray photoelectron, X-ray absorption, and Raman spectroscopy, was used to observe the dynamic behaviors of the catalysts’ surface structure, composition, speciation, and local environment during CO2 electrolysis. The two systems exhibited similar selectivity dependency on their surface composition. Cu-rich catalysts produce mainly CO, while Cu-poor catalysts were found to mainly produce HCOO–. Despite these similarities, the speciation of Sn and In at the surface differed from each other and was found to be strongly dependent on the applied potential and the catalyst composition. For Cu-rich compositions optimized for CO production (Cu85In15 and Cu85Sn15), indium was present predominantly in the reduced metallic form (In0), whereas tin mainly existed as an oxidized species (Sn2/4+). Meanwhile, for the HCOO–-selective compositions (Cu25In75 and Cu40Sn60), the indium exclusively exhibited In0 regardless of the applied potential, while the tin was reduced to metallic (Sn0) only at the most negative applied potential, which corresponds to the best HCOO– selectivity. Furthermore, while Cu40Sn60 enhances HCOO– selectivity by inhibiting H2 evolution, Cu25In75 improves the HCOO– selectivity at the expense of CO production. Due to these differences, we contend that identical mechanisms cannot be used to explain the behavior of these two bimetallic systems (Cu–In and Cu–Sn). Operando surface-enhanced Raman spectroscopy measurements provide direct evidence of the local alkalization and its impact on the dynamic transformation of oxidized Cu surface species (Cu2O/CuO) into a mixture of Cu(OH)2 and basic Cu carbonates [Cux(OH)y(CO3)y] rather than metallic Cu under CO2 electrolysis. This study provides unique insights into the origin of the switch in selectivity between CO and HCOO– pathways at Cu bimetallic catalysts and the nature of surface-active sites and key intermediates for both pathways.

Human Rights Due Diligence is a key topic in the debates among human rights advocates and the business world. Its understanding varies from a standard ofexpected care to a process to manage business risks. As introduced in the United Nations Guiding Principles on Business and Human Rights, it is a process through which business enterprises should identify, assess and properly address human rights risks. Today, the concept is used or tends to be incorporated in avariety of legal instruments, from international soft-law to regional and national regulations. However, the understanding of what is the objective of human rights due diligence, its content, and the required standard still vary. Relying on the international soft-law instruments and the developments in national law, this study analyzes the foundation and narrative of human rights due diligence, content, common elements, and scope of obligation in a way to identify similarities and/or differences in the concept within different jurisdictions.

De facto државите се уште познати и како „непризнати држави”, „делумно признатидржави”, држави со спорна егзистенција...Тие се мета на истражување, докажувањефакти, дебати и анализи, за апликативноста на меѓународните правила и сегментирањекои држави можат да влезат во групата на de facto држави, а кои не...Територии коисакаат да бидат држави, но će уште не се здобиле со независности меѓународнапризнатост. За многумина овде е апликативна Конвенцијата од Монтевидео, со целда се видат правата и обврските на државите. Но дали денес постои листа на овиедржави? Многумина ги споменуваат Косово, Северен Кипар, Абхазија и Јужна Осетија,Палестина, Транснистрија, Нагорно-Карабах, Народна Република Доњецк и ЛуганскатаНародна Република... Каков е статусот на овие држави и зошто уште немаат меѓународнопризнавање?

The development of earth-abundant catalysts for selective electrochemical CO2conversion is a central challenge. CuSn bimetallic catalysts can yield selective CO2reduction toward either CO or formate. This study presents oxide-derived CuSn catalysts tunable for either product and seeks to understand the synergetic effects between Cu and Sn causing these selectivity trends. The materials undergo significant transformations under CO2 reduction conditions, and their dynamic bulk and surface structures are revealed by correlating observations from multiple methods—X-ray absorption spectroscopy for in situ study, and quasi in situ X-ray photoelectron spectroscopy for surface sensitivity. For both types of catalysts, Cu transforms to metallic Cu0 under reaction conditions. However, the Sn speciation and content differ significantly between the catalyst types: the CO-selective catalysts exhibit a surface Sn content of 13 at. % predominantly present as oxidized Sn, while the formate-selective catalysts display an Sn content of ≈70 at. % consisting of both metallic Sn0 and Sn oxide species. Density functional theory simulations suggest that Snδ+ sites weaken CO adsorption, thereby enhancing CO selectivity, while Sn0 sites hinder H adsorption and promote formate production. This study reveals the complex dependence of catalyst structure, composition, and speciation with electrochemical bias in bimetallic Cu catalysts.

The world over, people drink in order to socialize, celebrate, and relax, despite the negative health effects of alcohol. Three periods of dynamic brain changes are evidenced to be particularly sensitive to the harmful effects of alcohol: gestation (from conception to birth), later adolescence (15-19 years), and older adulthood (over 65 years). This article is concentrated only on the negative effects of alcohol in children who have been exposed to alcohol before birth, known as foetal alcohol syndrome (FAS). This is a review based on published data in PubMed over the last two decades and is an analysis of more than 150 published papers. Alcohol use during pregnancy can cause miscarriage, stillbirth, and a range of lifelong physical, behavioural, and intellectual disabilities. The effects of ethanol are expressed on a set of molecules involved in neuroinflammation, myelination, neurotransmission, and neuron function. Modern neuroimaging techniques are able to specify some fine structural changes in the affected areas of the brain: volume reductions in the frontal lobe, including the middle frontal gyri in the prefrontal cortex, hippocampal structure, interhemispheric connectivity, abnormalities in glial cells, white matter deficits etc. Corpus callosum myelination is affected, resulting in a lack of the inter-hemispheric connectivity. This is known to facilitate autism, stroke, schizophrenia, as well as dementia, disrupts cognitive performance, and may lead to neurobehavioral deficits. It was pointed out that many symptoms and neuroimaging characteristics are similar in ADHD and FAS, thus the anamnesis for prenatal alcohol and nicotine exposure must be taken very seriously in order to better understand and interpret clinical symptoms.

Interleukin 10 (IL-10) is an immunosuppressive cytokine and its genetic variants could have an indirect impact on viral biology and human papillomavirus (HPV) E6/E7 messenger RNA (mRNA) expression as well. This study evaluates the association between IL-10-592 C/A (rs1800872) single-nucleotide polymorphism and HPV E6/E7 mRNA expression in a group of women from the Republic of North Macedonia. Using a commercial test, 272 women's cervical samples were analyzed for HPV E6/E7 mRNA and HPV DNA presence. The cases were stratified into three groups: double-positive (n = 108, positive for both tests), negative (n = 51, negative for HPV E6/E7 mRNA and HPV DNA positive), and the control group (n = 113, negative for both tests). The IL-10-592 C/A polymorphism was analyzed using polymerase chain reaction-restriction fragment length polymorphism. The results showed the CC genotype and the C allele frequencies of IL-10-592C/A were significantly higher in double-positive (59.3% and 78.2%) compared to negative group (39.2% and 65.7%), (p = 0.018, confidence interval [CI] = 2.25; 1.14-4.45 and p = 0.016, CI = 1.88; 1.11-3.16, respectively). The CC genotype and C allele of rs1800872 polymorphism were shown to be associated with HPV E6/E7 mRNA but not with HPV DNA positivity, which implies a possible role of this polymorphism in the course of the infection only after HPV onset, and lack of association with the susceptibility to HPV.

Severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) infection fatality rate (IFR) doubles with every 5 y of age from childhood onward. Circulating autoantibodies neutralizing IFN-α, IFN-ω, and/or IFN-β are found in ∼20% of deceased patients across age groups, and in ∼1% of individuals aged <70 y and in >4% of those >70 y old in the general population. With a sample of 1,261 unvaccinated deceased patients and 34,159 individuals of the general population sampled before the pandemic, we estimated both IFR and relative risk of death (RRD) across age groups for individuals carrying autoantibodies neutralizing type I IFNs, relative to noncarriers. The RRD associated with any combination of autoantibodies was higher in subjects under 70 y old. For autoantibodies neutralizing IFN-α2 or IFN-ω, the RRDs were 17.0 (95% CI: 11.7 to 24.7) and 5.8 (4.5 to 7.4) for individuals <70 y and ≥70 y old, respectively, whereas, for autoantibodies neutralizing both molecules, the RRDs were 188.3 (44.8 to 774.4) and 7.2 (5.0 to 10.3), respectively. In contrast, IFRs increased with age, ranging from 0.17% (0.12 to 0.31) for individuals <40 y old to 26.7% (20.3 to 35.2) for those ≥80 y old for autoantibodies neutralizing IFN-α2 or IFN-ω, and from 0.84% (0.31 to 8.28) to 40.5% (27.82 to 61.20) for autoantibodies neutralizing both. Autoantibodies against type I IFNs increase IFRs, and are associated with high RRDs, especially when neutralizing both IFN-α2 and IFN-ω. Remarkably, IFRs increase with age, whereas RRDs decrease with age. Autoimmunity to type I IFNs is a strong and common predictor of COVID-19 death.

The Impact of COVID-19 on Prison Conditions and Penal Policy presents the results of a worldwide exchange of information on the impact of COVID-19 in prisons. It also focuses on the human rights questions that have been raised during the pandemic, relating to the treatment of prisoners in institutions for both juveniles and adults worldwide.