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This paper reports the results of a detailed study of the optical response of boron difluoride curcuminoids to radiation exposure. Two lines of the dyes fundamentally different in structure (namely, symmetrical and asymmetrical) were tested. If the absorption responses of their solutions in chloroform to X-rays turns out to be quite close quantitatively (note that it has a very indicative visual manifestation - a gradual discoloration is observed in the dose range up to 300 Gy), the fluorescence ones differ notably: among other things, the former demonstrate much more sensitive reactions (the corresponding limit of detection values ​​differ by up to 2.36-fold). Nevertheless, in both parameters, these dyes generally show good linearity of the response as in classical coordinates (up to ≈ 100-150 Gy), as in semi-logarithmic ones (up to 1000 Gy). Since the main reason for such behavior seems to be the radiation-induced decomposition of the dyes, its possible scheme and corresponding "weak links" in the structure of the molecules (in other words, radiosensitive elements) are proposed for each case. For example, these include N(CH3)2 fragments at the ends of dimethylaminostyryl groups. It is precisely their detachment that determines the observed optical response of asymmetrical dyes. Thus, the results obtained provide some insight into the possibilities of controlling the sensitivity of organic dyes to irradiation by changing their structure.

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BACKGROUND: Drug-resistant TB (DR-TB) remains a major public health threat. In 2022, Uzbekistan reported 2,117 cases of DR-TB, with 69% tested for fluoroquinolone resistance. Limited information is available on the prevalence of resistance to bedaquiline, linezolid, and fluoroquinolone, which are key components of the all-oral treatment regimen for rifampicin-resistant TB in Uzbekistan. METHODS: A retrospective study was conducted using extensive programmatic data from 2019 to 2023 in Uzbekistan. We assessed second-line drug-resistant TB (SLDR-TB) rates using phenotypic drug susceptibility testing (pDST). Demographic and clinical characteristics associated with SLDR-TB were analysed using multivariable logistic regression models based on the Allen-Cady approach. RESULTS: In total, 2,405 patients with TB who had undergone pDST were included (median age 40 years, 47% female). The overall SLDR-TB resistance rate was 24% (95% CI 22-26). Prevalence of resistance to bedaquiline, linezolid, moxifloxacin, levofloxacin, and amikacin were respectively 3.1%, 0.8%, 15%, 13%, and 12%. Risk factors for SLDR-TB were resistance to rifampicin and/or isoniazid, exposure to clofazimine, retreatment status, contact with drug-susceptible TB case or DR-TB case, and diabetes. CONCLUSIONS: The high prevalence of SLDR-TB is of major concern, emphasising the need for baseline pDST in RR-TB treatment. Identified risk factors can aid early detection of at-risk individuals and inform clinical practice.

CONTEXTE: La TB résistante aux médicaments (DR-TB) reste une menace majeure pour la santé publique. En 2022, l'Ouzbékistan a signalé 2 117 cas de DR-TB, dont 69% ont été testés pour la résistance aux fluoroquinolones. Les informations sur la prévalence de la résistance à la bédaquiline, au linézolide et aux fluoroquinolones, qui sont des composants clés du traitement entièrement oral de la TB résistante à la rifampicine en Ouzbékistan, sont limitées. MÉTHODES: Une étude rétrospective a été menée en utilisant des données programmatiques exhaustives de 2019 à 2023 en Ouzbékistan. Nous avons évalué les taux de TB résistante aux médicaments de deuxième ligne (SLDR-TB, pour l'anglais, « second-line drug-resistant TB ¼) en utilisant des tests de sensibilité phénotypique aux médicaments (pDST). Les caractéristiques démographiques et cliniques associées à la SLDR-TB ont été analysées à l'aide de modèles de régression logistique multivariés basés sur l'approche Allen-Cady. RÉSULTATS: Au total, 2 405 patients atteints de TB ayant subi un pDST ont été inclus (âge médian de 40 ans, 47% de femmes). Le taux global de résistance à la SLDR-TB était de 24% (CI à 95% 22­26). La prévalence de la résistance à la bédaquiline, au linézolide, à la moxifloxacine, à la lévofloxacine et à l'amikacine était respectivement de 3,1%, 0,8%, 15%, 13% et 12%. Les facteurs de risque de SLDR-TB comprenaient la résistance à la rifampicine et/ou à l'isoniazide, l'exposition à la clofazimine, le statut de retraitement, le contact avec un cas de TB sensible aux médicaments ou de DR-TB, et le diabète. CONCLUSIONS: La prévalence élevée de la SLDR-TB est une source de préoccupation majeure, soulignant la nécessité de réaliser des pDST de base dans le traitement de la TB résistante à la rifampicine. Les facteurs de risque identifiés peuvent aider à la détection précoce des individus à risque et à informer la pratique clinique.

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In a Hilbert setting we aim to study a second order in time differential equation, combining viscous and Hessian-driven damping, containing a time scaling parameter function and a Tikhonov regularization term. The dynamical system is related to the problem of minimization of a nonsmooth convex function. In the formulation of the problem as well as in our analysis we use the Moreau envelope of the objective function and its gradient and heavily rely on their properties. We show that there is a setting where the newly introduced system preserves and even improves the well-known fast convergence properties of the function and Moreau envelope along the trajectories and also of the gradient of Moreau envelope due to the presence of time scaling. Moreover, in a different setting we prove strong convergence of the trajectories to the element of minimal norm from the set of all minimizers of the objective. The manuscript concludes with various numerical results.

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Platinum(II) metalla-N-heterocyclic carbene complexes featuring pyridyl heterocyclic moiety demonstrate remarkable catalytic efficiency in alkyne hydrosilylation under green light irradiation. The photocatalytic properties of complexes are rationalised by the photo-induced charge transfer occurring in extended condensed system identified with the help of various experimental (UV/vis and emission spectroscopy, cyclic voltammetry) and theoretical methods (DFT/TD-DFT, IFCT analysis).

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Polarization-dependent gain (PDG) effect was studied in a conventional core-pumping configuration of bismuth-doped fiber amplifiers (BDFAs) based on PANDA-type phospho- and germanosilicate core fibers. The PDG value was determined as the gain difference between the orthogonal signal polarizations, which was found to be in range of 2.5-3 dB at total gain of >20 dB in such BDFAs. This effect is more pronounced for BDFA with a germanosilicate fiber. The experimental results are in a good agreement with the calculated data derived from the simulation model, relying on the anisotropy parameter of bismuth active centers (BACs) obtained from the degree of luminescence polarization, which ranges between 9 and 12% for BACs-Si and 18 and 22% for BACs-P. The obtained data can be useful for the optimization of performance of BDFAs and studying structural peculiarities of BACs.

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Since orthopedic surgery has been slower to acknowledge the rise of social media for distributing medical information, this study aims to evaluate TikTok videos' quality and educational value in relation to carpal tunnel syndrome treatment exercises. TikTok was searched using the hashtags "#carpaltunnelexercises", "#carpaltunnelremedies", "#carpaltunnelrehab", and "#physicaltherapyforcarpaltunnel". The engagement indicators were documented and the video content quality was assessed using the DISCERN, CTEES, JAMA, and GQS grading scales. There were 101 videos included, which accumulated 20,985,730 views. The videos received 1,460,953 likes, 15,723 comments, 243,245 favorites, and 159,923 shares. Healthcare professionals were responsible for 72% of the video uploads, whereas general users contributed 28%. More healthcare professionals' videos were graded as "poor" (79%) compared to general users (21%). General users received slightly more video grades of "very poor" (52%) than healthcare professionals (48%). For the DISCERN grading, the videos by healthcare professionals were significantly better than those by general users in terms of reliability, achieving aims, and relevancy. They were also superior in the overall composition of the health information derived from the total DISCERN score. However, no significant differences were found between the two groups when using the CTEES, JAMA, and GQS grading scales. Overall, despite the emergence of TikTok as a medical information tool, the quality and educational value of the carpal tunnel syndrome exercise videos were poor.

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Cisplatin is one of the most well-known anti-cancer drugs and has demonstrated efficacy against numerous tumor types for many decades. However, a key challenge with cisplatin, as with any chemotherapeutic agent, is the development of resistance with a resultant loss of efficacy. This resistance is often associated with metabolic alterations that allow insensitive cells to divide and survive under treatment. These adaptations could vary greatly among different tumor types and may seem questionable and incomprehensible at first glance. Here we discuss the disturbances in glucose, lipid, and amino acid metabolism in cisplatin-resistant cells as well as the roles of ferroptosis and autophagy in acquiring this type of drug intolerance.

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In recent years, various technologies have emerged for the imaging of chromatin loci in living cells via catalytically inactive Cas9 (dCas9). These technologies facilitate a deeper understanding of the mechanisms behind the chromatin dynamics and provide valuable kinetic data that could not have previously been obtained via FISH applied to fixed cells. However, such technologies are relatively complicated, as they involve the expression of several chimeric proteins as well as sgRNAs targeting the visualized loci, a process that entails many technical subtleties. Therefore, the effectiveness in visualizing a specific target locus may be quite low. In this study, we directly compared two versions of a previously published CRISPR-Sirius method based on the use of sgRNAs containing eight MS2 or PP7 stem loops and the expression of MCP or PCP fused to fluorescent proteins. We assessed the visualization efficiency for several unique genomic loci by comparing the two approaches in delivering sgRNA genes (transient transfection and lentiviral transduction), as well as two CRISPR-Sirius versions (with PCP and with MCP). The efficiency of visualization varied among the loci, and not all loci could be visualized. However, the MCP-sfGFP version provided more efficient visualization in terms of the number of cells with signals than PCP-sfGFP for all tested loci. We also showed that lentiviral transduction was more efficient in locus imaging than transient transfection for both CRISPR-Sirius systems. Most of the target loci in our study were located at the borders of topologically associating domains, and we defined a set of TAD borders that could be effectively visualized using the MCP-sfGFP version of the CRISPR-Sirius system. Altogether, our study validates the use of the CRISPR-Sirius technology for live-cell visualization and highlights various technical details that should be considered when using this method.

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INTRODUCTION: In low- and middle-income countries such as Haiti, musculoskeletal injuries are the leading cause of morbidity and mortality. Untreated injuries can contribute to decreased mobility, leading to disability and reduced productivity for individuals. The accessibility of timely fracture care poses a substantial challenge in Haiti, where socioeconomic instability and recent surges in gang violence exacerbate an already strained healthcare infrastructure. This manuscript delves into the intricate barriers to sustainable fracture care in Haiti, shedding light on the sociopolitical landscape and clinical challenges that influence the delivery of orthopedic services. ETHICAL DISCUSSION: The ethical considerations in providing fracture care in Haiti are multifaceted, including classic medical principles, self-preservation in the face of violence, issues of justice in resource and service allocation, and concerns of nonmaleficence in the context of international volunteers. These ethical dilemmas arise from the complex interplay of limited resources, the dangers posed by the current sociopolitical climate, and the involvement of international aid in a vulnerable healthcare system. CONCLUSION: To address the clinical and ethical conflicts of providing fracture care in Haiti, solutions include education and training of Haitian orthopedic surgeons, capacity building of healthcare facilities, and establishing ethical standards for international volunteers. This comprehensive approach is vital for advancing sustainable fracture care in Haiti and other resource-limited settings.

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A preparation method for steroid-based difluoroboron complexes has been developed using lumiestrone as a steroid example. Previously inaccessible lumiestrone-based difluoroboron complexes annulated at positions 16 and 17 of the D ring have been prepared. Such difluoroboron complexes may have large synthetic potential for heterofunctionalization of steroids at the D ring. An application of a borylation mixture Ac2O-BF3•OEt2 significantly simplify the preparation of steroid "dimers" bearing two estrone moieties connected at positions 2 and 2' via a linker. Crystal structures of key representatives have been determined by X­ray diffraction.

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A series of novel organogermanium(IV) catecholates 1-9 of the general formula R'2Ge(Cat), where R' = Ph, Et, have been synthesized. Compounds were characterized by 1H, 13C NMR, IR spectroscopy, and elemental analysis. The molecular structures of 1-3, 6, and 8 in crystal state were established using single-crystal X-ray analysis. The complexes are tetracoordinate germanium(IV) compounds containing a dioxolene ligand in a dianion (catecholato) form. Electrochemical transformations of target germanium(IV) complexes have been studied by cyclic voltammetry. The electro-oxidation mechanism of complexes 1-5, 7, and 10 (the related complex Ph2Ge(3,5-Cat) where 3,5-Cat is 3,5-di-tert-butylcatecholate) involves the consecutive formation of mono- and dicationic derivatives containing the oxidized forms of redox-active ligands. The stability of the generated monocations depends both on the hydrocarbon groups at the germanium atom and on the substituents in the catecholate ring. Compounds 6, 8, and 9 are oxidized irreversibly under the electrochemical conditions with the formation of unstable complexes. The radical scavenging activity and antioxidant properties of new complexes were estimated in the reaction with DPPH radical, ABTS radical cation, and CUPRACTEAC assay. It has been found that compounds 8 and 9 with benzothiazole or phenol fragments are more active in DPPH test. The presence of electron-rich moieties in the catecholate ligand makes complexes 5 and 7-9 more reactive to ABTS radical cation. The value of CUPRACTEAC for organogermanium(IV) catecholates varies from 0.23 to 1.45. The effect of compounds 1-9 in the process of lipid peroxidation of rat liver (Wistar) homogenate was determined in vitro. It was found that most compounds are characterized by pronounced antioxidant activity. A feature of complexes 1, 3, and 5-9 is the intensification of the antioxidant action with the incubation time. In the presence of additives of complexes 3, 5, 6, and 8, an induction period was observed during the process of lipid peroxidation.

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This work provides a procedure and database for obtaining the vibrational frequency scale factors that align quantum chemically computed harmonic frequencies with experimental vibrational spectroscopic data. The database comprises 441 molecules of various sizes, from diatomics to the buckminsterfullerene C60. We provide scale factors for 27 dispersion-corrected methods, 24 of which are DF-Dn/B with DF=BLYP, PBE, B3LYP, PBE0, Dn=D3(BJ), D4, and B=6-31G, def2-SVP, def2-TZVP, and three of them are the 3c-family composite methods (HF-3c, PBEh-3c, and r2$SCAN-3c). The two scale factors are derived for each method: the absolute scaling, minimizing the absolute deviation of the scaled harmonic frequency from the experimental value, and the relative scaling, which minimizes an analogous relative deviation. The absolute type of scaling is recommended for frequencies above 2000 cm-1, while the relative scaling is optimal for frequencies below 2000 cm-1.

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Work function is an essential material's property playing important roles in electronics, photovoltaics, and more recently, in nanophotonics. We have studied effects of organic, and inorganic dielectric materials on work functions of Au films in single layered, and multilayered structures. We found that measured work function of metallic surfaces can be affected by dielectric materials situated 10-100 nm away from the metallic surface. We have found that, (i) the glass underneath ~ 50 nm gold slab reduces the work function of gold, (ii) Rh590:PMMA increases the work function of a gold film deposited on top of the polymer, and (iii) reduces it if Rh590:PMMA is deposited on top of Au. (iv) With increase of the Rh590 concentration in PMMA, n, the work function first decreases (at n < 64 g/l), and then increases (at n > 64 g/l). (v) The work function of a Fabry-Perot cavity or an MIM waveguide is almost the same as that of single Au films of comparable thickness. The experimental results can be qualitatively explained in terms of a simple model taking into account adhesion of charged molecules to a metallic surface, and formation of a double layer of charges accelerating or decelerating electrons exiting the metal and decreasing or increasing the work function.

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The oxygen reduction reaction (ORR) catalyzed by efficient and economical catalysts is critical for sustainable energy devices. Although the newly-emerging atomically dispersed platinum catalysts are highly attractive for maximizing atomic utilization, their catalytic selectivity and durability are severely limited by the inflexible valence transformation between Pt and supports. Here, we present a structure by anchoring Pt atoms onto valence-adjustable CuOx/Cu hybrid nanoparticle supports (Pt1-CuOx/Cu), in which the high-valence Cu (+2) in CuOx combined with zero-valent Cu (0) serves as a wide-range valence electron reservoir (0‒2e) to dynamically adjust the Pt 5d valence states during the ORR. In situ spectroscopic characterizations demonstrate that the dynamic evolution of the Pt 5d valence electron configurations could optimize the adsorption strength of *OOH intermediate and further accelerate the dissociation of O = O bonds for the four-electron ORR. As a result, the Pt1-CuOx/Cu catalysts deliver superior ORR performance with a significantly enhanced four-electron selectivity of over 97% and long-term durability.

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Organic rich sedimentary rocks of the Late Cretaceous Muwaqqar Formation from the Lajjun outcrop in the Lajjun Sub-basin, Western Central Jordan were geochemically analyzed. This study integrates kerogen microscopy of the isolated kerogen from 10 oil shale samples with a new finding from unconventional geochemical methods [i.e., ultimate elemental (CHNS), fourier transform infrared spectroscopy and pyrolysis-gas chromatography (Py-GC)] to decipher the molecular structure of the analyzed isolated kerogen fraction and evaluate the kerogen composition and characteristics. The optical kerogen microscopy shows that the isolated kerogen from the studied oil shales is originated from marine assemblages [i.e., algae, bituminite and fluorescence amorphous organic matter] with minor amounts of plant origin organic matter (i.e., spores). This finding suggests that the studied kerogen is hydrogen-rich kerogen, and has the potential to generate high paraffinic oil with low wax content. The dominance of such hydrogen-rich kerogen (mainly Type II) was confirmed from the multi-geochemical ratios, including high hydrogen/carbon atomic of more than 1.30 and high A-factor of more than 0.60. This claim agrees with the molecular structure of the kerogen derived from Py-GC results, which suggest that the studied kerogen is mainly Type II-S kerogen exhibiting the possibility of producing high sulphur oils during earlier stages of diagenesis, according to bulk kinetic modeling. The kinetic models of the isolated kerogen fraction suggest that the kerogen conversion, in coincidence with a vitrinite reflectance range of 0.55-0.60%, commenced at considerably lower temperature value ranges between 100 and 106 °C, which have produced oils during the early stage of oil generation. The kinetic models also suggest that the commercial amounts of oil can generate by kerogen conversion of up to 50% during the peak stage of oil window (0.71-0.83%) at relatively low geological temperature values in the range of 122-138 °C. Therefore, further development of the Muwaqqar oil shale successions is highly approved in the shallowly buried stratigraphic succession in the Lajjun Sub-basin, Western Central Jordan.

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PURPOSE: The purpose of this study was to evaluate clinical outcomes after tendon transfers in the setting of reverse total shoulder arthroplasty (RTSA). METHODS: PubMed and Embase were searched according to Preferred Reporting Items for Systematic reviews and Meta-Analyses guidelines to find primary clinical studies of any type of tendon transfer in the setting of RTSA. RESULTS: Overall, 17 studies (level of evidence [LOE] I: 1, LOE II: 0, LOE III: 3, LOE IV: 13) met inclusion criteria, with 300 shoulders. Most patients were female (56.7%), with an average age of 68.7 years (range 19 to 89) and a mean follow-up of 46.2 months (range 6 to 174). 11 studies reported outcomes after combined latissimus dorsi and teres major transfer (LDTM) while eight studies reported on latissimus dorsi transfer only (LD). Improvements in commonly reported subjective and functional outcome measures were as follows: external rotation +32° (LDTM) and +30° (LD), flexion +65° (LDTM) and +59° (LD), Visual Analog Score -5.4 (LDTM) and -4.5 (LD), subjective shoulder value +43.8% (LDTM) and +46.3% (LD), and overall Constant score +33.8 (LDTM) and +38.7 (LD). The overall complication rate was 11.3%, including tendon transfer ruptures (0.7%), instability (3.0%), infection (2.0%), and nerve injury (0.3%). The all-cause repeat operation rate was 7.3%, most commonly for arthroplasty revision (5.3%). Subgroup analysis revealed that lateralized implants with tendon transfer resulted in markedly greater improvements in Constant score, flexion, ER1, and ER2 while medialized implants with tendon transfer had markedly greater improvements in Visual Analog Score, subjective shoulder value, and abduction. CONCLUSION: Patients undergoing tendon transfer of either combined LDTM or latissimus dorsi alone in the setting of RTSA have markedly improved subjective and functional outcomes. A moderate incidence of complications (11.3%) was noted in this patient population.

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PURPOSE: To investigate a novel bioimpedance-based respiratory gating system (BRGS) designed for external beam radiotherapy and to evaluate its technical characteristics in comparison with existing similar systems. MATERIALS AND METHODS: The BRGS was tested on three healthy volunteers in free breathing and breath-hold patterns under laboratory conditions. Its parameters, including the time delay (TD) between the actual impedance change and the gating signal, temperature drift, root mean square (RMS) noise, and signal-to-noise ratio (SNR), were measured and analyzed. RESULTS: The gate-on TD and the gate-off TD were found to be 9.0 ± 2.0 ms [mean ± standard deviation (M ± SD)] and 7.2 ± 1.3 ms, respectively. The temperature drift of the BRGS output signal was 0.02 Ω after 30 min of operation. RMS noise averaged 0.14 ± 0.05 Ω (M ± SD) for all subjects and varied from 0.08 to 0.20 Ω with repeated measurements. A significant difference in SNR (p < 0.001) was observed between subjects, ranging from 4 to 15. CONCLUSION: The evaluated bioimpedance-based gating system showed a high performance in real-time respiratory monitoring and may potentially be used as an external surrogate guidance for respiratory-gated external beam radiotherapy. Direct comparison with commercially available systems, 4D correlation studies, and expansion of the patient sample are goals for future preclinical studies.

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BACKGROUND: Cells of different human organs and tissues contain different numbers of mitochondria. In these organelles, there are different copies of the mitochondrial genome, which is characteristic of a certain organ or tissue. OBJECTIVE: The aim of the investigation was to analyze the results of scientific works dedicated to the analysis of heteroplasmy levels of mitochondrial genome mutations in a number of organs and tissues. METHODS: Based on literature data, the level of heteroplasmy of mitochondrial genome mutations was analyzed in organs such as the liver, lungs, muscles, small intestine, large intestine, spleen, kidney, brain, heart, and hair. In addition, this parameter was studied in such tissues as leukocytes, buccal epithelium, and epithelial cells from urine. RESULTS: Significant differences in the mutational burden of the mitochondrial genome were found in various samples of organs and tissues. The highest heteroplasmy level for mtDNA mutations was in muscles; it was lower in buccal epithelium; and in human blood cells, the heteroplasmy level of mitochondrial mutations turned out to be significantly lower compared to other tissues. During the comparison of samples of patients with different diseases and healthy people, significant differences were found in the heteroplasmy level between some organs and tissues. CONCLUSION: The heteroplasmy level of mitochondrial genome mutations can significantly differ in the organs and tissues of individuals. In addition, in a number of literature sources, it is noted that there is a dependence on the mutational burden of the mitochondrial genome from the type of disease, sex, and age of a person.

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A systematic study of extraction systems for the separation of f-elements using the tetradentate N,O-donor diamide of 1,10-phenanthroline-2,9-dicarboxylic acid (L) in various molecular and ionic solvents was performed. It was demonstrated that the nature of a diluent has a significant impact on solvent extraction of Am(III) and Ln(III) and the stoichiometry of formed complexes with f-elements. The mechanism of complexation and forms of complexes in different diluents were investigated by radiometric methods, UV-vis titration, and XRD.