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1.
Nutrients ; 16(13)2024 Jun 28.
Article in English | MEDLINE | ID: mdl-38999817

ABSTRACT

Amygdalin is purported to exhibit anti-cancer properties when hydrolyzed to hydrogen cyanide (HCN). However, knowledge about amygdalin efficacy is limited. A questionnaire evaluating the efficacy, treatment, and dosing protocols, reasons for use, HCN levels, and toxicity was distributed to physicians and healers in Germany, providing amygdalin as an anti-cancer drug. Physicians (20) and healers (18) provided amygdalin over 8 (average) years to nearly 80 annually treated patients/providers. Information about amygdalin was predominantly obtained from colleagues (55%). Amygdalin was administered both intravenously (100%) and orally (32%). Intravenous application was considered to maximally delay disease progression (90%) and relieve symptoms (55%). Dosing was based on recommendations from colleagues (71%) or personal experience (47%). If limited success became apparent after an initial 3g/infusion, infusions were increased to 27g/infusion. Treatment response was primarily monitored with established (26%) and non-established tumor markers (19%). 90% did not monitor HCN levels. Negative effects were restricted to a few dizzy spells and nausea. Only 58% were willing to participate in clinical trials or contribute data for analysis (34%). Amygdalin infusions are commonly administered by healers and physicians with few side effects. The absence of standardized treatment calls for guidelines. Since intravenous application bypasses metabolization, re-evaluation of its mode of action is required.


Subject(s)
Amygdalin , Neoplasms , Amygdalin/administration & dosage , Humans , Neoplasms/drug therapy , Surveys and Questionnaires , Physicians , Germany , Female , Male , Middle Aged , Treatment Outcome
2.
Cureus ; 16(6): e62108, 2024 Jun.
Article in English | MEDLINE | ID: mdl-38993417

ABSTRACT

Cyanide is a lethal poison that induces immediate fatality. Infrequently employed as a homicidal poison, it is not an ideal choice for homicide as it causes a 'dramatic' death causing suspicion among others. Cyanide is a rapidly metabolized poison that also rapidly disintegrates after death, posing challenges for chemical analysis, particularly when dealing with decomposed bodies. Detection of cyanide from a decomposed body is infrequent. A suspected case of intentional poisoning resulting in death was interred without conducting a postmortem examination. The exhumation process revealed the presence of hydrogen cyanide in the postmortem fluids collected from the body cavities three years after interment.

3.
Chem ; 10(6): 1655-1667, 2024 Jun 13.
Article in English | MEDLINE | ID: mdl-38966253

ABSTRACT

The reduction of CO2 with low overpotential and high selectivity is a crucial challenge in catalysis. Fortunately, natural systems have evolved enzymes that achieve this catalytic reaction very efficiently at a complex nickel-iron-sulfur cluster within carbon monoxide dehydrogenase (CODH). Extensive biochemical, crystallographic, and spectroscopic work has been done to understand the structures and mechanism involved in the catalytic cycle, which are summarized here from the perspective of mechanistic organometallic chemistry. We highlight the ambiguities in the data and suggest experiments that could lead to clearer understanding of the mechanism and structures of intermediates at the active-site cluster. These include parallel crystallography and spectroscopy, as well as the preparation of synthetic analogues that help to interpret structural and spectroscopic signatures.

4.
Adv Sci (Weinh) ; : e2402884, 2024 Jun 14.
Article in English | MEDLINE | ID: mdl-38874086

ABSTRACT

The construction of large and complex supramolecular architectures through self-assembly is at the forefront of contemporary coordination chemistry. Notwithstanding great success in various systems using anionic bridges (e.g., O2- or S2-) or organic ligands (e.g., pyridine or carboxylate ligands), the assembly of large cyanide-bridged clusters with increasing nuclearity remains a formidable synthetic challenge. In this study, it is achieved in preparing two heterometallic cyanometallate clusters with unprecedented complexity, [Fe20Co20] (1) and [Fe12Co15] (2), by creating the "flexibility" through a versatile ligand of bis((1H-imidazol-4-yl)methylene)hydrazine (H2L) and low-coordinate cobalt. Complex 1 features a super-square array of four cyanide-bridged [Fe4Co4] cube subunits as the corners that are interconnected by four additional [FeCo] units, resulting in a torus-shaped architecture. Complex 2 contains a lantern-like core-shell cluster with a triple-helix kernel of [Co3L3] enveloped by a [Fe12Co12] shell. The combined structure analysis and mass spectrometry study reveal a hierarchical assembly mechanism, which sheds new light on constructing cyanometallate nanoclusters with atomic precision. Moreover, complex 1 undergoes a thermally induced electron-transfer-coupled spin transition (ETCST) between the diamagnetic {FeII LS(µ-CN)CoIII LS} and paramagnetic {FeIII LS(µ-CN)CoII HS} configurations (LS = low spin, HS = high spin) above room temperature, representing the largest molecule displaying electron transfer and spin transition characteristic.

5.
Int J Mol Sci ; 25(12)2024 Jun 12.
Article in English | MEDLINE | ID: mdl-38928184

ABSTRACT

Simple and efficient sample pretreatment methods are important for analysis and detection of chemical warfare agents (CWAs) in environmental and biological samples. Despite many commercial materials or reagents that have been already applied in sample preparation, such as SPE columns, few materials with specificity have been utilized for purification or enrichment. In this study, ionic magnetic mesoporous nanomaterials such as poly(4-VB)@M-MSNs (magnetic mesoporous silicon nanoparticles modified by 4-vinyl benzene sulfonic acid) and Co2+@M-MSNs (magnetic mesoporous silicon nanoparticles modified by cobalt ions) with high absorptivity for ethanol amines (EAs, nitrogen mustard degradation products) and cyanide were successfully synthesized. The special nanomaterials were obtained by modification of magnetic mesoporous particles prepared based on co-precipitation using -SO3H and Co2+. The materials were fully characterized in terms of their composition and structure. The results indicated that poly(4-VB)@M-MSNs or Co2+@M-MSNs had an unambiguous core-shell structure with a BET of 341.7 m2·g-1 and a saturation magnetization intensity of 60.66 emu·g-1 which indicated the good thermal stability. Poly(4-VB)@M-MSNs showed selective adsorption for EAs while the Co2+@M-MSNs were for cyanide, respectively. The adsorption capacity quickly reached the adsorption equilibrium within the 90 s. The saturated adsorption amounts were MDEA = 35.83 mg·g-1, EDEA = 35.00 mg·g-1, TEA = 17.90 mg·g-1 and CN-= 31.48 mg·g-1, respectively. Meanwhile, the adsorption capacities could be maintained at 50-70% after three adsorption-desorption cycles. The adsorption isotherms were confirmed as the Langmuir equation and the Freundlich equation, respectively, and the adsorption mechanism was determined by DFT calculation. The adsorbents were applied for enrichment of targets in actual samples, which showed great potential for the verification of chemical weapons and the destruction of toxic chemicals.


Subject(s)
Amines , Cyanides , Ethanol , Cyanides/chemistry , Cyanides/isolation & purification , Adsorption , Amines/chemistry , Ethanol/chemistry , Porosity , Cobalt/chemistry , Magnetite Nanoparticles/chemistry , Nanostructures/chemistry
6.
Molecules ; 29(11)2024 May 27.
Article in English | MEDLINE | ID: mdl-38893393

ABSTRACT

Despite being a major cyanide species in the process water, it is unclear how iron cyanide influences pyritic gold ore flotation as well as how lead ions influence pyritic gold ore flotation in the presence of iron cyanide. This study aims at revealing the interaction of Fe(CN)63- and lead ions in pyrite flotation to investigate the strong depressing effect of Fe(CN)63- on pyritic gold ore flotation and the significant activating effect of lead ions on pyritic gold ore flotation in the presence of Fe(CN)63- using flotation, zeta potential measurement and surface analysis methods. The flotation results showed that upon 5 × 10-5 mol/L Fe(CN)63- addition, pyrite recovery drastically decreased from about 51.3% to 8.6%, while the subsequent addition of 9.5 × 10-4 mol/L lead ions significantly activated pyrite with the recovery increasing from 8.6% to 91%, which demonstrated that Fe(CN)63- strongly depressed pyrite flotation, while lead ions completely activated pyrite in the presence of Fe(CN)63-. Zeta potential measurement, surface analysis using Cryogenic X-ray photoelectron spectroscopy (Cryo-XPS) and electrochemical impedance spectroscopy (EIS) revealed that Fe(CN)63- depression was attributed to the chemical adsorption of Fe(CN)63- on iron sites of pyrite as Prussian Blue (Fe[Fe(CN)6]); however, this hydrophilic layer could be covered totally by lead ions which adsorbed on as lead hydroxide/oxide through electrostatic interactions, which resulted in the significant activation effect of lead ions. The results from this study will lead to improved flotation of gold associated with pyrite in gold flotation plants.

7.
Sci Total Environ ; 945: 174034, 2024 Oct 01.
Article in English | MEDLINE | ID: mdl-38885716

ABSTRACT

Gold cyanidation facilities in the Arequipa Region of Peru are challenged by the availability and quality of water for processing in an arid environment. The facilities reuse decant water which recycles residual cyanide but also undesirable constituents. To understand the impact of intensive water recycling on cyanide and metals concentrations, we collected barren water, decant water, and tailings samples from six gold cyanidation facilities with ore capacities of 10-430 tons per day. Processing facilities in Arequipa recycle all effluents, with decant waters making up 58 ± 11 % of process waters. Decant water contained non-target metals: copper (394 ± 161 mg/L), iron (59 ± 34 mg/L), and zinc (74 ± 42 mg/L). In addition, decant water mean free and complexed cyanide concentrations were 534 ± 129 mg/L and 805 ± 297 mg/L, respectively. Complexed cyanide concentrations remained more constant than free cyanide concentrations with 786 ± 299 mg/L for barren water and 805 ± 297 mg/L for decant water. Cyanide mass balances showed between 21 % and 42 % of unaccounted free cyanide from the start of gold cyanidation and discharge to the tailings storage facility (TSF). Free cyanide estimated losses due to volatilization were 0.8 kg and 2.5 kg of hydrogen cyanide per ton of ore processed at barren water pH of 10.1 and 9.7. Together these results indicate two acute hazards: 1) volatilization of free cyanide during processing and 2) loading and retention of cyanides and metals into TSFs. This study elucidates the extent of uncontrolled vapor phase cyanide release during gold processing operation and contaminant concentrations in the tailings storage facilities. The data highlights the need for improvement oversight, accountability, and regulation of gold processing facilities practicing intensive recycling and zero discharge.

8.
Food Chem ; 456: 139872, 2024 Oct 30.
Article in English | MEDLINE | ID: mdl-38865818

ABSTRACT

The release of hydrogen cyanide (HCN) after food ingestion can pose a serious health risk to consumers. This study aimed to simultaneously quantify four cyanogenic glycosides (lotaustralin, prunasin, taxiphyllin, and dhurrin) using liquid chromatography-tandem mass spectrometry. The analysis scope extended beyond agricultural products to various consumer foods to estimate dietary exposure to cyanogenic glycosides and assess its risk levels. The major exposure sources are cassava chips (lotaustralin), apples (seeds) (prunasin and dhurrin), and Prunus mume axis (taxiphyllin). In addition to quantifying specific cyanogenic glycosides, this study proposed the development of a preliminary risk assessment framework based on the dietary exposure assessment and the calculation of theoretical levels of HCN derived from cyanogenic glycoside concentrations. In the absence of established guidelines for the permissible intake of foods containing cyanogenic glycosides, this study provides initial guidance for assessing the risks associated with a range of commonly consumed foods.


Subject(s)
Food Contamination , Glycosides , Hydrogen Cyanide , Manihot , Glycosides/chemistry , Glycosides/analysis , Hydrogen Cyanide/analysis , Hydrogen Cyanide/chemistry , Humans , Food Contamination/analysis , Manihot/chemistry , Republic of Korea , Tandem Mass Spectrometry , Malus/chemistry , Adult , Prunus/chemistry , Dietary Exposure/analysis , Risk Assessment , Young Adult
9.
Heliyon ; 10(11): e31606, 2024 Jun 15.
Article in English | MEDLINE | ID: mdl-38841478

ABSTRACT

The recovery of gold by adsorption using activated carbon from sodium cyanide and thiourea leached solutions are reported in this study. The leached solutions were obtained under real operating conditions from the beneficiation plant "Paz Borja", Machala-Ecuador. Calgon Carbon DG-11 6X12 type, widely used in the local metallurgical industry was used as adsorbent material. The operational parameters varied during the adsorption process experiments included the concentration of leaching agent, agitation speed, dose of activated carbon and initial concentration of gold. The control parameters included density, percentage of solid, pH, temperature, and solution potential. The obtained results were adjusted to mass transfer model by diffusion through the interface and the Freundlich model for the equilibrium isotherms. The analysis of the results indicates a higher adsorption rate of the gold di-cyanide complex on activated carbon compared to gold-thiourea complexes.

10.
Biosensors (Basel) ; 14(6)2024 May 27.
Article in English | MEDLINE | ID: mdl-38920580

ABSTRACT

Metal-organic frameworks (MOFs) are frequently utilized as sensing materials. Unfortunately, the low conductivity of MOFs hinder their further application in electrochemical determination. To overcome this limitation, a novel modification strategy for MOFs was proposed, establishing an electrochemical determination method for cyanides in Baijiu. Co and Ni were synergistically used as the metal active centers, with meso-Tetra(4-carboxyphenyl)porphine (TCPP) and Ferrocenecarboxylic acid (Fc-COOH) serving as the main ligands, synthesizing Ni/Co-MOF-TCPP-Fc through a hydrothermal method. The prepared MOF exhibited improved conductivity and stable ratio signals, enabling rapid and sensitive determination of cyanides. The screen-printed carbon electrodes (SPCE) were suitable for in situ and real-time determination of cyanide by electrochemical sensors due to their portability, low cost, and ease of mass production. A logarithmic linear response in the range of 0.196~44 ng/mL was demonstrated by this method, and the limit of detection (LOD) was 0.052 ng/mL. Compared with other methods, the sensor was constructed by a one-step synthesis method, which greatly simplifies the analysis process, and the determination time required was only 4 min. During natural cyanide determinations, recommended readouts match well with GC-MS with less than 5.9% relative error. Moreover, this electrochemical sensor presented a promising method for assessing the safety of cyanides in Baijiu.


Subject(s)
Cyanides , Electrochemical Techniques , Limit of Detection , Metal-Organic Frameworks , Cyanides/analysis , Metal-Organic Frameworks/chemistry , Electrodes , Biosensing Techniques , Nickel/chemistry , Ferrous Compounds/chemistry , Metallocenes/chemistry , Cobalt/chemistry
11.
Article in English | MEDLINE | ID: mdl-38900251

ABSTRACT

Little is known about how pharmacological and toxicological knowledge evolves. The aim of this study was to investigate the changes in the presentation of the poison hydrogen cyanide in sixteen German-language pharmacology and toxicology textbooks from 1878 to 2020. The categories of structure, molecular mechanism of action, occurrence, effects, resorption, areas of application, lethal dose, acute symptoms of intoxication, treatment of hydrogen cyanide poisoning, and recommended therapeutic preparations were evaluated. The knowledge on the structure, lethal dosage, and occurrence of hydrogen cyanide has remained constant. In contrast, knowledge on molecular mechanism of action and recommended preparations of the poison has changed dramatically. Until 1944, the binding of hydrogen cyanide to hemoglobin was considered the mechanism of action, whereas from 1951 onwards, the interaction of hydrogen cyanide with the Fe3+ of cytochrome oxidase was described. The number of preparations containing hydrogen cyanide decreased into obsolescence until 1951. The areas of application of hydrogen cyanide also show a change, as from 1919 onwards, mainly industrial areas of application of the poison are described instead of medical ones, and from 1951 onwards, criminalistic areas of application are also mentioned. Thus, pharmacological and toxicological knowledge develops non-linearly, molecular mechanism and uses being the most dynamic areas, whereas the knowledge about hydrogen cyanide's chemical structure, lethal dose, and occurrence remained constant. Older pharmacology and toxicology textbooks were better than newer ones at discussing changes in scientific concepts. Pharmacology and toxicology textbooks also mostly failed to discuss the misuse of hydrogen cyanide (Zyklon B) during the Nazi regime, missing an important opportunity to showcase the ethical responsibility of pharmacology and toxicology. Thus, future pharmacology and toxicology textbooks should improve on discussing the development of pharmacological and toxicological concepts and the ethical responsibility of the discipline.

13.
Forensic Toxicol ; 42(2): 221-231, 2024 Jul.
Article in English | MEDLINE | ID: mdl-38739353

ABSTRACT

PURPOSE: Forensic verification of cyanide (CN) poisoning by direct CN analysis in postmortem blood is challenging due to instability of CN in biological samples. CN metabolites, thiocyanate (SCN-) and 2-aminothiazoline-4-carboxylic acid (ATCA), have been proposed as more stable biomarkers, yet it is unclear if either is appropriate for this purpose. In this study, we evaluated the behavior of CN biomarkers in postmortem swine and postmortem blood to determine which serves as the best biomarker of CN exposure. METHODS: CN, SCN-, and ATCA were measured in postmortem swine (N = 8) stored at 4 °C and postmortem blood stored at 25 °C (room temperature, RT) and 37 °C (typical human body temperature, HBT). RESULTS: Following CN poisoning, the concentration of each CN biomarker increased well above the baseline. In postmortem swine, CN concentrations declined rapidly (t1/2 = 34.3 h) versus SCN- (t1/2 = 359 h, 15 days) and ATCA (t1/2 = 544 h, 23 days). CN instability in postmortem blood increased at RT (t1/2 = 10.7 h) and HBT (t1/2 = 6.6 h). SCN- and ATCA were more stable than CN at all storage conditions. In postmortem swine, the t1/2s of SCN- and ATCA were 15 and 23 days, respectively. While both the t1/2s of SCN- and ATCA were relatively lengthy, endogenous levels of SCN- were much more variable than ATCA. CONCLUSION: While there are still questions to be answered, ATCA was the most adept forensic marker of CN poisoning (i.e., ATCA produced the longest half-life, the largest increase above baseline levels, and most stable background concentrations).


Subject(s)
Biomarkers , Cyanides , Animals , Cyanides/poisoning , Cyanides/blood , Biomarkers/blood , Swine , Thiocyanates/poisoning , Thiocyanates/blood , Thiocyanates/metabolism , Forensic Toxicology/methods , Models, Animal , Temperature , Specimen Handling/methods , Thiazoles
14.
Metabolites ; 14(5)2024 May 10.
Article in English | MEDLINE | ID: mdl-38786756

ABSTRACT

Purines are the building blocks of DNA/RNA, energy substrates, and cofactors. Purine metabolites, including ATP, GTP, NADH, and coenzyme A, are essential molecules in diverse biological processes such as energy metabolism, signal transduction, and enzyme activity. When purine levels increase, excess purines are either recycled to synthesize purine metabolites or catabolized to the end product uric acid. Purine catabolism increases during states of low oxygen tension (hypoxia and ischemia), but this metabolic pathway is incompletely understood in the context of histotoxic hypoxia (i.e., inhibition of oxygen utilization despite normal oxygen tension). In rabbits exposed to cyanide-a classical histotoxic hypoxia agent-we demonstrated significant increases in several concordant metabolites in the purine catabolic pathway (including plasma levels of uric acid, xanthosine, xanthine, hypoxanthine, and inosine) via mass spectrometry-based metabolite profiling. Pharmacological inhibition of the purine catabolic pathway with oxypurinol mitigated the deleterious effects of cyanide on skeletal muscle cytochrome c oxidase redox state, measured by non-invasive diffuse optical spectroscopy. Finally, plasma uric acid levels correlated strongly with those of lactic acid, an established clinical biomarker of cyanide exposure, in addition to a tissue biomarker of cyanide exposure (skeletal muscle cytochrome c oxidase redox state). Cumulatively, these findings not only shed light on the in vivo role(s) of cyanide but also have implications in the field of medical countermeasure (MCM) development.

15.
Biosensors (Basel) ; 14(5)2024 May 13.
Article in English | MEDLINE | ID: mdl-38785718

ABSTRACT

A novel indolium-based fluorescent probe for the detection of CN- was developed based on the conjugation of 1, 2, 3, 3-Tetramethyl-3H-indolium iodide and 2-acetyl benzothiophene. The introduction of external CN- caused a nucleophilic attack to the quaternary amine salt structure in the probe and resulted in the departure of iodide ions and the steric rotation of the index salt group, which caused fluorescence quenching. The titration experiments showed that the probe had rapid qualitative and quantitative analysis capabilities for CN-. Moreover, the relevant biocompatibility experiments also demonstrated the potential application value of the probe.


Subject(s)
Cyanides , Fluorescent Dyes , Indoles , Spectrometry, Fluorescence , Fluorescent Dyes/chemistry , Indoles/chemistry , Cyanides/analysis , Biosensing Techniques
16.
Prep Biochem Biotechnol ; : 1-10, 2024 May 02.
Article in English | MEDLINE | ID: mdl-38696619

ABSTRACT

Klebsiella oxytoca JCM 1665 was subjected to extracellular rhodanese production using a submerged fermentation technique. The organism was further engineered for higher cyanide tolerance and rhodanese yield using ethylmethanesulfonate as a mutagen. Mutagenesis resulted in an improved mutant with high cyanide tolerance (100 mM) and rhodanese yield (26.7 ± 0.67 U/mL). This yield was 4.34-fold higher than the wild strain (6.15 ± 0.65 U/mL). At temperatures ranging from 30 to 80 °C, the first-order thermal denaturation constant (Kd) for free enzyme increases from 0.00818 to 0.0333 min-1 while the immobilized enzyme increases from 0.003 to 0.0204 min-1. The equivalent half-life reduces from 99 to 21 minutes and 231 to 35 minutes, respectively. Residual activity tests were used to assess the thermodynamic parameters for both enzyme preparations. For the free enzyme, the parameters obtained were enthalpy (29.40 to 29.06 kJ.mol-1), entropy (-194.24 to -197.50 J.mol-1K-1) and Gibbs free energy (90.20 to 98.80 kJ.mol-1). In addition, for immobilized rhodanese, we obtained enthalpy (40.40 to 40.07 kJ.mol-1), entropy (-164.21 to - 165.20 J.mol-1K-1) and Gibbs free energy (91.80 to 98.40 kJ.mol-1. Regarding its operational stability, the enzyme was able to maintain 63% of its activity after being used for five cycles. Immobilized K. oxytoca rhodanese showed a marked resistance to heat inactivation compared to free enzyme forms; making it of utmost significance in many biotechnological applications.

17.
Plant Sci ; 345: 112118, 2024 Aug.
Article in English | MEDLINE | ID: mdl-38776983

ABSTRACT

Understanding the complex interactions between plants and herbivores is essential for improving crop resistance. Aiming to expand the role of cyanogenesis in plant defence, we investigated the response of the cyanogenic Phaseolus lunatus (lima bean) and the non-cyanogenic Phaseolus vulgaris (common bean) to Tetranychus urticae (spider mite) infestation. Despite mite infesting both legumes, leaf damage infringed by this feeder was reduced in lima bean. Comparative transcriptome analyses revealed that both species exhibited substantial metabolic and transcriptional changes upon infestation, although alterations in P. lunatus were significantly more pronounced. Specific differences in amino acid homeostasis and key genes associated with the cyanogenic pathway were observed in these species, as well as the upregulation of the mandelonitrile lyase gene (PlMNL1) following T. urticae feeding. Concomitantly, the PIMNL1 activity increased. Lima bean plants also displayed an induction of ß-cyanoalanine synthase (PlCYSC1), a key enzyme for cyanide detoxification, suggesting an internal regulatory mechanism to manage the toxicity of their defence responses. These findings contribute to our understanding of the legume-herbivore interactions and underscore the potential role of cyanogenesis in the elaboration of specific defensive responses, even within the same genus, which may reflect distinctive evolutionary adaptations or varying metabolic capabilities between species.


Subject(s)
Phaseolus , Tetranychidae , Tetranychidae/physiology , Animals , Phaseolus/parasitology , Phaseolus/physiology , Phaseolus/genetics , Plant Proteins/metabolism , Plant Proteins/genetics , Plant Defense Against Herbivory , Herbivory , Gene Expression Regulation, Plant , Plant Leaves/parasitology , Plant Leaves/metabolism
18.
Acta Crystallogr C Struct Chem ; 80(Pt 6): 212-220, 2024 Jun 01.
Article in English | MEDLINE | ID: mdl-38700936

ABSTRACT

The crystal structures of three mixed-valence copper cyanide alkanolamine polymers are presented, together with thermogravimetric analysis (TGA) and electron spin resonance (ESR) data. In all three structures, a CuII moiety on a crystallographic center of symmetry is coordinated by two alkanolamines and links two CuICN chains via cyanide bridging groups to form diperiodic sheets. The sheets are linked together by cuprophilic CuI-CuI interactions to form a three-dimensional network. In poly[bis(µ-3-aminopropanolato)tetra-µ-cyanido-dicopper(I)dicopper(II)], [Cu4(CN)4(C3H8NO)2]n, 1, propanolamine bases have lost their hydroxyl H atoms and coordinate as chelates to two CuII atoms to form a dimeric CuII moiety bridged by the O atoms of the bases with CuII atoms in square-planar coordination. The ESR spectrum is very broad, indicating exchange between the two CuII centers. In poly[bis(2-aminopropanol)tetra-µ-cyanido-dicopper(I)copper(II)], [Cu3(CN)4(C3H9NO)2]n, 2, and poly[bis(2-aminoethanol)tetra-µ-cyanido-dicopper(I)copper(II)], [Cu3(CN)4(CH7NO)2]n, 3, a single CuII atom links the CuICN chains together via CN bridges. The chelating alkanolamines are not ionized, and the OH groups form rather long bonds in the axial positions of the octahedrally coordinated CuII atoms. The coordination geometries of CuII in 2 and 3 are almost identical, except that the Cu-O distances are longer in 2 than in 3, which may explain their somewhat different ESR spectra. Thermal decomposition in 2 and 3, but not in 1, begins with the loss of HCN(g), and this can be correlated with the presence of OH protons on the ligands in 2 and 3, which are not present in 1.

19.
Chemistry ; 30(40): e202303370, 2024 Jul 16.
Article in English | MEDLINE | ID: mdl-38727553

ABSTRACT

The first example of a bis(cyaphido) complex, trans-[Ru(dppe)2(C≡P)2], is described, unequivocally demonstrating the synthetic accessibility and stability of complexes that feature more than one cyaphido ligand. Synthesis is achieved from the precedent cation [Ru(dppe)2(C≡P)]+ via sequential coordination and desilylation of the phosphaalkyne Me3SiC≡P. The heteroleptic analogue trans-[Ru(dppe)2(C≡N)(C≡P)] is also prepared from the same cation and NaCN; both cyaphido complexes are structurally characterized, enabling the first direct comparison of cyaphide with cyanide, its isoelectronic and isolobal counterpart. This demonstrates an enhanced π-acidity for -C≡P over -C≡N, while computational studies reveal also a higher π-donor character for the cyaphido ligand.

20.
Emerg Med Australas ; 36(4): 650-651, 2024 Aug.
Article in English | MEDLINE | ID: mdl-38807508

ABSTRACT

OBJECTIVE: Vitamin B17 tablets are sold (online) as an alternative cancer therapy medication. Its use however is not benign, given that it is metabolised into hydrogen cyanide. We aimed to measure the number of calls received by the New South Wales Poisons Information Centre (NSW PIC) regarding Amygdalin exposures. METHODS: A retrospective review of all amygdalin/cyanogenic glycoside product ingestion exposure calls to NSW PIC between 2015 and 2022. RESULTS: There were 120 unique exposure calls. Eighty-two (68%) were regarding minor exposures, with the remaining 38 (32%) of calls involving patients who had either a signifcant history or symptoms to prompt referral to hospital or were already seeking advice from a treating hospital clinican. CONCLUSION: There is a significant burden of concern generated from the misuse of cyanogenic glycoside products for cancer prevention and treatment, which can result in hospital admission carrying significant health risk and expenditure.


Subject(s)
Amygdalin , Neoplasms , Humans , Retrospective Studies , New South Wales/epidemiology , Male , Amygdalin/therapeutic use , Amygdalin/pharmacology , Female , Adult , Middle Aged , Poison Control Centers/statistics & numerical data , Aged , Adolescent , Child , Glycosides/therapeutic use , Glycosides/pharmacology
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