Toluene Oxidation: CO2 vs Benzaldehyde: Current Status and Future Perspectives.

Toluene is a common and significant volatile organic compound (VOC). Although it finds extensive application in various industrial processes (chemical manufacturing, paint and adhesive production, and as a solvent), it creates a huge environmental impact when emitted freely into the atmosphere. Two solutions were found to mitigate the emission of this pollutant: the total oxidation to CO2 and H2O and the selective oxidation into benzaldehyde. This review discusses the two main alternatives for tackling this problem: converting the toluene into carbon dioxide by total oxidation or into benzaldehyde by selective oxidation. It presents new catalytic advances, new trends, and the advantages and disadvantages of both methods.

CO2-Driven N-Formylation/N-Methylation of Amines Using C-Scorpionate Metal Complexes.

C-scorpionate metal complexes, specifically, [NiCl2(tpm)]·3H2O, [CoCl2(tpm)]·3H2O and [PdCl2(tpm)] [tpm = hydrotris(1H-pyrazol-1-yl)methane], were effective in the N-formylation and N-methylation of amines using carbon dioxide, as carbon source, in the presence of sodium borohydride. Various parameters were studied, including reaction time, temperature, solvent volume, presence of additives, and catalyst amount. These parameters were found to have a significant impact on the selectivity of the product. [NiCl2(tpm)]·3H2O exhibited good conversion at 80 °C, but its selectivity towards formamide decreased with prolonged reaction time. Increasing the amount of [NiCl2(tpm)]·3H2O, the selectivity changed. [PdCl2(tpm)] showed different selectivity compared to [NiCl2(tpm)]·3H2O, while [CoCl2(tpm)]·3H2O presented poor results. Monitoring the reaction course by 1H NMR revealed the presence of an intermediate species that influenced product formation. These results highlight the versatility and catalytic potential of C-scorpionate metal complexes in the N-formylation/N-methylation of amines in the catalytic system (NaBH4/MeCN/CO2).

Vaginal hysterectomy for the treatment of low-risk endometrial cancer: Surgical technique, costs, and perioperative and oncologic results.

OBJECTIVES: This study aimed to describe an operative technique for vaginal hysterectomy (VH) and assess the costs, perioperative, and oncological outcomes for this procedure when used in the treatment of patients with low-risk endometrial cancer (LREC). METHODS: A retrospective analysis of medical records was conducted on patients who underwent VH to treat precursor and invasive endometrial lesions between April 2019 and November 2021 at a single center in São Paulo, Brazil. RESULTS: Thirty-four patients met the inclusion criteria. The mean patient age was 61.9 years, and the mean body mass index (BMI) was 34. Obese patients (BMI ≥ 30) accounted for 77% of the sample. Preoperative functional capacity measures were Eastern Cooperative Oncology Group (ECOG) 0-1 and ECOG-2 for 91% and 9% of the patients, respectively. The mean operative time and length of hospital stay were 109 min and 1.2 days, respectively. Four patients had a conversion of the surgical route to laparotomy. No major intraoperative complications were observed. Patients who underwent surgical conversion had a greater uterine volume (227 versus 107 mL, p = 0.006) and longer operative time (177 versus 96 min, p = 0.001). The total cost associated with VH was, on average, US$ 2058.77 (R$ 10,925.91), representing 47% of the cost associated with non-vaginal routes. Twenty-eight patients received a definitive diagnosis of endometrial carcinoma; of these, three received adjuvant radiotherapy. The mean follow-up period was 34.6 months for the patients diagnosed with cancer. One case of disease recurrence occurred 16.6 months after surgery, with one death at 28.6 months of follow-up. CONCLUSIONS: These findings suggest that VH could be a feasible and cost-effective alternative for selected patients with LREC in low-resource settings.

Ultrasound Assisted Coextraction of Cornicabra Olives and Thyme to Obtain Flavored Olive Oils.

Flavoring olive oils is a new trend in consumer preferences, and different enrichment techniques can be used. Coextraction of olives with a flavoring agent is an option for obtaining a flavored product without the need for further operations. Moreover, ultrasound (US) assisted extraction is an emergent technology able to increase extractability. Combining US and coextraction, it is possible to obtain new products using different types of olives (e.g., cultivar and ripening stage), ingredient(s) with the greatest flavoring and/or bioactive potential, as well as extraction conditions. In the present study, mastic thyme (Thymus mastichina L.) (TM) and lemon thyme (Thymus x citriodorus) (TC) were used for flavoring Cornicabra oils by coextraction. The coextraction trials were performed by (i) thyme addition to the olives during crushing or malaxation and (ii) US application before malaxation. Several parameters were evaluated in the oil: quality criteria parameters, total phenols, fatty acid composition, chlorophyll pigments, phenolic profile and oxidative stability. US application did not change the phenolic profile of Cornicabra olive oils, while the enrichment of olive oils with phenolic compounds or pigments by coextraction was very dependent on the thyme used. TM enrichment showed an improvement of several new phenolic compounds in the oils, while with TC, fewer new phenols were observed. In turn, in the trials with TC, the extraction of chlorophyll pigments was higher, particularly in crushing coprocessing. Moreover, the oils obtained with US and TM added in the mill or in the malaxator showed lower phenol decrease (59%) than oils flavored with TC (76% decrease) or Cornicabra virgin olive oil (80% decrease) over an 8-month storage period. Multivariate data analysis, considering quality parameters, pigments and phenolic contents, showed that flavored oils were mainly grouped by age.

Hepatitis C and Human Pegivirus Coinfection in Patients with Chronic Hepatitis C from the Brazilian Amazon Region: Prevalence, Genotypes and Clinical Data.

Coinfection of HPgV-1 with hepatitis C virus (HCV) is common due to shared modes of transmission, with a prevalence of HPgV-1 viremia of approximately 20% among individuals with chronic HCV infection. The aim of the present study was to estimate the prevalence of HPgV-1 RNA and circulating genotypes in patients with hepatitis C from a health service located in the city of Belém, in the state of Pará, Northern Brazil. A total of 147 samples were included in the study from February to December 2019. Among the participants, 72.1% (106/147) were monoinfected with HCV, with detectable HCV viral RNA, and 27.9% (41/147) were coinfected with HCV/HPgV-1. The most frequently found genotypes were HPgV-1 genotypes 1 and 2 (36.6% and 63.4%), respectively. While for HCV there was a predominance of genotypes 1 and 3 (58.5% and 41.5%). No significant differences were found when comparing any risk, sociodemographic, or clinical factors between groups. Also, there was no statistically significant difference when relating the viral genotypes of both agents. This study indicated that the prevalence of infection by HPgV-1 is high in HCV carriers in Belém, Pará, and probably does not change the clinical course of HCV infection, however, further studies are still needed.

Correction: The reaction of acetonitrile with hydrogen peroxide in alkaline medium: a DFT mechanistic study of green production of amides.

Correction for 'The reaction of acetonitrile with hydrogen peroxide in alkaline medium: a DFT mechanistic study of green production of amides' by Girolamo Casella et al., Phys. Chem. Chem. Phys., 2023, https://doi.org/10.1039/d3cp02024j.

Exploring the Mechanisms behind the Anti-Tumoral Effects of Model C-Scorpionate Complexes.

The growing worldwide cancer incidence, coupled to the increasing occurrence of multidrug cancer resistance, requires a continuous effort towards the identification of new leads for cancer management. In this work, two C-scorpionate complexes, [FeCl2(κ3-Tpm)] (1) and [Co(κ3-TpmOH)2](NO3)2 (2), (Tpm = hydrotris(pyrazol-1-yl)methane and TpmOH = 2,2,2-tris(pyrazol-1-yl)ethanol), were studied as potential scaffolds for future anticancer drug development. Their cytotoxicity and cell migration inhibitory activity were analyzed, and an untargeted metabolomics approach was employed to elucidate the biological processes significantly affected by these two complexes, using two tumoral cell lines (B16 and HCT116) and a non-tumoral cell line (HaCaT). While [FeCl2(κ3-Tpm)] did not display a significant cytotoxicity, [Co(κ3-TpmOH)2](NO3)2 was particularly cytotoxic against the HCT116 cell line. While [Co(κ3-TpmOH)2](NO3)2 significantly inhibited cell migration in all tested cell lines, [FeCl2(κ3-Tpm)] displayed a mixed activity. From a metabolomics perspective, exposure to [FeCl2(κ3-Tpm)] was associated with changes in various metabolic pathways involving tyrosine, where iron-dependent enzymes are particularly relevant. On the other hand, [Co(κ3-TpmOH)2](NO3)2 was associated with dysregulation of cell adhesion and membrane structural pathways, suggesting that its antiproliferative and anti-migration properties could be due to changes in the overall cellular adhesion mechanisms.

The reaction of acetonitrile with hydrogen peroxide in alkaline medium: a DFT mechanistic study of green production of amides.

We have investigated using DFT methods the reaction mechanism of the Radzisewski reaction to obtain an amide via the reaction of ACN and H2O2 under alkaline conditions. The direct reaction between ACN and H2O2 showed a quite high activation energy (about 45 kcal mol-1) rendering this path unreliable. Instead, a fast reaction between ACN and HOO- forming the deprotonated species (PAIA-) of the peroxyacetimidic acid (PAIA) was observed. From this, PAIA- was guessed to form PAIA through a fast reaction of hydrolysis. Moreover, a second way of formation of PAIA, through an OH- catalyzed path, made the rate determining step (RDS) in very good agreement with experimental data, hence neglecting the contribution of the kinetically favored hydrolysis of PAIA-. This discrepancy was reconciled by considering that the final amide was obtained through a regioselective path forming the PAIA and the further reaction involving the decomposition of PAIA and PAIA-. Indeed, the PAIA obtained from the hydrolysis reaction showed a configuration which did not match the configurational behavior required. Conversely, the PAIA formed from the RDS path matched the required configuration needed to obtain the amide. Our findings also disentangled the experimenal debate on the assignment of the RDS.

The Naked Neck Gene in the Domestic Chicken: A Genetic Strategy to Mitigate the Impact of Heat Stress in Poultry Production-A Review.

The poultry sector is one of the most important food industries in the world. Poultry production generates high-value protein products (meat and eggs) that are produced efficiently without the need for large areas. In poultry production, especially in the tropics, environmental factors, such as temperature and humidity, play a major role. Heat stress (HS) causes behavioral, physical, and physiological changes in poultry, with severe financial impacts. Therefore, it is important to find strategies to minimize it. The naked neck (Na) is an autosomal, incompletely dominant gene. Compared with normal feathered birds, these animals are known for their ability to adapt, perform, and reproduce under hot and humid climate conditions. Due to the absence of feathers on the neck, these animals increase heat dissipation, alleviating adverse heat effects, especially on productive performance. Genetic improvement of heat tolerance may provide a low-cost solution, of particular interest for developing countries in the tropics. The focus of this review is to evaluate the impact of HS in poultry with a special emphasis on the advantages of using the Na gene.

p-Xylene Oxidation to Terephthalic Acid: New Trends.

Large-scale terephthalic acid production from the oxidation of p-xylene is an especially important process in the polyester industry, as it is mainly used in polyethylene terephthalate (PET) manufacturing, a polymer that is widely used in fibers, films, and plastic products. This review presents and discusses catalytic advances and new trends in terephthalic acid production (since 2014), innovations in terephthalic acid purification processes, and simulations of reactors and reaction mechanisms.

Glycerol Valorization-The Role of Biochar Catalysts.

The conversion of renewable feedstocks into new added-value products is a current hot topic that includes the biodiesel industry. When converting vegetable oils into biodiesel, approximately 10% of glycerol byproduct is produced. Glycerol can be envisaged as a chemical platform due to its chemical versatility, as a scaffold or building block, in producing a wide range of added-value chemicals. Thus, the development of sustainable routes to obtain glycerol-based products is crucial and urgent. This certainly encompasses the use of raw carbonaceous materials from biomass as heterogeneous acid catalysts. Moreover, the integration of surface functional groups, such as sulfonic acid, in carbon-based solid materials, makes them low cost, exhibiting high catalytic activity with concomitant stability. This review summarizes the work developed by the scientific community, during the last 10 years, on the use of biochar catalysts for glycerol transformation.

Syphilis and Co-Infections with HIV-1, HBV, and HCV among People Who Use Crack-Cocaine in Northern Brazil.

The rates of syphilis and viral co-infections among people who use crack-cocaine (PWUCC) were assessed in this study. This cross-sectional study relied on biological and self-reported socio-behavioral data from a convenience sample of 990 PWUCC from twenty-six municipalities in the states of Amapá and Pará, northern Brazil. Blood samples were collected to assess the presence of Treponema pallidum using the Rapid Qualitative Test (RQT) and the Venereal Disease Research Laboratory (VDRL). Reactive samples by RQT were used to assess the presence of HBV, HCV, and HIV-1 using Enzyme Immunoassay (EIA) and Polymerase Chain Reaction (PCR). Logistic regression models were used to determine the association of variables assessed with syphilis. In total, 287 (29.0%) of the PWUCC sample had reactive results for syphilis. HBV (15.7%), HCV (5.9%), and HIV-1 (9.8%) were detected among PWUCC with syphilis. Young age, low monthly income and education level, long duration of crack-cocaine use, condomless sex, multiple sex partners, and exchange of sex for money/drugs were associated with syphilis. The present study provides unique insights on the epidemiological status of syphilis among PWUCC in northern Brazil, with multiple implications for improving urgent interventions for diagnosis, prevention, and treatment.

Spread of Human T-Lymphotropic Virus 1 and 2 Among Relatives of People Who Use Illicit Drugs in Northern Brazil.

The human T-lymphotropic virus 1 (HTLV-1) and 2 (HTLV-2) can be transmitted between humans by mechanisms associated with horizontal and vertical routes. Recently, high prevalence rates and levels of genetic diversity for HTLV-1 and HTLV-2 were detected among people who use illicit drugs (PWUDs) in the Brazilian state of Pará. None of the PWUDs with HTLV-1 or HTLV-2 were aware of their carrier condition of the retrovirus, and they ability to spread it to their family group, sexual partners, and other contacts. Thus, this study evaluated the presence of HTLV-1 and HTLV-2 in families of PWUDs in the state of Pará, in Northern Brazil. This descriptive study used convenience sampling and accessed 37 PWUDs and their respective families (n = 97) in 18 municipalities in the state of Pará, northern Brazil. All participants provided personal data and were tested for the presence of HTLV-1 and HTLV-2 using enzyme-linked immunosorbent assay and western blotting. HTLV positive samples were selected for Nested-PCR, and viral genotyping by nucleotide sequencing and phylogenetic analysis. HTLV-1 or HTLV-2 infections were detected in 15 families of PWUDs: 27 family members of PWUDs were infected with HTLV-1 (27.8%) and another 20 of them with HTLV-2 (20.6%). Subtypes 1a [subgroup A (54.5%)], 2b (20.5%), and 2c (25.0%) were detected. High horizontal (76.9%) and vertical (61.4%) transmission rates of HTLV were ascertained. Factors that facilitate the acquisition and transmission of HTLV-1 and HTLV-2 were reported by the participants, such as long-term relationships, unprotected sex, breastfeeding, and lack of knowledge about the condition of being a carrier of the retrovirus. Evidence indicates intrafamilial transmission of HTLV from PWUDs to members of their respective families. Key interventions should urgently be employed for the control and prevention of HTLV-1 and HTLV-2 to reduce the spread of this retrovirus in PWUDs and the general population in Northern Brazil and elsewhere.

Metabolomic Profiling of Peripheral Plasma by GC-MS and Correlation With Size of Uterine Leiomyomas.

Background: Uterine leiomyomas are benign monoclonal tumors originating from the myometrium. Little information exists concerning metabolomics and the presence of leiomyomas. Objective: The present study evaluated circulating metabolites in the plasma and their correlation with the presence and size of leiomyomas. Study Design: Cross-sectional observational study, including women divided into 3 groups: 37 with leiomyomas and uterus >500 cm3, 17 with leiomyomas and uterus ≤150 cm3, and 21 leiomyoma-free. Patients underwent peripheral blood collection using untargeted metabolic assessment by gas chromatography coupled to mass spectrometer. Results: There was no statistical difference between patients' anthropometric and demographic features and laboratory tests. Statistical differences in uterus volume (P < 0.0001) were found. Forty-six metabolites were identified (35% amino acids and derivatives, 22% fatty acids, and 18% carbohydrates). Statistically significant metabolic distinction (P < 0.05, false discovery rate< 0.05) was observed for 14 metabolites. Most amino acids (L-isoleucine, L-valine, and pyroglutamic acid) were significantly reduced in plasma levels of patients with large leiomyomas. The only exception was L-glutamine, with a significant increase. Fatty acids (arachidonic acid, alfa-tocopherol, palmitic acid, and stearic acid) were similarly reduced in large leiomyomas patients, except for alpha-linolenic acid, which increased. For carbohydrates (myo-inositol, D-threitol, and D-ribose), there was a decrease in the plasma of patients with leiomyomas. Conclusion: There are different plasma metabolites levels of amino acids, fatty acids, and carbohydrates among patients with leiomyomas, most of them reduced, but some significantly increased in large leiomyomas, compared to leiomyoma-free patients.

Comparison of Patients Monoinfected with Hepatitis C Virus and Coinfected with Hepatitis B/C in the Amazon Region of Brazil.

Hepatitis B and C are the most common causes of liver disease worldwide. The two infections share many similarities such as a global distribution, the same routes of transmission, hepatotropism, and the ability to cause chronic infection. The consequences of HBV/HCV coinfection are still being studied. The aim of this study is to describe and compare the epidemiological and laboratory profile and the degree of hepatic fibrosis between HCV-monoinfected and HBV/HCV-coinfected patients in the Brazilian Amazon region. ELISA tests were used for the investigation of HBV and HCV serological markers, and molecular tests were used for the detection and genotyping of these viruses. Additionally, transaminases were measured, and a FibroScan was performed for the analysis of liver function. A total of 328 patients with HCV participated in the study. The serological prevalence of HCV/HBV coinfection was 10.77%. A comparison of risk factors between the monoinfected and coinfected groups showed that illicit drug use, sharing sharp instruments, and tattooing/piercing are significantly associated with coinfection. The monoinfected patients had a higher HCV load than the coinfected patients. A viral interaction was observed in this study in which the presence of a coinfection with HBV appears to influence HCV replication. Further studies are necessary to better understand this interaction.

Diastereomeric dinickel(II) complexes with non-innocent bis(octaazamacrocyclic) ligands: isomerization, spectroelectrochemistry, DFT calculations and use in catalytic oxidation of cyclohexane.

Diastereomeric dinickel(II) complexes with bis-octaazamacrocyclic 15-membered ligands [Ni(L1-3-L1-3)Ni] (4-6) have been prepared by oxidative dehydrogenation of nickel(II) complexes NiL1-3 (1-3) derived from 1,2- and 1,3-diketones and S-methylisothiocarbohydrazide. The compounds were characterized by elemental analysis, ESI mass spectrometry, and IR, UV-vis, 1H NMR, and 13C NMR spectroscopy. Single crystal X-ray diffraction (SC-XRD) confirmed the isolation of the anti and syn isomers of bis-octaazamacrocyclic dinickel(II) complexes 4a and 4s, the syn-configuration of 5s and the anti-configuration of the dinickel(II) complex 6a. Dimerization of prochiral nickel(II) complexes 1-3 generates two chiral centers at the bridging carbon atoms. The anti-complexes were isolated as meso-isomers (4a and 6a) and the syn-compounds as racemic mixtures of R,R/S,S-enantiomers (4s and 5s). The syn-anti isomerization (epimerization) of the isolated complexes in chloroform was disclosed. The isomerization kinetics of 5a was monitored at five different temperatures ranging from 20 °C to 50 °C by 1H NMR spectroscopy indicating the clean conversion of 5a into 5s. The activation barrier determined from the temperature dependence of the rate constants via the Eyring equation was found to be ΔH‡ = 114 ± 1 kJ mol-1 with activation entropy ΔS‡ = 13 ± 3 J K-1 mol-1. The complexes contain two low-spin nickel(II) ions in a square-planar coordination environment. The electrochemical behavior of 4a, 4s, 5s and 6a and the electronic structure of the oxidized species were studied by UV-vis-NIR-spectroelectrochemistry (SEC) and DFT calculations indicating the redox non-innocent behavior of the complexes. The dinickel(II) complexes 4a, 4s, 5s and 6a/6s were investigated as catalysts for microwave-assisted solvent-free oxidation of cyclohexane by tert-butyl hydroperoxide to produce a mixture of cyclohexanone and cyclohexanol (KA oil). The best value for KA oil yield (16%) was obtained with a mixture of 6a/6s after 2 h of microwave irradiation at 100 °C.

Unprecedented Mechanochemical Synthesis and Heterogenization of a C-Scorpionate Au(III) Catalyst for Microwave-Assisted Biomass Valorization.

The transformation of biomass, a carbon resource presenting a huge potential to produce valuable chemicals, requires the search for sustainable catalytic routes. This work proposes the microwave-assisted oxidation of biomass -derived substrates, such as glycerol and the furfural derivatives 5-(hydroxymethyl)furfural (HMF) and 5-hydroxymethyl-2-furancarboxylic acid (HFCA), using the C-scorpionate dichloro-gold(III) complex [AuCl2(κ2-Tpm)]Cl (Tpm = HCpz3; pz = pyrazol-1-yl) as a catalyst, as prepared and supported on graphene, in solvent-free conditions. The unprecedented application of a mechanochemical procedure (in a planetary ball mill, in solid state) to synthesize a C-scorpionate complex, the [AuCl2(κ2-Tpm)]Cl, is disclosed. The immobilization of [AuCl2(κ2-Tpm)]Cl on graphene was performed using different methods, including some (e.g., microwave irradiation and liquid assisted grinding) for the first time. The structural properties and the performance of the prepared catalytic materials are presented and discussed.

A sex specific approach of ophthalmic and middle cerebral arteries Doppler in smokers.

Vascular dysfunctions can progress and lead to stroke and cardiovascular disease, especially in smokers. The presence of particular vascular changes according to sex has been described and they can be identified by the Doppler method. This study evaluated Doppler velocimetry parameters of the Ophthalmic Artery (OA) and the Middle Cerebral Artery (MCA) according to sex in smokers regarding a non-smoker group. This cross-sectional observational study included 178 subjects: 93 women and 85 men. Doppler parameters were assessed in OA and MCA. Student's t-test was used, with p < 0.05. There were no significant differences in OA and MCA Doppler velocimetry data between male non-smokers and smokers. However, female smokers presented several differences compared with non-smokers: lower pulsatility index (PI) and higher peak ratio in OA, and higher PI and resistance index and lower end diastolic velocity in MCA. There were different brain vascular waveforms in the group of female smokers compared with non-smokers. Cigarette smoking also led to opposite arterial patterns in OA and MCA in the female group, with signs of falling impedance in OA and increased impedance in MCA. An individualized approach regarding arterial changes according to sex is desirable.