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Objective: Evaluate the impact of a "fast" crystallization and simultaneous-glazing on the physicochemical properties of lithium-disilicate CAD/CAM-ceramic., Methods: Lithium-disilicate bars and crowns (IPS e.max CAD, Ivoclar-Vivadent) were divided into four groups (n = 30): WG/F (WG=with glaze/F=fast crystallization), NG/F (NG=no glaze), WG/C (C=conventional crystallization), and NG/C. A liquid/powder glaze system was used (IPS Ivocolor®, Ivoclar-Vivadent). Specimens were crystallized (Programat P310, Ivoclar-Vivadent) using the P161 program for C (approx. 20-25 min), and P165 for F (approx. 14-16 min). Bars (n = 30) underwent three-point bending tests (flexural strength-FS in MPa and modulus of elasticity-E in GPa) using a universal testing machine. Crowns were analyzed via scanning electron microscopy (SEM) after selective etching, and to Raman, FTIR-ATR, and X-ray diffraction (XRD) spectroscopies to assess chemical composition., Results: For FS, both factors/interaction were statistically significant. C (427.48±42.41 MPa) showed significantly higher values than F (409.82±38.82 MPa). WG (398.32±29.80 MPa) exhibited significantly lower FS than NG (438.21±41.77 MPa). For E data, both factors/interaction were significant. NG (90.28±14.71 GPa) displayed higher E than WG (83.07±5.69 GPa), while C (90.08±12.98 GPa) exhibited higher E than F (83.46±9.40 GPa). NG/C showed the best results for both variables. F groups showed (SEM) porous surfaces and crack-like marks on crystals. FTIR, Raman and XRD spectra confirmed the typical composition of a lithium-disilicate glass ceramic, and some attenuated signals and structural variations (XRD) in WG., Conclusions: "Fast" crystallization and simultaneous-glazing produced weaker/less-rigid structures with irregular crystals and glassy phases. Simultaneous glazing may have hindered proper thermal distribution during crystallization., Significance: "Fast" crystallization and simultaneous glazing with non-recommended systems, can adversely affect the final properties of lithium disilicate restorations., Competing Interests: Declaration of competing interest The authors of the work “Effect of “fast”-crystallization and simultaneous glazing on physicochemical properties of lithium-disilicate CAD/CAM ceramic” declare that they have no known competing financial interests or personal relationships that could have influenced the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

Despite many interventions, science education remains highly inequitable throughout the world. Internet-enabled experimental learning has the potential to reach underserved communities and increase the diversity of the scientific workforce. Here, we demonstrate the use of lab-on-a-chip (LoC) technologies to expose Latinx life science undergraduate students to introductory concepts of computer programming by taking advantage of open-loop cloud-integrated LoCs. We developed a context-aware curriculum to train students at over 8000 km from the experimental site. Through this curriculum, the students completed an assignment testing bacteria contamination in water using LoCs. We showed that this approach was sufficient to reduce the students' fear of programming and increase their interest in continuing careers with a computer science component. Altogether, we conclude that LoC-based internet-enabled learning can become a powerful tool to train Latinx students and increase the diversity in STEM., (© 2024. The Author(s).)

Precise modulation of brain activity is fundamental for the proper establishment and maturation of the cerebral cortex. To this end, cortical organoids are promising tools to study circuit formation and the underpinnings of neurodevelopmental disease. However, the ability to manipulate neuronal activity with high temporal resolution in brain organoids remains limited. To overcome this challenge, we introduce a bioelectronic approach to control cortical organoid activity with the selective delivery of ions and neurotransmitters. Using this approach, we sequentially increased and decreased neuronal activity in brain organoids with the bioelectronic delivery of potassium ions (K + ) and γ-aminobutyric acid (GABA), respectively, while simultaneously monitoring network activity. This works highlights bioelectronic ion pumps as tools for high-resolution temporal control of brain organoid activity toward precise pharmacological studies that can improve our understanding of neuronal function., Competing Interests: Declaration of interests The authors declare no competing interests., (Copyright © 2023 The Authors. Published by Elsevier Inc. All rights reserved.)

Fentanyl is a powerful synthetic opioid used to treat severe pain. New administration routes toward its illegal consumption for recreational purposes pose a growing threat to public health, either due to misuse or abuse of this substance. As a result, the rapid qualitative and quantitative determination of fentanyl in biofluids is of great interest. A novel enzymatic biosensor based on adsorptive-stripping cyclic voltammetry is proposed as a cost-effective, reliable, and efficient device for fentanyl determination in urine samples. Disposable screen-printed carbon electrodes modified with multi-walled carbon nanotubes and cytochrome c were used to develop the testing platform. The electrochemical behavior of fentanyl exhibited a well-defined anodic wave around 0.66 V vs. pseudo reference electrode. The experimental conditions were optimized to obtain the best analytical response, and linear regression analysis of increasing concentration standards was applied to estimate the performance parameters. The results suggest a simple method with a wide linearity range, high sensitivity, low limits of detection (0.086 μg/mL) and quantification, and satisfactory precision (2.9% RSD). The feasibility and applicability of the voltammetric approach were assessed by fentanyl-spiked urine samples by standard additions calibration curves in two levels of enrichment with an accuracy of 92% and 100%., (© 2022. The Author(s), under exclusive licence to Springer-Verlag GmbH Austria, part of Springer Nature.)

The synthetic cathinones mephedrone (4-MMC) and 4-methylethcathinone (4-MEC) are two designer drugs that represent the rise and fall effect of this drug category within the stimulants market and are still available in several countries around the world. As a result, the qualitative and quantitative determination of 'legal highs', and their mixtures, are of great interest. This work explores for the first time the spectroelectrochemical response of these substances by coupling cyclic voltammetry (CV) with Raman spectroscopy in a portable instrument. It was found that the stimulants exhibit a voltammetric response on a gold screen-printed electrode while the surface is simultaneously electro-activated to achieve a periodic surface-enhanced Raman spectroscopy (SERS) substrate with high reproducibility. The proposed method enables a rapid and reliable determination in which both substances can be selectively analyzed through the oxidation waves of the molecules and the characteristic bands of the electrochemical SERS (EC-SERS) spectra. The feasibility and applicability of the method were assessed in simulated seized drug samples and spiked synthetic urine. This time-resolved spectroelectrochemical technique provides a cost-effective and user-friendly tool for onsite screening of synthetic stimulants in matrices with low concentration analytes for forensic applications.

The electric field is an important parameter to vary in a single-molecule experiment, because it can directly affect the charge distribution around the molecule. Yet, performing such an experiment with a well-defined electric field for a model chemical reaction at an interface has proven to be extremely difficult. Here, by combining a graphene field-effect transistor and a gate-tunable scanning tunneling microscope (STM), we reveal how this strategy enables the intramolecular H atom transfer of a metal-free macrocycle to be controlled with an external field. Experiments and theory both elucidate how the energetic barrier to tautomerization decreases with increasing electric field. The consistency between the two results demonstrates the potential in using electric fields to engineer molecular switching mechanisms that are ubiquitous in nanoscale electronic devices.

Direct (photo)electrochemical production of non-fossil fuels from water and CO 2 requires water-oxidation catalysis at near-neutral pH in the presence of appropriate anions that serve as proton acceptors. We investigate the largely enigmatic structural role of anions in water oxidation for the prominent cobalt-phosphate catalyst (CoCat), an amorphous and hydrated oxide material. Co 3 ([(P/As)O] 4 ) 2 ·8H 2 O served, in conjunction with phosphate-arsenate exchange, as a synthetic model system. Its structural transformation was induced by prolonged operation at catalytic potentials and probed by X-ray absorption spectroscopy not only at the metal (Co), but for the first time also at the anion (As) K-edge. For initially isostructural microcrystals, anion exchange determined the amorphization process and final structure. Comparison to amorphous electrodeposited Co oxide revealed that in CoCat, the arsenate binds not only at oxide-layer edges, but also arsenic substitutes cobalt positions within the layered-oxide structure in an unusual AsO 6 coordination. Our results show that in water oxidation catalysis at near-neutral pH, anion type and exchange dynamics correlate with the catalyst structure and redox properties.

Chemical functionalization of graphene is achieved by hyperthermal reaction with azopyridine molecular ions. The one-step, room temperature process takes place in high vacuum (10(-7) mbar) using an electrospray ion beam deposition (ES-IBD) setup. For ion surface collisions exceeding a threshold kinetic energy of 165 eV, molecular cation beams of 4,4'-azobis(pyridine) covalently attach to chemical vapor deposited (CVD) graphene. A covalent functionalization degree of 3% of the carbon atoms of graphene is reached after 3-5 h of ion exposure of 2 × 10(14) azopyridinium/cm(2) of which 50% bind covalently. This facile approach for the controlled modification of graphene extends the scope of candidate species that would not otherwise react via existing conventional methods.

This combined experimental (STM, XPS) and molecular dynamics simulation study highlights the complex and subtle interplay of solvent effects and surface interactions on the 2-D self-assembly pattern of a Schiff-base macrocycle containing catechol moieties at the liquid-solid interface. STM imaging reveals a hexagonal ordering of the macrocycles at the n-tetradecane/Au(111) interface, compatible with a desorption of the lateral chains of the macrocycle. Interestingly, all the triangular-shaped macrocycles are oriented in the same direction, avoiding a close-packed structure. XPS experiments indicate the presence of a strong macrocycle-surface interaction. Also, MD simulations reveal substantial solvent effects. In particular, we find that co-adsorption of solvent molecules with the macrocycles induces desorption of lateral chains, and the solvent molecules act as spacers stabilizing the open self-assembly pattern.

The incidence of cervical cancer in Costa Rica is about twice as high in the coastal regions as in the interior. To study these regional variations, we used data from a 1986-1987 case-control study of 192 Costa Rican women with invasive cervical cancer and 372 controls. Risk factors identified included the following: The study participant's (1) number of sexual partners, (2) age at first sexual intercourse, (3) number of live births, (4) presence of type 16/18 human papillomavirus (HPV) DNA, (5) venereal disease (VD) history, (6) Pap smear history, and (7) socioeconomic status. The adjusted relative risks (RR) and 95% confidence intervals (CI) for each of these risk factors were as follows: (1) > or = 4 vs. 1 sexual partner: RR = 2.0, 95% CI = 1.1-3.5; (2) age of initiation < or = 15 vs. > or = 18 years: RR = 1.5, 95% CI = 0.9-2.5; (3) > or = 6 vs. < or = 1 live birth: RR = 1.7, 95% CI = 0.7-3.9; (4) HPV 16/18 DNA in cervix: RR = 2.8, 95% CI = 1.9-4.2; (5) VD history: RR = 2.2, 95% CI = 1.2-4.0; (6) no Pap smear: RR = 2.4, 95% CI = 1.5-3.8; and (7) low socioeconomic status: RR = 2.0, 95% CI = 1.2-3.2. The population-attributable risks related to HPV detection, four or more sexual partners, six or more live births, no prior Pap smear, and low socioeconomic status were 39%, 38%, 29%, 23%, and 22%, respectively. Several of the sexual and reproductive risk factors were relatively more prevalent in the high-risk region, but Pap screening and detection of HPV were equally prevalent in the high-risk and low-risk regions. Though differences in screening quality (laboratory and follow-up) may have been involved, we conclude that the observed regional differences reflect behavioral more than screening differences. This suggests that screening programs should be more aggressive in the high-risk area, given the more frequent occurrence of the disease there. Failure to detect a higher prevalence of HPV in the high-risk region could reflect weaknesses in the in situ hybridization test employed. Alternatively, cofactors may have to be present in order for HPV to exert its role in cervical carcinogenesis.

The apparent area of the abnormal transformation zone (TZ) of the cervix was measured in a total of 104 patients by a simple method with the use of the 1 and 5 mm. diameter circle in the center of the field of the Leisegang colposcope and the field of the colposcope itself. The visible area (mean +/- S.E.M.) of the abnormal TZ for five patients with microinvasive or occult carcinoma of the cervix (180.8 mm.2 +/- 62.2) was significantly larger (p less than 0.01) than that of 64 patients with major intraepithelial lesions (62.5 sq. mm.2 +/- 7.3) and 35 patients with minor intraepithelial lesions (45.8 sq. mm.2 +/- 11.7). The visible area of the abnormal TZ measured over 40 mm.2 in each of the five patients with invasive lesions but in only 42 of 99 (42%) patients with intraepithelial lesions. The TZ extended into the endocervical canal and could not be fully visualized in four (80%) of the patients with invasive lesions, 24 (38%) of patients with major intraepithelial lesions, and 11 (31%) of patients with minor intraepithelial lesions. The implications of these findings are discussed.

A 64-year-old woman with a 45,X karyotype and Turner's syndrome and recent onset of right lower quadrant pain was found to have a mucinous cystadenoma with focal areas of borderline malignancy and a typical Brenner tumor in the right adnexa. Ovarian tumors in patients with a 45,X karyotype and Turner's syndrome are extremely rare. The present paper is the first report of concurrence of these 2 tumors in an affected individual. The simultaneous occurrence and intimate admixture of these tumors in a patient believed to be devoid of germ cells would seem to favor a common histogenesis from the germinal epithelium.

A case of low-grade ovarian stromal sarcoma in a postmenopausal woman is described. Although pelvic recurrences of the tumor followed 5 and 7 years after the original surgery, the patient has remained well and without evidence of tumor 3 years since the last operation. Histopathologic, electronmicroscopic, and hormonal studies are described. There was evidence of estrogenic stimulation by the theca elements of the tumor in this patient. Cases previously reported in the world literature as malignant thecoma were analyzed, and most of them were considered inadequately documented; indeed most of them were probably either sarcomatoid granulosa cell tumors, stromal sarcomas, or fibrosarcomas. If a thecoma ever becomes malignant, the tumor cells dedifferentiate so that they cannot be recognized any longer as theca cells; instead, they proliferate as a stromal sarcoma or fibrosarcoma. It is proposed, therefore, that the term "malignant thecoma" not be used. On the other hand, very rare malignant ovarian stromal tumors do exist, consisting of undifferentiated stromal cells, fibroblasts, and theca cells, which can show evidence of hormonal activity.

Basement membranes of 33 samples of in situ or invasive squamous cell carcinomas of the cervix uteri, vagina, and vulva were studied by defined immunofluorescence technics. Pooled serum from patients with bullous pemphigoid, containing specific antibody to squamous epithelial basement membrane, was utilized. Essentially normal basement membranes were found in all cases of in situ carcinoma and in 18 cases of invasive carcinoma. Basement membranes appeared poorly formed in three specimens with invasion and were absent in the remaining three. These findings support the premise that penetration of the basement membrane is not a valid criterion for distinguishing in situ from invasive squamous cell carcinoma.

A total of 259 patients underwent endocervical curettage as an integral part of colposcopic examination of patients with abnormal cervical cytology. The transformation zone was entirely visualized in 140 patients (54.1 per cent), and, in 8.6 per cent of this group, the endocervical curettings were abnormal. On no occasion did the endocervical curettage harbor the worst lesion when compared to the histology of the ectocervical biopsy, cone biopsy, and hysterectomy specimens. In 117 patients (45.2 per cent), the transformation zone could not be visualized in its entirety, and in 57.3 per cent the endocervical curettings were abnormal. In one patient of this group invasive carcinoma was present in the endocervical curettage, and in another patient invasive carcinoma was present in both the ectocervical biopsy and the endocervical curettage. Thus, when the entire transformation zone is not visualized in its entirety or at all, endocervical curettage appears to be of value since a frank invasive carcinoma may be diagnosed and a cone biopsy avoided.