Low-cost inkjet-printed nanostructured biosensor based on CRISPR/Cas12a system for pathogen detection.

The escalating global incidence of infectious diseases caused by pathogenic bacteria, especially in developing countries, emphasises the urgent need for rapid and portable pathogen detection devices. This study introduces a sensitive and specific electrochemical biosensing platform utilising cost-effective electrodes fabricated by inkjet-printing gold and silver nanoparticles on a plastic substrate. The biosensor exploits the CRISPR/Cas12a system for detecting a specific DNA sequence selected from the genome of the target pathogen. Upon detection, the trans-activity of Cas12a/gRNA is triggered, leading to the cleavage of rationally designed single-strand DNA reporters (linear and hairpin) labelled with methylene blue (ssDNA-MB) and bound to the electrode surface. In principle, this sensing mechanism can be adapted to any bacterium by choosing a proper guide RNA to target a specific sequence of its DNA. The biosensor's performance was assessed for two representative pathogens (a Gram-negative, Escherichia coli, and a Gram-positive, Staphylococcus aureus), and results obtained with inkjet-printed gold electrodes were compared with those obtained by commercial screen-printed gold electrodes. Our results show that the use of inkjet-printed nanostructured gold electrodes, which provide a large surface area, in combination with the use of hairpin reporters containing a poly-T loop can increase the sensitivity of the assay corresponding to a signal variation of 86%. DNA targets amplified from various clinically isolated bacteria, have been tested and demonstrate the potential of the proposed platform for point-of-need applications.

Preparation of different conjugated polymers characterized by complementary electronic properties from an identical precursor.

The possibility of generating regions with different electronic properties within the same organic semiconductor thin film could offer novel opportunities for designing and fabricating organic electronic devices and circuits. This study introduces a new approach based on a novel type of highly processable polymer precursor that can yield two different conjugated polymers characterized by complementary electronic properties, i.e. promoting electron or hole transport, from the same starting material. In particular, these multipotent precursors comprise functionalized dihydroanthracene units that can offer several functionalization opportunities to improve the solubility or insert specific functionalities. This strategy also allows for the preparation of high-molecular-weight conjugated polymers comprising diethynylanthracene and anthraquinone units without the need for solubilizing side chains. Thin films of the polymer precursor can be used, after solid-state transformations, to prepare single organic layers comprising regions characterized by different chemical nature and electronic properties. Here, we present a detailed characterization of the chemical and electronic properties of the precursor and the obtained conjugated polymers, showing how it is possible to harvest their characteristics for potential applications such as electrochromic surfaces and organic field-effect transistors.

From M6 to M12, M19 and M38 molecular alloy Pt-Ni carbonyl nanoclusters: selective growth of atomically precise heterometallic nanoclusters.

Heterometallic Chini-type clusters [Pt6-xNix(CO)12]2- (x = 0-6) were obtained by reactions of [Pt6(CO)12]2- with Ni-clusters such as [Ni6(CO)12]2-, [Ni9(CO)18]2- and [H2Ni12(CO)21]2-, or from [Pt9(CO)18]2- and [Ni6(CO)12]2-. The Pt/Ni composition of [Pt6-xNix(CO)12]2- (x = 0-6) depended on the nature of the reagents employed and their stoichiometry. Reactions of [Pt9(CO)18]2- with [Ni9(CO)18]2- and [H2Ni12(CO)21]2-, as well as reactions of [Pt12(CO)24]2- with [Ni6(CO)12]2-, [Ni9(CO)18]2- and [H2Ni12(CO)21]2-, afforded [Pt9-xNix(CO)18]2- (x = 0-9) species. [Pt6-xNix(CO)12]2- (x = 1-5) were converted into [Pt12-xNix(CO)21]4- (x = 2-10) upon heating in CH3CN at 80 °C, with almost complete retention of the Pt/Ni composition. Reaction of [Pt12-xNix(CO)21]4- (x ≈ 8) with HBF4·Et2O afforded the [HPt14+xNi24-x(CO)44]5- (x ≈ 0.7) nanocluster. Finally, [Pt19-xNix(CO)22]4- (x = 2-6) could be obtained by heating [Pt9-xNix(CO)18]2- (x = 1-3) in CH3CN at 80 °C, or [Pt6-xNix(CO)12]2- (2-4) in DMSO at 130 °C. The molecular structures of these new alloy nanoclusters have been determined by single crystal X-ray diffraction. The site preference of Pt and Ni within their metal cages has been computationally investigated. The electrochemical and IR spectroelectrochemical behavior of [Pt19-xNix(CO)22]4- (x = 3.11) has been studied and compared to the isostructural homometallic nanocluster [Pt19(CO)22]4-.

Emerging Biosensing Technologies towards Early Sepsis Diagnosis and Management.

Sepsis is defined as a systemic inflammatory dysfunction strictly associated with infectious diseases, which represents an important health issue whose incidence is continuously increasing worldwide. Nowadays, sepsis is considered as one of the main causes of death that mainly affects critically ill patients in clinical settings, with a higher prevalence in low-income countries. Currently, sepsis management still represents an important challenge, since the use of traditional techniques for the diagnosis does not provide a rapid response, which is crucial for an effective infection management. Biosensing systems represent a valid alternative due to their characteristics such as low cost, portability, low response time, ease of use and suitability for point of care/need applications. This review provides an overview of the infectious agents associated with the development of sepsis and the host biomarkers suitable for diagnosis and prognosis. Special focus is given to the new emerging biosensing technologies using electrochemical and optical transduction techniques for sepsis diagnosis and management.

Atomically Precise Platinum Carbonyl Nanoclusters: Synthesis, Total Structure, and Electrochemical Investigation of [Pt27(CO)31]4- Displaying a Defective Structure.

The molecular Pt nanocluster [Pt27(CO)31]4- (14-) was obtained by thermal decomposition of [Pt15(CO)30]2- in tetrahydrofuran under a H2 atmosphere. The reaction of 14- with increasing amounts of HBF4·Et2O afforded the previously reported [Pt26(CO)32]2- (32-) and [Pt26(CO)32]- (3-). The new nanocluster 14- was characterized by IR and UV-visible spectroscopy, single-crystal X-ray diffraction, direct-current superconducting quantum interference device magnetometry, cyclic voltammetry, IR spectroelectrochemistry (IR SEC), and electrochemical impedance spectroscopy. The cluster displays a cubic-close-packed Pt27 framework generated by the overlapping of four ABCA layers, composed of 3, 7, 11, and 6 atoms, respectively, that encapsulates a fully interstitial Pt4 tetrahedron. One Pt atom is missing within layer 3, and this defect (vacancy) generates local deformations within layers 2 and 3. These local deformations tend to repair the defect (missing atom) and increase the number of Pt-Pt bonding contacts, minimizing the total energy. The cluster 14- is perfectly diamagnetic and displays a rich electrochemical behavior. Indeed, six different oxidation states have been characterized by IR SEC, unraveling the series of 1n- (n = 3-8) isostructural nanoclusters. Computational studies have been carried out to further support the interpretation of the experimental data.

Atomically Precise Ni-Pd Alloy Carbonyl Nanoclusters: Synthesis, Total Structure, Electrochemistry, Spectroelectrochemistry, and Electrochemical Impedance Spectroscopy.

The molecular nanocluster [Ni36-xPd5+x(CO)46]6- (x = 0.41) (16-) was obtained from the reaction of [NMe3(CH2Ph)]2[Ni6(CO)12] with 0.8 molar equivalent of [Pd(CH3CN)4][BF4]2 in tetrahydrofuran (thf). In contrast, [Ni37-xPd7+x(CO)48]6- (x = 0.69) (26-) and [HNi37-xPd7+x(CO)48]5- (x = 0.53) (35-) were obtained from the reactions of [NBu4]2[Ni6(CO)12] with 0.9-1.0 molar equivalent of [Pd(CH3CN)4][BF4]2 in thf. After workup, 35- was extracted in acetone, whereas 26- was soluble in CH3CN. The total structures of 16-, 26-, and 35- were determined with atomic precision by single-crystal X-ray diffraction. Their metal cores adopted cubic close packed structures and displayed both substitutional and compositional disorder, in light of the fact that some positions could be occupied by either Ni or Pd. The redox behavior of these new Ni-Pd molecular alloy nanoclusters was investigated by cyclic voltammetry and in situ infrared spectroelectrochemistry. All three compounds 16-, 26-, and 35- displayed several reversible redox processes and behaved as electron sinks and molecular nanocapacitors. Moreover, to gain insight into the factors that affect the current-potential profiles, cyclic voltammograms were recorded at both Pt and glassy carbon working electrodes and electrochemical impedance spectroscopy experiments performed for the first time on molecular carbonyl nanoclusters.

Three-Dimensional (3D) Laser-Induced Graphene: Structure, Properties, and Application to Chemical Sensing.

Notwithstanding its relatively recent discovery, graphene has gone through many evolution steps and inspired a multitude of applications in many fields, from electronics to life science. The recent advancements in graphene production and patterning, and the inclusion of two-dimensional (2D) graphenic materials in three-dimensional (3D) superstructures, further extended the number of potential applications. In this Review, we focus on laser-induced graphene (LIG), an intriguing 3D porous graphenic material produced by direct laser scribing of carbonaceous precursors, and on its applications in chemical sensors and biosensors. LIG can be shaped in different 3D forms with a high surface-to-volume ratio, which is a valuable characteristic for sensors that typically rely on phenomena occurring at surfaces and interfaces. Herein, an overview of LIG, including synthesis from various precursors, structure, and characteristic properties, is first provided. The discussion focuses especially on transport and surface properties, and on how these can be controlled by tuning the laser processing. Progresses and trends in LIG-based chemical sensors are then reviewed, discussing the various transduction mechanisms and different LIG functionalization procedures for chemical sensing. A comparative evaluation of sensors performance is then provided. Finally, sensors for glucose detection are reviewed in more detail, since they represent the vast majority of LIG-based chemical sensors.