Small variations in reaction conditions tune carbon dot fluorescence.

The development of robust and reproducible synthetic strategies for the production of carbon dots (CDs) with improved fluorescence quantum yields and distinct emission profiles is of great relevance given the vast range of applications of CDs. The fundamental understanding at a molecular level of their formation mechanism, chemical structure and how these parameters are correlated to their photoluminescence (PL) properties is thus essential. In this study, we describe the synthesis and structural characterization of a range of CDs with distinct physico-chemical properties. The materials were prepared under three minutes of microwave irradiation using the same common starting materials (D-glucosamine hydrochloride 1 and ethylenediamine 2) but modifying the stoichiometry of the reagents. We show that small variation in reaction conditions leads to changes in the fluorescent behaviour of the CDs, especially in the selective enhancement of overlapped fluorescence bands. Structural analysis of the different CD samples suggested different reaction pathways during the CD formation and surface passivation, with the latter step being key to the observed differences. Moreover, we demonstrate that these materials have distinct reversible response to pH changes, which we can be attribute to different behaviour towards protonation/deprotonation events of distinct emission domains present within each nanomaterial. Our results highlight the importance of understanding the reaction pathways that lead to the formation of this carbon-based nanomaterials and how this can be exploited to develop tailored materials towards specific applications.

Photosynthesis and crop productivity are enhanced by glucose-functionalised carbon dots.

From global food security to textile production and biofuels, the demands currently made on plant photosynthetic productivity will continue to increase. Enhancing photosynthesis using designer, green and sustainable materials offers an attractive alternative to current genetic-based strategies and promising work with nanomaterials has recently started to emerge. Here we describe the in planta use of carbon-based nanoparticles produced by low-cost renewable routes that are bioavailable to mature plants. Uptake of these functionalised nanoparticles directly from the soil improves photosynthesis and also increases crop production. We show for the first time that glucose functionalisation enhances nanoparticle uptake, photoprotection and pigment production, unlocking enhanced yields. This was demonstrated in Triticum aestivum 'Apogee' (dwarf bread wheat) and resulted in an 18% increase in grain yield. This establishes the viability of a functional nanomaterial to augment photosynthesis as a route to increased crop productivity.

Functional nanomaterials to augment photosynthesis: evidence and considerations for their responsible use in agricultural applications.

At the current population growth rate, we will soon be unable to meet increasing food demands. As a consequence of this potential problem, considerable efforts have been made to enhance crop productivity by breeding, genetics and improving agricultural practices. While these techniques have traditionally been successful, their efficacy since the 'green revolution' has begun to significantly plateau. This stagnation of gains combined with the negative effects of climate change on crop yields has prompted researchers to develop novel and radical methods to increase crop productivity. Recent work has begun exploring the use of nanomaterials as synthetic probes to augment how plants use light. Photosynthesis in crops is often limited by their ability to absorb and exploit solar energy for photochemistry. The capacity to interact with and optimize how plants use light has the potential to increase the productivity of crops and enable the tailoring of crops for different environments and to compensate for predicted climate changes. Advances in the synthesis and surface modification of nanomaterials have overcome previous drawbacks and renewed their potential use as synthetic probes to enhance crop yields. Here, we review the current applications of functional nanomaterials in plants and will make an argument for the continued development of promising new nanomaterials and future applications in agriculture. This will highlight that functional nanomaterials have the clear potential to provide a much-needed route to enhanced future food security. In addition, we will discuss the often-ignored current evidence of nanoparticles present in the environment as well as inform and encourage caution on the regulation of nanomaterials in agriculture.

Surface functionalisation significantly changes the physical and electronic properties of carbon nano-dots.

Biomolecule functionalisation of carbon nano-dots (CDs) greatly enhances their biocompatibility and applicability, however, little is known about their molecular structure. Using an arsenal of spectroscopic and analytical techniques, we provide new insights into the physical and electronic structure of uncoated and glycan-functionalised CDs. Our studies reveal that surface functionalisation does not always result in a homogenous corona surrounding the core, and the choice of carbohydrate significantly affects the electronic structure of the surface CD states. Further, the average surface coverage of an ensemble of CDs can be probed via transient absorption spectroscopy. These findings have implications for CDs targeted at interactions with biological systems or local sensors.

Multi-drug and metabolite quantification in postmortem blood by liquid chromatography-high-resolution mass spectrometry: comparison with nominal mass technology.

High-resolution mass spectrometry (HRMS) is being applied in postmortem drug screening as an alternative to nominal mass spectrometry, and additional evaluation in quantitative casework is needed. We report quantitative analysis of benzoylecgonine, citalopram, cocaethylene, cocaine, codeine, dextromethorphan, dihydrocodeine, diphenhydramine, 2-ethylidene-1,5-dimethyl-3,3-diphenylpyrrolidine, hydrocodone, hydromorphone, meperidine, methadone, morphine, oxycodone and oxymorphone in postmortem blood by ultra-performance liquid chromatography (UPLC)-MS(E)/time-of-flight (TOF). The method employs analyte-matched deuterated internal standardization and MS(E) acquisition of precursor and product ions at low (6 eV) and ramped (10-40 eV) collision energies, respectively. Quantification was performed using precursor ion data obtained with a mass extraction window of ± 5 ppm. Fragment and residual precursor ion acquisitions at ramped collision energies were evaluated as additional analyte identifiers. Extraction recovery of >60% and matrix effect of <20% were determined for all analytes and internal standards. Defined limits of detection (10 ng/mL) and quantification (25 ng/mL) were validated along with a linearity analytical range of 25-3,000 ng/mL (R(2) > 0.99) for all analytes. Parallel UPLC-MS(E)/TOF and UPLC-MS/MS analysis showed comparable precision and bias along with concordance of 253 positive (y = 1.002x + 1.523; R(2) = 0.993) and 2,269 negative analyte findings in 159 postmortem cases. Analytical performance and correlation studies demonstrate accurate quantification by UPLC-MS(E)/TOF and extended application of HRMS in postmortem casework.

Drug screening in medical examiner casework by high-resolution mass spectrometry (UPLC-MSE-TOF).

Postmortem drug findings yield important analytical evidence in medical examiner casework, and chromatography coupled with nominal mass spectrometry (MS) serves as the predominant general unknown screening approach. We report screening by ultra performance liquid chromatography (UPLC) coupled with hybrid quadrupole time-of-flight mass spectrometer (MS(E)-TOF), with comparison to previously validated nominal mass UPLC-MS and UPLC-MS-MS methods. UPLC-MS(E)-TOF screening for over 950 toxicologically relevant drugs and metabolites was performed in a full-spectrum (m/z 50-1,000) mode using an MS(E) acquisition of both molecular and fragment ion data at low (6 eV) and ramped (10-40 eV) collision energies. Mass error averaged 1.27 ppm for a large panel of reference drugs and metabolites. The limit of detection by UPLC-MS(E)-TOF ranges from 0.5 to 100 ng/mL and compares closely with UPLC-MS-MS. The influence of column recovery and matrix effect on the limit of detection was demonstrated with ion suppression by matrix components correlating closely with early and late eluting reference analytes. Drug and metabolite findings by UPLC-MS(E)-TOF were compared with UPLC-MS and UPLC-MS-MS analyses of postmortem blood in 300 medical examiner cases. Positive findings by all methods totaled 1,528, with a detection rate of 57% by UPLC-MS, 72% by UPLC-MS-MS and 80% by combined UPLC-MS and UPLC-MS-MS screening. Compared with nominal mass screening methods, UPLC-MS(E)-TOF screening resulted in a 99% detection rate and, in addition, offered the potential for the detection of nontargeted analytes via high-resolution acquisition of molecular and fragment ion data.

Postmortem drug screening by non-targeted and targeted ultra-performance liquid chromatography-mass spectrometry technology.

In the medical examiner setting, comprehensive drug screening is an essential analytical tool in the investigation of cause and manner of death.We have validated non-targeted and targeted screening assays for drugs and metabolites using ultra-performance liquid chromatography (UPLC) interfaced with mass spectrometry (MS) in single and tandem stages. For non-targeted screening by UPLC-MS electrospray interface, in-source fragmentation was used along with MS scanning (m/z 80-650) and library search for over 700 drug and metabolite analytes. Targeted detection of over 200 analytes by UPLC-MS-MS was performed with dual transition ion monitoring. Validation studies confirmed reproducibility of both mass spectra produced by in-source fragmentation and transition ion ratios by collision-cell dissociation. Lower limit of detection by UPLC-MS (10-150 ng/mL) and UPLC-MS-MS (1-50 ng/mL) was determined for a subset of drugs and correlated with extraction recovery and matrix effect. Drug findings by UPLC-MS and UPLC- MS-MS were compared with gas chromatography-mass spectrometry (GC-MS) screening in postmortem blood from 410 medical examiner cases with 1121 positive drug findings by all methods. Accuracy, based on results of confirmation testing, was high (98-99%) across all screening assays and detection sensitivity by GC-MS (71%), UPLC-MS (73%), and UPLC-MS-MS (76%) was determined. UPLC-MS plus UPLC-MS-MS screening resulted in the highest drug detection rate (95%) and provided optimal dual-screening for the postmortem casework.

Ethylene glycol and glycolic acid in postmortem blood from fatal poisonings.

Ethylene glycol (EG), a relatively infrequent cause of fatal intoxication, presents an analytical challenge for forensic confirmation in postmortem toxicology. We report EG and glycolic acid (GA) quantification in postmortem blood by gas chromatography coupled with ion trap mass spectrometry (GC-MS) analysis using a modification of a previously reported clinical method. The method is linear from 50 to 4000 mg/L with a limit of detection of 25 mg/L for both EG and GA. Interassay coefficient of variation (2.1-8.6%, 4.3-6.0%) and accuracy (96-101%, 92-105%) were determined for EG and GA, respectively. EG concentration by ion trap GC-MS correlated closely (R(2) = 0.995) with EG quantified by GC-flame-ionization detection. Analysis of blood from 20 autopsies with no evidence of EG exposure did not reveal detectable EG or GA. In 12 medical examiner cases with EG poisoning as cause of death, EG concentrations ranged widely from 58 to 7790 mg/L with a mean of 1830 mg/L, and the GA concentration averaged 1360 mg/L with a narrower range of 810-1770 mg/L. EG and GA levels correlate poorly (R(2) = 0.15) in postmortem blood with discordantly low EG concentrations in two cases. Birefringent oxylate crystals in renal tissue was a consistent finding. In conclusion, a sensitive and specific GC-MS method for detection and quantification of EG and GA has been validated and a study of fatal EG poisonings revealed forensic application of the method.

Immunoassay of estradiol: unanticipated suppression by unconjugated estriol.

BACKGROUND: Accurate measurement of estradiol is important in clinical settings. The quality of laboratory estimations of estradiol may be assessed through external quality-assurance surveys. METHODS: Estradiol was measured by microparticle enzyme immunoassay (MEIA) and other immunoassays. Proficiency testing of medical laboratories was conducted using samples prepared from normal male human serum supplemented with exogenous estradiol and other steroid and nonsteroid hormones, and participant laboratories measured estradiol by a variety of commonly used immunoassay techniques. RESULTS: The imprecision (CV) for measurement of estradiol [100-300 ng/L (367-1102 pmol/L)] was 1.5 microg/L (>5.2 nmol/L) interfered with the MEIA method, leading to decreased recovery of added estradiol by up to 50%. This suppression in estradiol measurement was prevented by dilution of the specimen before measurement. Addition of unconjugated estriol gave a positive bias in some other immunoassay methods for estradiol. Poor comparability among the immunoassay methods for measurement of estradiol at clinically relevant concentrations [ approximately 60 ng/L (220 pmol/L)] was revealed. CONCLUSIONS: A negative interference of unconjugated estriol with the MEIA method is a source of error for estradiol measurement. Lack of specificity and lack of comparability among immunoassay methods for estradiol may have detrimental effects on medical practice.