Developing a sense of belonging is one of the Essential Elements of a positive youth development experience. Creating an inclusive environment in your 4-H club programs and activities can help you achieve this goal. Providing many forms of recognition for all, not just for those who excel in competition with other youth, supports this sense of belonging.

This is an invited Account and Perspective, providing observations and advice on writing for review derived from a 40-year academic career that has included 27 years' service as an Associate Editor for the Journal of the American Society for Mass Spectrometry (JASMS) and nearly 14 years at the National Science Foundation. This work describes an Associate Editor's perspective. It offers observations on what editors and reviewers look for in manuscripts, and some of the more common, best avoided mistakes. Emphasis is on JASMS guidelines, but many elements should be generally applicable and are intended for use by both authors and reviewers.

This is an invited Account and Perspective, providing observations and advice derived from a 40 year academic career that has included over 14 years' service as a program officer at the National Science Foundation (NSF) and 27 years of service as an Associate Editor of the Journal of the American Society for Mass Spectrometry. This work describes the program officer's perspective, with observations on what reviewers look for in proposals, and what are some of the more common, best avoided mistakes. Emphasis is on NSF guidelines, but many elements are general and intended for use by both proposal authors and reviewers.

Pharmacogenetic testing (PGT) is increasingly being used as a tool to guide clinical decisions. This article describes the development of an outpatient, pharmacist-led, pharmacogenetics consult clinic within internal medicine, its workflow, and early results, along with successes and challenges. A pharmacogenetics-trained pharmacist encouraged primary care physicians (PCPs) to refer patients who were experiencing side effects/ineffectiveness from certain antidepressants, opioids, and/or proton pump inhibitors. In clinic, the pharmacist confirmed the need for and ordered CYP2C19 and/or CYP2D6 testing, provided evidence-based pharmacogenetic recommendations to PCPs, and educated PCPs and patients on the results. Operational and clinical metrics were analyzed. In two years, 91 referred patients were seen in clinic (mean age 57, 67% women, 91% European-American). Of patients who received PGT, 77% had at least one CYP2C19 and/or CYP2D6 phenotype that would make conventional prescribing unfavorable. Recommendations suggested that physicians change a medication/dose for 59% of patients; excluding two patients lost to follow-up, 87% of recommendations were accepted. Challenges included PGT reimbursement and referral maintenance. High frequency of actionable results suggests physician education on who to refer was successful and illustrates the potential to reduce trial-and-error prescribing. High recommendation acceptance rate demonstrates the pharmacist’s effectiveness in providing genotype-guided recommendations, emphasizing a successful pharmacist–physician collaboration.

Tht parametric dependenoe of aeroaol ionio redistribution (AIR) for the determination of eopper in laminar flame atomic epeotroeeopy is investigated. Speoifioally. effeots of flame oomposition. sample uptake rate, and impact bead position are considered Little dependenoe is noted, reflecting the high atomisation effi­ ciency of the analyte under the varied conditions. Surfaotant charge effeots. as predicted by the AIK model, were confirmed for both absorption and emission, and oharaeterised with respeot to surfaotant oonoentration. In addition to previously reported en­ hancements with the addition of anionio surfaotants. a desensiti. sation was observed with oationie surfaotants. The effeots of either ionic surfaotants were seen to be muoh larger than surfaoe tension effects as studied using a nonionio surfactant. In omis­ sion studies using a total consumption burner no effeots of AXh were noted, although an enhancement was observed at high concentra­ tions and is believed to be due to a change in flame oonditions.

Clostridium thermocellum has emerged as a leading bioenergy-relevant microbe due to its ability to solubilize cellulose into carbohydrates, mediated by multicomponent membrane-attached complexes termed cellulosomes. To probe microbial cellulose utilization rates, it is desirable to be able to measure the concentrations of saccharolytic enzymes and estimate the total amount of cellulosome present on a mass basis. Current cellulase determination methodologies involve labor-intensive purification procedures and only allow for indirect determination of abundance. We have developed a method using multiple reaction monitoring (MRM-MS) to simultaneously quantitate both enzymatic and structural components of the cellulosome protein complex in samples ranging in complexity from purified cellulosomes to whole cell lysates, as an alternative to a previously developed enzyme-linked immunosorbent assay (ELISA) method of cellulosome quantitation. The precision of the cellulosome mass concentration in technical replicates is better than 5% relative standard deviation for all samples, indicating high precision for determination of the mass concentration of cellulosome components.

The evolution of droplet temperatures in an electrospray plume was measured via ratiometric fluorescence. Under typical operating conditions, droplet temperatures decrease ∼30 K over the first 5.0 mm along the spray axis, followed by a slight (∼2-3 K) rewarming. Experimental axial profiles (Z-axis) were fit by use of diffusion-controlled and surface-controlled evaporation models. Both models fit the experimental data well for the cooling portion of the spray (Pearson correlation coefficient R ≥ 0.994), but the surface-controlled model required unrealistic droplet radius values to obtain a good fit. In lateral profiles at a given Z near the emitter tip, temperatures are lower (by 3.0-10 K) in the periphery than on the spray axis. This behavior is consistent with the expected enrichment of the spray periphery with smaller droplets. At longer axial distances, lateral profiles were relatively flat. Droplet temperature as a function of axial displacement fell more rapidly at lower liquid flow rates, possibly attributable to changes in droplet size and/or velocity with flow rate.

Post-translational modifications (PTMs) are known to play a significant role in many biological functions. The focus of this study is to optimize an integrated experimental/informatics approach to more confidently characterize the range of post-translational modifications of the cellulosome protein complex used by the bacterium Clostridium thermocellum to better understand how this protein machine is tuned for enzymatic cellulose solubilization. To enhance comprehensive characterization, the extracellular cellulosome proteins were analyzed using multiple proteolytic digests (trypsin, Lys-C, Glu-C) and multiple fragmentation techniques (collisionally activated dissociation, electron transfer dissociation, decision tree). As expected, peptide and protein identifications were increased by utilizing alternate proteases and fragmentation methods, in addition to the increase in protein sequence coverage. The complementarity of these experiments also allowed for a global exploration of PTMs associated with the cellulosome based upon a set of defined PTMs that included methylation, oxidation, acetylation, phosphorylation, and signal peptide cleavage. In these experiments, 85 modified peptides corresponding to 28 cellulosome proteins were identified. Many of these modifications were located in active cellulolytic or structural domains of the cellulosome proteins, suggesting a level of possible regulatory control of protein function in various cellulotyic conditions. The use of complementary proteolytic digestion/peptide fragmentation processes allowed for independent verification of PTMs in different experiments, thus leading to increased confidence in PTM identifications.

Although qualitative and/or semiquantitative real-time monitoring of chemical reactions have been reported with a few mass spectrometric approaches, to our knowledge, no quantitative mass spectrometric approach has been reported so far to have a calibration valid up to molar concentrations as required by process control. This is mostly due to the absence of a practical solution that could well address the sample overloading issue. In this study, a novel autosampling flow injection analysis coupled with an atmospheric pressure chemical ionization mass spectrometry (FIA/APCI-MS) system, consisting of a 1 μL automatic internal sample injector, a postinjection splitter with 1:10 splitting ratio, and a detached APCI source connected to the mass spectrometer using a 4.5 in. long, 0.042 in. inner diameter (ID) stainless-steel capillary, was thus introduced. Using this system together with an optional FIA solvent modifier, e.g., 0.05% (v/v) isopropylamine, a linear quantitative calibration up to molar concentration has been achieved with 3.4-7.2% relative standard deviations (RSDs) for 4 replicates. As a result, quantitative real-time monitoring of a model reaction was successfully performed at the 1.63 M level. It is expected that this novel autosampling FIA/APCI-MS system can be used in quantitative real-time monitoring of a wide range of reactions under diverse reaction conditions.

Liquid chromatography dopant-assisted atmospheric pressure chemical ionization (LC/DA-APCI-MS) has been introduced and demonstrated as a promising method for the analysis of non-polar compounds. Polycyclic aromatic hydrocarbons (PAHs) were studied as non-polar representatives. Chlorobenzene, toluene and anisole were explored as dopants with anisole achieving the best results. Using anisole as the dopant, signal to noise ratio (S/N) for PAHs were up to two orders of magnitude better than those achieved with LC/APCI-MS under identical conditions. While predominant M+ ions were observed for fourteen of the sixteen PAHs by LC/DA-APCI-MS, predominant [M−H]+ ions were observed for acenaphthene and fluorene whose structure is different from other PAHs by containing cyclopenta-fused rings formed by methylene (–CH2–) insertion. PAH and solvent adduct ions, e.g., [M+CH2CN]+, were also observed for a few PAHs. Reactant ion mass spectra of LC/DA-APCI-MS were examined in detail. All three dopants generated chemical background ions at m/z≤250, which possibly limited the use of high dopant flow rates to improve the S/N of low-molecular-mass PAHs. They also generated predominant D+ ions. In comparison with toluene, almost two and seven times more D+ ions were observed by chlorobenzene and anisole, respectively. In addition to predominant D+ ions, anisole also generated noticeable amount of [D+H]+ ions. Toluene generated not only [D+H]+ but also [D−H]+ ions. Therefore, while a charge exchange reaction could be mainly responsible for the ionization of PAHs, a proton transfer reaction followed by in-source fragmentation could also be responsible.

Batch slurry reactions are widely used in the industrial manufacturing of chemicals, pharmaceuticals, petrochemicals and polymers. However, onsite monitoring of batch slurry reactions is still not feasible in production plants due to the challenge in analyzing heterogeneous samples without complicated sample preparation procedures. In this study, direct analysis in real time mass spectrometry (DART-MS) has been evaluated for the onsite monitoring of a model batch slurry reaction. The results suggested that automation of the sampling process of DART-MS is important to achieve quantitative results. With a sampling technique of manual sample deposition on melting point capillaries followed by automatic sample introduction across the helium beam, relative standard deviation (RSD) of the protonated molecule signals from the reaction product of the model batch slurry reaction ranged from 6 to 30%. This RSD range is improved greatly over a sampling technique of manual sample deposition followed by manual sample introduction where the RSDs are up to 110%. Furthermore, with the semi-automated sampling approach, semi-quantitative analysis of slurry samples has been achieved. Better quantification is expected with a fully automated sampling approach.

The Cultural Heritage Science (CHS, formerly SCIART) Program seeks to enhance opportunities for chemistry and materials research at the interface between science and art. The objective is to promote collaboration between cultural heritage scientists, mainly located in US museums and chemists and/or materials scientists in US academic institutions to address grand challenges in the science of cultural heritage. Through the first competition, eight projects, two to three years in duration, were funded at $270,000 to 495,000 each. Every successful proposal demonstrated a clear need for collaboration with good synergy between the collaborating groups, and provided plans for meaningful training experiences for students and/or postdoctoral researchers in the field of cultural heritage science. It is anticipated that the CHS Program will continue for two additional years in a similar fashion. During this period, researchers should be able to more easily identify the disciplinary programs in materials research or chemistry relevant to their work, and their proposals will be reviewed together in panels. Proposals falling outside of the CHS specifications may be submitted directly to the relevant program/s of interest at the National Science Foundation (NSF) as unsolicited proposals. After the CHS Program ends, unsolicited proposals will remain the key mechanism for obtaining NSF funding in this research area.

A transient microenvironment mechanism (TMEM) is proposed to address matrix effects for direct analysis in real time (DART). When the DART gas stream is in contact with the sample, a transient microenvironment (TME), which can shield analytes from direct ionization, may be generated through the desorption of the matrix containing the analyte. The DART gas stream can directly ionize the matrix molecules, but the analytes will be ionized primarily through gas-phase ion/molecule reactions with the matrix ions. Experimental results showed that as little as 10 nL of liquid or 10 microg of solid was able to generate an efficient TME. Generated TMEs were able to control the ionization of an analyte below an analyte-to-matrix ratio that was dependent on the DART temperature and the boiling points of the analyte and matrix. TMEs generated by common solvents were studied in detail. The ionization of both polar and nonpolar compounds, present in a solvent or another analyte below a ratio of 1:100, were found to be mainly controlled by the generated TMEs at a DART temperature of 300 degrees C.