Quantitative Analysis of Photochemical Reactions in Pentacene Precursor Films.

On-surface reactions are rapidly gaining attention as a chemical technique for synthesizing organic functional materials, such as graphene nanoribbons and molecular semiconductors. Quantitative analysis of such reactions is essential for fabricating high-quality film structures, but until our recent work using p-polarized multiple-angle incidence resolution spectrometry (pMAIRS), no analytical technique is available to quantify the reaction rate. In the present study, the pMAIRS technique is employed to analyze the photochemical reaction from 6,13-dihydro-6,13-ethanopentacene-15,16-dione to pentacene in thin films. The spectral analysis on a pMAIRS principle readily reveals the photoconversion rate accurately without other complicated calculations. Thus, this study underlines that the pMAIRS technique is a powerful tool for quantitative analysis of on-surface reactions, as well as molecular orientation.

An Atropisomerism Study of Large Cycloarylenes: [n]Cyclo-4,10-Pyrenylenes' Case.

An atropisomerism of large cycloarylenes was studied using [n]cyclo-4,10-pyrenylenes (n=6-21) as an illustrative example with two simple assumptions: (1) alternating configurations (R,S,R,S,…) are thermodynamically most stable, and (2) three consecutive identical configurations (R,R,R or S,S,S) are prevented. Ni-mediated coupling of a 5,9-diiodopyrene gave a series of directly-linked cyclic pyrene oligomers in one-pot reaction. As-synthesized cyclic hexamer was assigned as an (R,S,S,R,R,S) structure, converted into an (R,S,R,S,R,S)-form upon heating. Cyclic heptamer consists of two types of C2 symmetric structures predicted from assumption (2), one of which was convergent to one another by heating. Three atropisomers of cyclic octamer were analyzed from the possible five candidates by means of 1 H nuclear magnetic resonance (NMR) spectroscopy, and the conversion process to (R,S,R,S,R,S,R,S) configurations upon heating was investigated. In total, according to two simple rules, the analysis of atropisomerism could be performed smoothly.

Motor-evoked potential monitoring from urinary sphincter muscle during pediatric untethering surgery: a case series.

PURPOSE: Postoperative urinary dysfunction following untethering surgery for spinal lipoma is devastating. To assess urinary function, we invented a pediatric urinary catheter equipped with electrodes for the direct transurethral recording of myogenic potential from the external urethral sphincter (EUS). This paper presents two cases in which urinary function was monitored intraoperatively by recording of motor-evoked potential (MEP) from EUS during untethering surgery in children. METHODS: Two children (aged 2 and 6 years) were included in this study. One patient had no preoperative neurological dysfunction, while the other had frequent urination and urinary incontinence. A pair of surface electrodes was attached to a silicone rubber urethral catheter (6 or 8 Fr; diameter, 2 or 2.6 mm). The MEP from the EUS was recorded to assess the function of the centrifugal tract from the motor cortex to the pudendal nerve. RESULTS: Baseline MEP waveforms from the EUS were successfully recorded with latency and amplitude of 39.5 ms and 66 µV in patient 1 and 39.0 ms and 113 µV in patient 2, respectively. A significant decrease in amplitude was not observed during surgery in the two cases. No new urinary dysfunction and complications associated with the urinary catheter-equipped electrodes developed postoperatively. CONCLUSION: Using an electrode-equipped urinary catheter, monitoring of MEP from the EUS could be applicable during untethering surgery in pediatric patients.

Utility of desflurane as an anesthetic in motor-evoked potentials in spine surgery and the facilitating effect in tetanic stimulation of bilateral median nerves.

Although desflurane is a safe and controllable inhalation anesthetic used in spinal surgery, to our knowledge, there have been no reports of successful motor-evoked potential (MEP) recordings under general anesthesia with desflurane alone. A high desflurane concentration may reduce the risk of intraoperative awareness but can also reduce the success of MEP recording. Therefore, we aimed to evaluate the reliability of MEP monitoring and investigate whether tetanic stimulation can augment MEP amplitude under general anesthesia with high-concentration desflurane during spinal surgery. We prospectively evaluated 46 patients who were scheduled to undergo lumbar surgery at a single center between 2018 and 2020. Anesthesia was maintained with an end-tidal concentration of 4% desflurane and remifentanil. Compound muscle action potentials were recorded bilaterally from the abductor pollicis brevis, abductor hallucis, tibialis anterior, gastrocnemius, and quadriceps. For post-tetanic MEPs (p-MEPs), tetanic stimulation was applied to the median nerves (p-MEPm) and tibial nerves (p-MEPt) separately before transcranial stimulation. The average success rates for conventional MEP (c-MEP), p-MEPm, and p-MEPt were 77.9%, 80%, and 79.3%, respectively. The p-MEPm amplitudes were significantly higher than the c-MEP amplitudes in all muscles (P < 0.05), whereas the p-MEPt amplitudes were not significantly different from the c-MEP amplitudes. The MEP recording success rates for the gastrocnemius and quadriceps were inadequate. However, bilateral median nerve tetanic stimulation can effectively augment MEPs safely under general anesthesia with high-concentration desflurane in patients who undergo spinal surgery.

Synthesis of oligoacenes using precursors for evaluation of their electronic structures.

Acenes, which are hydrocarbons comprising linearly fused benzene rings, have attracted considerable attention owing to their electronic structures and utility as organic electronic materials. However, the ease with which oligoacenes undergo oxidation increases with the number of linearly fused benzene rings owing to the increased energy of the highest occupied molecular orbital. The synthesis of naked oligoacenes with seven or more benzene rings is difficult because their open-shell structure renders them unstable. The recent development of a precursor method has enabled the in situ synthesis of oligoacenes under specific conditions and the spectroscopic observation of oligoacene in single crystals, in film matrices and under cryogenic conditions. Scanning tunneling microscopy and non-contact atomic force microscopy under ultra-high vacuum conditions have also made significant advances in the study of oligoacenes and oligoazaacenes. This paper reviews the recent progress in the synthesis of oligoacenes using precursors, with a particular focus on the chemical structures, synthesis, and reactivity of the precursors. The electronic properties of oligoacenes are also discussed in relation to the number of fused benzene rings, including their energy levels and spin states. These results will contribute to the synthesis and development of carbon nanomaterials with applications in the field of organic electronics.

Tetanic stimulation of the peripheral nerve augments motor evoked potentials by re-exciting spinal anterior horn cells.

Tetanic stimulation of the peripheral nerve, immediately prior to conducting transcranial electrical stimulation motor evoked potential (TES-MEP), increases MEP amplitudes in both innervated and uninnervated muscles by the stimulated peripheral nerve; this is known as the remote augmentation of MEPs. Nevertheless, the mechanisms underlying the remote augmentation of MEPs remain unclear. Although one hypothesis was that remote augmentation of MEPs results from increased motoneuronal excitability at the spinal cord level, the effect of spinal anterior horn cells has not yet been investigated. We aimed to investigate the effect of tetanic stimulation of the peripheral nerve on spinal cord anterior horn cells by analyzing the F-wave. We included 34 patients who underwent elective spinal surgeries and compared the changes in F-waves and TES-MEPs pre- and post-tetanic stimulation of the median nerve. F-wave analyses were recorded by stimulating the median and tibial nerves. TES-MEPs and F-wave analyses were compared between baseline and post-tetanic stimulation time periods using Wilcoxon signed-rank tests. A significant augmentation of MEPs, independent of the level corresponding to the median nerve, was demonstrated. Furthermore, F-wave persistence was significantly increased not only in the median nerve but also in the tibial nerve after tetanic stimulation of the median nerve. The increased F-wave persistence indicates an increase of re-excited motor units in spinal anterior horn cells. These results confirm the hypothesis that tetanic stimulation of the peripheral nerve may cause remote augmentation of MEPs, primarily by increasing the excitability of the anterior horn cells.

Cautionary findings for motor evoked potential monitoring in intracranial aneurysm surgery after a single administration of rocuronium to facilitate tracheal intubation.

Administration of rocuronium to facilitate intubation has traditionally been regarded as acceptable for intraoperative motor evoked potential (MEP) monitoring because of sufficiently rapid spontaneous neuromuscular blockade recovery. We hypothesized that residual neuromuscular blockade, in an amount that could hinder optimal neuromonitoring in patients undergoing intracranial aneurysm clipping, was still present at dural opening. We sought to identify how often this was occurring and to identify factors which may contribute to prolonged blockade. Records of 97 patients were retrospectively analyzed. Rocuronium was administered to facilitate intubation with no additional neuromuscular blockade given. Prolonged spontaneous recovery time to a train-of-four (TOF) ratio of 0.75 after rocuronium administration was defined as 120 min, which was approximately when dural opening and the setting of baseline MEPs were occurring. Logistic regression analysis was used to identify factors related to prolonged spontaneous recovery time. Prolonged spontaneous recovery time to a TOF ratio of 0.75 was observed in 44.3% of patients. Multivariable analysis showed that only the dosage of rocuronium based on ideal body weight had a positive correlation with prolonged spontaneous recovery time (P = 0.01). There was no significant association between dosage of rocuronium based on total body weight, age, sex, or body temperature and prolonged recovery time. This study demonstrates that the duration of relaxation for MEP monitoring purposes is well-beyond the routinely recognized clinical duration of rocuronium. Residual neuromuscular blockade could result in lower amplitude MEP signals and/or lead to higher required MEP stimulus intensities which can both compromise monitoring sensitivity.

Ocular blood flow by laser speckle flowgraphy to detect cerebral ischemia during carotid endarterectomy.

Laser speckle flowgraphy (LSFG) is a noninvasive technique that can measure relative blood flow velocity in the optic fundus contributed by the ophthalmic artery, the main first branch originating from the internal carotid artery (ICA). The aim of this study was to assess the feasibility of ocular blood flow measurement by LSFG to detect ischemic stress due to carotid clamping during carotid endarterectomy (CEA). Nineteen patients undergoing CEA with ocular blood flow measurement by LSFG and intraoperative monitoring (IOM) were prospectively enrolled between August 2016 and March 2019. The mean blur rate (MBR) of ocular blood flow by LSFG, representing relative blood flow of the branch of the retinal artery originating from the optic nerve head, was compared between before and after carotid clamping during CEA. The correlation between the reduction ratio of MBR and the regional saturation oxygen (rSO2) index by near infrared spectroscopy was investigated. Ocular blood flow measurement by LSFG could not be performed in one patient with a severe cataract. In the other 18 patients, LSFG could be performed in all 106 sessions during surgery. The MBR reduction ratio between before and after carotid clamping ranged from - 12 to 100%. The MBR reduction ratio was positively correlated with the rSO2 index (r = 0.694, 95% confidence interval: 0.336-0.877, p = 0.001). The MBR reduction ratio of ocular blood flow by LSFG after carotid clamping was significantly correlated with the rSO2 index. The ocular blood flow by LSFG could be considered an adjunct modality for evaluating cerebral ischemic tolerance during CEA.

Visible-Light-Induced Heptacene Generation under Ambient Conditions: Utilization of Single-crystal Interior as an Isolated Reaction Site.

The photo-induced generation of unstable molecules generally requires stringent conditions to prevent oxidation and the concomitant decomposition of the products. The visible-light-induced conversion of two heptacene precursors to heptacene was studied. Single crystals of bis- and mono-α-diketone-type heptacene precursors (7-DK2 and 7-DK1, respectively), were prepared to investigate the effect of precursor structure on reactivity. The photoirradiation of a 7-DK2 single crystal cleaved only one α-diketone group, forming an intermediate bearing a pentacene subunit, while that of a 7-DK1 single crystal gave rise to characteristic absorption peaks of heptacene and their increase in intensity with photoirradiation time, indicating the generation of heptacene without decomposition. Heptacene production was not observed when the precursors were photoirradiated in solution, implying that the single crystal interior provided isolation from the external environment, thus preventing heptacene oxidation.

Orbital-Energy Modulation of Tetrabenzoporphyrin-Derived Non-Fullerene Acceptors for Improved Open-Circuit Voltage in Organic Solar Cells.

Tetrabenzoporphyrin (BP) holds attractive characteristics for optoelectronic applications, such as the large π-conjugated framework and high photoabsorption capability. However, its use in organic solar cells (OSCs) has been limited because of the extremely low solubility that hampers direct solution processing and also the high frontier-orbital energies that lead to low open-circuit voltage (VOC). Herein, we examine BP derivatives equipped with multiple strongly electron-withdrawing groups for photovoltaic applications. The derivatives are generated in thin films through a thermal precursor approach, wherein the corresponding bicyclo[2.2.2]octadiene-fused porphyrin derivatives are solution-cast, and then annealed to carry out the in situ retro-Diels-Alder reaction. The frontier-orbital energies of the resulting derivatives are effectively stabilized as compared to pristine BP to such a degree that they afford high VOC of up to 0.94 V when used as a donor or can even work as a new class of nonfullerene acceptor in OSCs. Single-crystal X-ray diffraction analyses demonstrate that the conformation of the BP framework largely varies from being near planar to highly curved depending on its substituents. The morphology of polymer:BP-derivative bulk-heterojunction films prepared by the thermal precursor approach also varies between the BP derivatives. These results can greatly extend the scope of both molecular design and morphology control for utilization of the BP chromophore toward achieving viable organic optoelectronic devices.

Somatosensory evoked potential loss due to intraoperative pulse lavage during spine surgery: case report and review of signal change management.

Intraoperative neurophysiologic monitoring (IONM) includes various neurophysiologic tests which assess the functional integrity of the central and peripheral nervous systems during surgical procedures which place these structures at risk for iatrogenic injury. The rational for using IONM is to provide timely feedback of changes in neural function to enable the reversal of such insult before the development of irreversible neural injury. There are various causes of intraoperative loss of neuromonitoring signals and it is important to systematically rule out all possible causes quickly and thoroughly in order to target the cause of signal loss, correct it and take measures to prevent the same in the future. One such rare cause, is targeted and pressurized cold (room temperature) irrigation of the surgical site, which may induce irritation and vasospasm leading to ischemia of the affected portion of the spinal cord, hence leading to signal changes. We present this case to stress the importance of having knowledgeable members of the team who are well acquainted with all aspects of monitoring in close proximity to the operating room, so as to minimize troubleshooting time. Furthermore, we suggest the use of warm (body temperature) saline during irrigation to the surgical site, especially when using pressurized irrigation systems.

A practical guide for anesthetic management during intraoperative motor evoked potential monitoring.

Postoperative motor dysfunction can develop after spinal surgery, neurosurgery and aortic surgery, in which there is a risk of injury of motor pathway. In order to prevent such devastating complication, intraoperative monitoring of motor evoked potentials (MEP) has been conducted. However, to prevent postoperative motor dysfunction, proper understanding of MEP monitoring and proper anesthetic managements are required. Especially, a variety of anesthetics and neuromuscular blocking agent are known to attenuate MEP responses. In addition to the selection of anesthetic regime to record the baseline and control MEP, the measures to keep the level of hypnosis and muscular relaxation at constant are crucial to detect the changes of MEP responses after the surgical manipulation. Once the changes of MEP are observed based on the institutional alarm criteria, multidisciplinary team members should share the results of MEP monitoring and respond to check the status of monitoring and recover the possible motor nerve injury. Prevention of MEP-related adverse effects is also important to be considered. The Working Group of Japanese Society of Anesthesiologists (JSA) developed this practical guide aimed to help ensure safe and successful surgery through appropriate anesthetic management during intraoperative MEP monitoring.

Direct borylation of terrylene and quaterrylene.

The preparation of large rylenes often needs the use of solubilizing groups along the rylene backbone, and all the substituents of the terrylenes and quaterrylenes were introduced before creating the rylene skeleton. In this work, we successfully synthesized 2,5,10,13-tetrakis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)terrylene (TB4) by using an iridium-catalyzed direct borylation of C-H bonds in terrylene in 56% yield. The product is soluble in common organic solvents and could be purified without column chromatography. Single crystal X-ray diffraction analysis revealed that the terrylene core is not disturbed by the substituents and is perfectly flat. The photophysical properties of TB4 are also unchanged by the substituents because the carbon atoms at 2,5,10,13-positions have less coefficients on its HOMO and LUMO, estimated by theoretical calculations. Finally, the same borylation reaction was applied for quaterrylene, resulting in the formation of soluble tetra-borylated quaterrylene despite a low yield. The post modification of rylenes enables us to prepare their borylated products as versatile units after creating the rylene skeletons.

Synthesis of Anthracene Derivatives with Azaacene-Containing Iptycene Wings and the Utilization as a Dopant for Solution-Processed Organic Light-Emitting Diodes.

Substituted acene derivatives are regarded as promising materials for organic electronic devices such as organic light-emitting diodes (OLEDs). In particular, anthracene derivatives are known to exhibit good fluorescence property, with the air stability and solubility in common organic solvents expected to give advantages for solution-processed device fabrication. In this study, a series of bistriisopropylsilyl(TIPS)ethynyl anthracene derivatives with azaacene-containing iptycene wings have been synthesized by using condensation reactions. Effects of size of azaacenes on optical properties and packing structures were investigated. UV/Vis absorption and fluorescence spectra indicate that the π-elongation of iptycene units has small effects on the overall π-system, which is also supported by electrochemical measurements. Secondly, single-crystal X-ray analysis implies that the molecules likely have interactions with the iptycene units of adjacent molecules, while the iptycene wings and TIPSethynyl groups can prevent the central anthracene unit from undesirable non-radiative energy loss. Finally, the most emissive derivative was used as a dopant for solution-processed OLEDs, showing obvious electroluminescence with a luminance of over 920 cd m-2 .

Effect of Edge Functionalization on the Bottom-Up Synthesis of Nano-Graphenes.

We demonstrate the effect of edge functionalization on the on-surface Ullmann coupling of nano-carbon materials. Unlike 10,10'-Dibromo-9,9'-bianthryl (DBBA), which is widely known to form anthracene polymers and armchair-edge graphene nanoribbons on Au(111), newly-developed precursor named 5-bromo-11(10-bromoanthracene-9-yl)anthra[2,3-b : 7,6-b']dithiophene (BABAT) with isomers, which has similar structure as DBBA with one anthracene substituted with anthradithiophene, was found to make intramolecular C-C bonding instead of long anthracene polymers after annealing at 200 °C on Au(111). The mechanism was investigated using first-principle density functional theory, which revealed that on-surface polymerization is not kinetically preferred in case of BABAT. The reaction rate of intramolecular C-C bonding of BABAT is ∼206 times faster than that of DBBA. The intramolecular C-C bonding in DBBA biradicals, on the other hand, do not take place because of faster reverse reaction. By referring to electron density of BABAT biradicals, it was concluded that thiophene functionalization modifies distribution of electron density in BABAT radicals and facilitates electrophilic addition, leading to intramolecular C-C bonding after 200 °C annealing. These results indicate that the design of radical moiety is particularly important in the on-surface Ullmann-type coupling.

Overcoming Steric Hindrance in Aryl-Aryl Homocoupling via On-Surface Copolymerization.

On-surface synthesis is a unique tool for growing low-dimensional carbon nanomaterials with precise structural control down to the atomic level. This novel approach relies on carefully designed precursor molecules, which are deposited on suitable substrates and activated to ultimately form the desired nanostructures. One of the most applied reactions to covalently interlink molecular precursors is dehalogenative aryl-aryl coupling. Despite the versatility of this approach, many unsuccessful attempts are also known, most of them associated to the poor capability of the activated precursors to couple to each other. Such failure is often related to the steric hindrance between reactants, which may arise due to their coplanarity upon adsorption on a surface. Here, we propose a copolymerization approach to overcome the limitations that prevent intermolecular homocoupling. We apply the strategy of using suitable linkers as additional reactants to the formation of fully conjugated polycyclic nanowires incorporating non-benzenoid rings.

Intraoperative feasibility of bulbocavernosus reflex monitoring during untethering surgery in infants and children.

Bulbocavernosus reflex (BCR) monitoring is used to assess the integrity of urinary and bowel function. In this study, we evaluated the feasibility of BCR monitoring during untethering surgery in infants and children to predict postoperative urinary and bowel dysfunction. The records of 22 patients ranging from 4 days to 10 years old (mean 2.7 ± 3.3 years) were reviewed. Anesthesia was maintained by propofol or sevoflurane/opioid without neuromuscular blockade. BCR waveforms induced by electrical stimulation (20-40 mA, train-of-four pulses with 500 Hz) to the penis or clitoris were recorded from bilateral external anal sphincters. To assess the sensitivity and specificity of BCR monitoring, we investigated the association between a significant continuous decrease in BCR amplitude at the end of surgery and postoperative urinary and bowel dysfunction after surgery. Reproducible baseline BCR waveforms were successfully recorded in 20 of 22 patients (90.9%). A significant continuous decrease in BCR amplitude was observed in 8 patients. The results of intraoperative BCR monitoring included three true-positives, twelve true-negatives, five false-positives, and zero false-negatives. Therefore, the sensitivity and specificity of BCR monitoring used to predict postoperative urinary and bowel dysfunction were 100 and 70.6%, respectively. BCR monitoring during untethering surgery in infants and children under general anesthesia was found to be a feasible method to prevent postoperative urinary and bowel dysfunction.

Semiconducting π-Extended Tetrathiafulvalene Derivatives.

Tetrathiafulvalene (TTF) has been one of the most studied compounds, since the discovery of electrical conductivity as a charge-transfer complex in combination with tetracyano-p-quinodimethane (TCNQ) in 1973. In 2004, TTF was realized in a new light as an innate semiconductor material, as well as conductor and superconductor material. Because of the ready modification of its core skeleton and better solubility than that of acene compounds, many TTF derivatives have been reported to attain better charge-carrier mobility for field-effect transistor devices. Considering the high charge-carrier mobility of acene and TTF derivatives, annulation of the acene and TTF moieties is expected to improve the charge-carrier mobilities. This Minireview focuses on the syntheses, crystal structures, and electronic properties of state-of-the-art π-extended TTF derivatives, based on the history of the development of TTF derivatives. The relationship between the packing structure and charge-carrier mobilities is also discussed.

An Ethynylene-Bridged Pentacene Dimer: Two-Step Synthesis and Charge-Transport Properties.

A rigid and planar ethynylene-bridged pentacene dimer (PenD) was synthesized from pentacenequinone in two steps, skipping the conventional stepwise approach. A brickwork motif in the single crystal shows two-dimensionally extended electronic interaction in the solid state. Highly crystalline dip-coated films exhibited average hole mobility of 0.24 cm2 V-1 s-1 , comparable to that of the single-crystal organic field-effect transistors. This discovery and understanding of the reaction for the facile synthesis of ethynylene-bridged π-conjugated systems enables to the synthesis of a wide range of organic semiconducting materials.

Clinical Utility of Intraoperative Motor-Evoked Potential Monitoring to Prevent Postoperative Spinal Cord Injury in Thoracic and Thoracoabdominal Aneurysm Repair: An Audit of the Japanese Association of Spinal Cord Protection in Aortic Surgery Database.

BACKGROUND: Spinal cord ischemic injury is the most devastating sequela of descending and thoracoabdominal aortic surgery. Motor-evoked potentials (MEPs) have been used to intraoperatively assess motor tract function, but it remains unclear whether MEP monitoring can decrease the incidence of postoperative motor deficits. Therefore, we reviewed multicenter medical records of patients who had undergone descending and thoracoabdominal aortic repair (both open surgery and endovascular repair) to assess the association of MEP monitoring with postoperative motor deficits. METHODS: Patients included in the study underwent descending or thoracoabdominal aortic repair at 12 hospitals belonging to the Japanese Association of Spinal Cord Protection in Aortic Surgery between 2000 and 2013. Using multivariable mixed-effects logistic regression analysis, we investigated whether intraoperative MEP monitoring was associated with postoperative motor deficits at discharge after open and endovascular aortic repair. RESULTS: We reviewed data from 1214 patients (open surgery, 601 [49.5%]; endovascular repair, 613 [50.5%]). MEP monitoring was performed in 631 patients and not performed in the remaining 583 patients. Postoperative motor deficits were observed in 75 (6.2%) patients at discharge. Multivariable logistic regression analysis revealed that postoperative motor deficits at discharge did not have a significant association with MEP monitoring (adjusted odds ratio [OR], 1.13; 95% confidence interval [CI], 0.69-1.88; P = .624), but with other factors: history of neural deficits (adjusted OR, 6.08; 95% CI, 3.10-11.91; P < .001), spinal drainage (adjusted OR, 2.14; 95% CI, 1.32-3.47; P = .002), and endovascular procedure (adjusted OR, 0.45; 95% CI, 0.27-0.76; P = .003). The sensitivity and specificity of MEP <25% of control value for motor deficits at discharge were 37.8% (95% CI, 26.5%-49.5%) and 95.5% (95% CI, 94.7%-96.4%), respectively. CONCLUSIONS: MEP monitoring was not significantly associated with motor deficits at discharge.